Radial growth rate increases in naturally occurring ponderosa pine trees: a late-20th century CO2 fertilization effect?

PubMed

Soulé, Peter T; Knapp, Paul A

2006-01-01

The primary objective of this study was to determine if gradually increasing levels of atmospheric CO2, as opposed to 'step' increases commonly employed in controlled studies, have a positive impact on radial growth rates of ponderosa pine (Pinus ponderosa) in natural environments, and to determine the spatial extent and variability of this growth enhancement. We developed a series of tree-ring chronologies from minimally disturbed sites across a spectrum of environmental conditions. A series of difference of means tests were used to compare radial growth post-1950, when the impacts of rising atmospheric CO2 are best expressed, with that pre-1950. Spearman's correlation was used to relate site stress to growth-rate changes. Significant increases in radial growth rates occurred post-1950, especially during drought years, with the greatest increases generally found at the most water-limited sites. Site harshness is positively related to enhanced radial growth rates. Atmospheric CO2 fertilization is probably operative, having a positive effect on radial growth rates of ponderosa pine through increasing water-use efficiency. A CO2-driven growth enhancement may affect ponderosa pine growing under both natural and controlled conditions.

Methods and apparatus for managing corrosion in buildings

DOEpatents

Chey, S Jay; Hamann, Hendrik F; Klein, Levente Ioan; Schappert, Michael Alan; Stepanchuk, Andriy

2015-02-03

Principles of the invention provide methods and apparatus for providing corrosion management in buildings. In one aspect, an exemplary method includes the step of receiving first data relating corrosion rate to a plurality of environmental conditions. This first data is subsequently utilized to determine a quantitative relationship between corrosion rate and the plurality of environmental conditions. In another step, second data indicative of one or more environmental conditions within a building is received. A corrosion rate in the building is then determined at least in part by applying the determined quantitative relationship to this second data.

Group sequential designs for stepped-wedge cluster randomised trials

PubMed Central

Grayling, Michael J; Wason, James MS; Mander, Adrian P

2017-01-01

Background/Aims: The stepped-wedge cluster randomised trial design has received substantial attention in recent years. Although various extensions to the original design have been proposed, no guidance is available on the design of stepped-wedge cluster randomised trials with interim analyses. In an individually randomised trial setting, group sequential methods can provide notable efficiency gains and ethical benefits. We address this by discussing how established group sequential methodology can be adapted for stepped-wedge designs. Methods: Utilising the error spending approach to group sequential trial design, we detail the assumptions required for the determination of stepped-wedge cluster randomised trials with interim analyses. We consider early stopping for efficacy, futility, or efficacy and futility. We describe first how this can be done for any specified linear mixed model for data analysis. We then focus on one particular commonly utilised model and, using a recently completed stepped-wedge cluster randomised trial, compare the performance of several designs with interim analyses to the classical stepped-wedge design. Finally, the performance of a quantile substitution procedure for dealing with the case of unknown variance is explored. Results: We demonstrate that the incorporation of early stopping in stepped-wedge cluster randomised trial designs could reduce the expected sample size under the null and alternative hypotheses by up to 31% and 22%, respectively, with no cost to the trial’s type-I and type-II error rates. The use of restricted error maximum likelihood estimation was found to be more important than quantile substitution for controlling the type-I error rate. Conclusion: The addition of interim analyses into stepped-wedge cluster randomised trials could help guard against time-consuming trials conducted on poor performing treatments and also help expedite the implementation of efficacious treatments. In future, trialists should consider incorporating early stopping of some kind into stepped-wedge cluster randomised trials according to the needs of the particular trial. PMID:28653550

Group sequential designs for stepped-wedge cluster randomised trials.

PubMed

Grayling, Michael J; Wason, James Ms; Mander, Adrian P

2017-10-01

The stepped-wedge cluster randomised trial design has received substantial attention in recent years. Although various extensions to the original design have been proposed, no guidance is available on the design of stepped-wedge cluster randomised trials with interim analyses. In an individually randomised trial setting, group sequential methods can provide notable efficiency gains and ethical benefits. We address this by discussing how established group sequential methodology can be adapted for stepped-wedge designs. Utilising the error spending approach to group sequential trial design, we detail the assumptions required for the determination of stepped-wedge cluster randomised trials with interim analyses. We consider early stopping for efficacy, futility, or efficacy and futility. We describe first how this can be done for any specified linear mixed model for data analysis. We then focus on one particular commonly utilised model and, using a recently completed stepped-wedge cluster randomised trial, compare the performance of several designs with interim analyses to the classical stepped-wedge design. Finally, the performance of a quantile substitution procedure for dealing with the case of unknown variance is explored. We demonstrate that the incorporation of early stopping in stepped-wedge cluster randomised trial designs could reduce the expected sample size under the null and alternative hypotheses by up to 31% and 22%, respectively, with no cost to the trial's type-I and type-II error rates. The use of restricted error maximum likelihood estimation was found to be more important than quantile substitution for controlling the type-I error rate. The addition of interim analyses into stepped-wedge cluster randomised trials could help guard against time-consuming trials conducted on poor performing treatments and also help expedite the implementation of efficacious treatments. In future, trialists should consider incorporating early stopping of some kind into stepped-wedge cluster randomised trials according to the needs of the particular trial.

THE EFFECT OF STEP RATE MANIPULATION ON FOOT STRIKE PATTERN OF LONG DISTANCE RUNNERS.

PubMed

Allen, Darrell J; Heisler, Hollie; Mooney, Jennifer; Kring, Richard

2016-02-01

Running gait retraining to change foot strike pattern in runners from a heel strike pattern to a non heel- strike pattern has been shown to reduce impact forces and may help to reduce running related injuries. Step rate manipulation above preferred is known to help decrease step length, foot inclination angle, and vertical mass excursion, but has not yet been evaluated as a method to change foot strike pattern. The purpose of this study was to investigate the effect of step rate manipulation on foot strike pattern in shod recreational runners who run with a heel strike pattern. A secondary purpose was to describe the effect of step rate manipulation at specific percentages above preferred on foot inclination angle at initial contact. Forty volunteer runners, who were self-reported heel strikers and had a weekly running mileage of at least 10 miles, were recruited. Runners were confirmed to be heel strikers during the warm up period on the treadmill. The subject's step rate was determined at their preferred running pace. A metronome was used to increase step rate above the preferred step rate by 5%, 10% and 15%. 2D video motion analysis was utilized to determine foot strike pattern and to measure foot inclination angle at initial contact for each step rate condition. There was a statistically significant change in foot strike pattern from a heel strike pattern to a mid-foot or forefoot strike pattern at both 10% and 15% step rates above preferred. Seven of the 40 subjects (17.5%) changed from a heel- strike pattern to a non- heel strike pattern at +10% and 12 of the 40 subjects (30%) changed to a non-heel strike pattern at +15%. Mean foot inclination angle at initial contact showed a statistically significant change (reduction) as step rate increased. Step rate manipulation of 10% or greater may be enough to change foot strike pattern from a heel strike to a mid-foot or forefoot strike pattern in a small percentage of recreational runners who run in traditional running shoes. If changing the foot strike pattern is the main goal, other gait re-training methods may be needed to make a change from a heel strike to a non-heel strike pattern. Step rate manipulation shows a progressive reduction of foot inclination angle at 5%, 10%, and 15% above preferred step rate which reduces the severity of the heel strike at initial contact. Step rate manipulation of at least +10% above preferred may be an effective running gait retraining method for clinicians to decrease the severity of heel strike and possibly assist a runner to change to a non-heel strike pattern. 3.

Selling Your Child Care Business: Determining Its Value.

ERIC Educational Resources Information Center

Neugebauer, Roger

1997-01-01

Reviews steps to determine the sale value of a privately owned child care business, including determining current pre-tax earnings, calculating add-backs, applying discounts, determining discretionary earnings, determining the appropriate multiple, and computing the center's value. Presents common structures of center purchases and negotiating…

Analysis of reaction schemes using maximum rates of constituent steps

PubMed Central

Motagamwala, Ali Hussain; Dumesic, James A.

2016-01-01

We show that the steady-state kinetics of a chemical reaction can be analyzed analytically in terms of proposed reaction schemes composed of series of steps with stoichiometric numbers equal to unity by calculating the maximum rates of the constituent steps, rmax,i, assuming that all of the remaining steps are quasi-equilibrated. Analytical expressions can be derived in terms of rmax,i to calculate degrees of rate control for each step to determine the extent to which each step controls the rate of the overall stoichiometric reaction. The values of rmax,i can be used to predict the rate of the overall stoichiometric reaction, making it possible to estimate the observed reaction kinetics. This approach can be used for catalytic reactions to identify transition states and adsorbed species that are important in controlling catalyst performance, such that detailed calculations using electronic structure calculations (e.g., density functional theory) can be carried out for these species, whereas more approximate methods (e.g., scaling relations) are used for the remaining species. This approach to assess the feasibility of proposed reaction schemes is exact for reaction schemes where the stoichiometric coefficients of the constituent steps are equal to unity and the most abundant adsorbed species are in quasi-equilibrium with the gas phase and can be used in an approximate manner to probe the performance of more general reaction schemes, followed by more detailed analyses using full microkinetic models to determine the surface coverages by adsorbed species and the degrees of rate control of the elementary steps. PMID:27162366

Analysis of reaction schemes using maximum rates of constituent steps

DOE PAGES

Motagamwala, Ali Hussain; Dumesic, James A.

2016-05-09

In this paper, we show that the steady-state kinetics of a chemical reaction can be analyzed analytically in terms of proposed reaction schemes composed of series of steps with stoichiometric numbers equal to unity by calculating the maximum rates of the constituent steps, r max,i, assuming that all of the remaining steps are quasi-equilibrated. Analytical expressions can be derived in terms of r max,i to calculate degrees of rate control for each step to determine the extent to which each step controls the rate of the overall stoichiometric reaction. The values of r max,i can be used to predict themore » rate of the overall stoichiometric reaction, making it possible to estimate the observed reaction kinetics. This approach can be used for catalytic reactions to identify transition states and adsorbed species that are important in controlling catalyst performance, such that detailed calculations using electronic structure calculations (e.g., density functional theory) can be carried out for these species, whereas more approximate methods (e.g., scaling relations) are used for the remaining species. Finally, this approach to assess the feasibility of proposed reaction schemes is exact for reaction schemes where the stoichiometric coefficients of the constituent steps are equal to unity and the most abundant adsorbed species are in quasi-equilibrium with the gas phase and can be used in an approximate manner to probe the performance of more general reaction schemes, followed by more detailed analyses using full microkinetic models to determine the surface coverages by adsorbed species and the degrees of rate control of the elementary steps.« less

Mechanism of Urea Crystal Dissolution in Water from Molecular Dynamics Simulation.

PubMed

Anand, Abhinav; Patey, G N

2018-01-25

Molecular dynamics simulations are used to determine the mechanism of urea crystal dissolution in water under sink conditions. Crystals of cubic and tablet shapes are considered, and results are reported for four commonly used water models. The dissolution rates for different water models can differ considerably, but the overall dissolution mechanism remains the same. Urea dissolution occurs in three stages: a relatively fast initial stage, a slower intermediate stage, and a final stage. We show that the long intermediate stage is well described by classical rate laws, which assume that the dissolution rate is proportional to the active surface area. By carrying out simulations at different temperatures, we show that urea dissolution is an activated process, with an activation energy of ∼32 kJ mol -1 . Our simulations give no indication of a significant diffusion layer, and we conclude that the detachment of molecules from the crystal is the rate-determining step for dissolution. The results we report for urea are consistent with earlier observations for the dissolution of NaCl crystals. This suggests that the three-stage mechanism and classical rate laws might apply to the dissolution of other ionic and molecular crystals.

Towards quality by design in pharmaceutical manufacturing: modelling and control of air jet mills

NASA Astrophysics Data System (ADS)

Bhonsale, Satyajeet; Telen, Dries; Stokbroekx, Bard; Van Impe, Jan

2017-06-01

Milling is an important step in pharmaceutical manufacturing as it not only determines the final formulation of the drug product, but also influences the bioavailability and dissolution rate of the active pharmaceutical ingredient (API). In this respect, the air jet mill (AJM) is most commonly used in the pharmaceutical industry as it is a non-contaminating and non-degrading self-classifying process capable of delivering narrow particle size distributions (PSD). Keeping the principles of Quality by Design in mind, the Critical Process Parameters (CPPs) of the AJM have been identified to be the pressures at the grinding nozzles, and the feed rate which affect the PSD, surface charge and the morphology of the product (i.e. the Critical Material Attributes (CMAs)). For the purpose of this research, the PSD is considered to be the only relevant CMA. A population balance based model is proposed to simulate the dynamics milling operation by utilizing the concept of breakage functions. This model agrees qualitatively with experimental observations of the air jet mill unit present at Janssen Pharmaceutica but further steps for model validation need to be carried out.

Why do paediatricians prescribe antibiotics? Results of an Italian regional project

PubMed Central

Moro, Maria Luisa; Marchi, Massimiliano; Gagliotti, Carlo; Di Mario, Simona; Resi, Davide

2009-01-01

Background To investigate determinants of antibiotic prescription in paediatric care, as a first step of a multilevel intervention to improve prescribing for common respiratory tract infections (RTIs) in a northern Italian region with high antibiotic prescription rate. Methods A two-step survey was performed: in phase I, knowledge, and attitudes were explored involving all family and hospital paediatricians of Emilia-Romagna and a sample of parents. In phase II, patient care practices were explored in a stratified random sample of visits, both in hospitals and family physician's clinics; parent expectations were investigated in a sub-sample of these visits. Results Out of overall 4352 visits for suspected RTIs, in 38% of children an antibiotic was prescribed. Diagnostic uncertainty was perceived by paediatricians as the most frequent cause of inappropriate prescription (56% of 633 interviewed paediatricians); but, rapid antigen detecting tests was used in case of pharyngitis/pharyngotonsillitis by 36% and 21% of family and hospital paediatricians only. More than 50% of paediatricians affirmed to not adopt a "wait and see strategy" in acute otitis. The perceived parental expectation of antibiotics was not indicated by paediatricians as a crucial determinant of prescription, but this perception was the second factor most strongly associated to prescription (OR = 12.8; 95% CI 10.4 - 15.8), the first being the presence of othorrea. Regarding parents, the most important identified factors, potentially associated to overprescribing, were the lack of knowledge of RTIs and antibiotics (41% of 1029 parents indicated bacteria as a possible cause of common cold), and the propensity to seek medical care for trivial infections (48% of 4352 children accessing ambulatory practice presented only symptoms of common cold). Conclusion A wide gap between perceived and real determinants of antibiotic prescription exists. This can promote antibiotic overuse. Inadequate parental knowledge can also induce inappropriate prescription. The value of this study is that it simultaneously explored determinants of antimicrobial prescribing in an entire region involving both professionals and parents. PMID:19895678

Determining irrigation distribution uniformity and efficiency for nurseries

Treesearch

R. Thomas Fernandez

2010-01-01

A simple method for testing the distribution uniformity of overhead irrigation systems is described. The procedure is described step-by-step along with an example. Other uses of distribution uniformity testing are presented, as well as common situations that affect distribution uniformity and how to alleviate them.

Unexpected Reaction Pathway for butyrylcholinesterase-catalyzed inactivation of “hunger hormone” ghrelin

NASA Astrophysics Data System (ADS)

Yao, Jianzhuang; Yuan, Yaxia; Zheng, Fang; Zhan, Chang-Guo

2016-02-01

Extensive computational modeling and simulations have been carried out, in the present study, to uncover the fundamental reaction pathway for butyrylcholinesterase (BChE)-catalyzed hydrolysis of ghrelin, demonstrating that the acylation process of BChE-catalyzed hydrolysis of ghrelin follows an unprecedented single-step reaction pathway and the single-step acylation process is rate-determining. The free energy barrier (18.8 kcal/mol) calculated for the rate-determining step is reasonably close to the experimentally-derived free energy barrier (~19.4 kcal/mol), suggesting that the obtained mechanistic insights are reasonable. The single-step reaction pathway for the acylation is remarkably different from the well-known two-step acylation reaction pathway for numerous ester hydrolysis reactions catalyzed by a serine esterase. This is the first time demonstrating that a single-step reaction pathway is possible for an ester hydrolysis reaction catalyzed by a serine esterase and, therefore, one no longer can simply assume that the acylation process must follow the well-known two-step reaction pathway.

Specific effects of background electrolytes on the kinetics of step propagation during calcite growth

NASA Astrophysics Data System (ADS)

Ruiz-Agudo, Encarnación; Putnis, Christine V.; Wang, Lijun; Putnis, Andrew

2011-07-01

The mechanisms by which background electrolytes modify the kinetics of non-equivalent step propagation during calcite growth were investigated using Atomic Force Microscopy (AFM), at constant driving force and solution stoichiometry. Our results suggest that the acute step spreading rate is controlled by kink-site nucleation and, ultimately, by the dehydration of surface sites, while the velocity of obtuse step advancement is mainly determined by hydration of calcium ions in solution. According to our results, kink nucleation at acute steps could be promoted by carbonate-assisted calcium attachment. The different sensitivity of obtuse and acute step propagation kinetics to cation and surface hydration could be the origin of the reversed geometries of calcite growth hillocks (i.e., rate of obtuse step spreading < rate of acute step spreading) observed in concentrated (ionic strength, IS = 0.1) KCl and CsCl solutions. At low IS (0.02), ion-specific effects seem to be mainly associated with changes in the solvation environment of calcium ions in solution. With increasing electrolyte concentration, the stabilization of surface water by weakly paired salts appears to become increasingly important in determining step spreading rate. At high ionic strength (IS = 0.1), overall calcite growth rates increased with increasing hydration of calcium in solution (i.e., decreasing ion pairing of background electrolytes for sodium-bearing salts) and with decreasing hydration of the carbonate surface site (i.e., increasing ion pairing for chloride-bearing salts). Changes in growth hillock morphology were observed in the presence of Li +, F - and SO42-, and can be interpreted as the result of the stabilization of polar surfaces due to increased ion hydration. These results increase our ability to predict crystal reactivity in natural fluids which contain significant amounts of solutes.

Simplified Two-Time Step Method for Calculating Combustion and Emission Rates of Jet-A and Methane Fuel With and Without Water Injection

NASA Technical Reports Server (NTRS)

Molnar, Melissa; Marek, C. John

2005-01-01

A simplified kinetic scheme for Jet-A, and methane fuels with water injection was developed to be used in numerical combustion codes, such as the National Combustor Code (NCC) or even simple FORTRAN codes. The two time step method is either an initial time averaged value (step one) or an instantaneous value (step two). The switch is based on the water concentration in moles/cc of 1x10(exp -20). The results presented here results in a correlation that gives the chemical kinetic time as two separate functions. This two time step method is used as opposed to a one step time averaged method previously developed to determine the chemical kinetic time with increased accuracy. The first time averaged step is used at the initial times for smaller water concentrations. This gives the average chemical kinetic time as a function of initial overall fuel air ratio, initial water to fuel mass ratio, temperature, and pressure. The second instantaneous step, to be used with higher water concentrations, gives the chemical kinetic time as a function of instantaneous fuel and water mole concentration, pressure and temperature (T4). The simple correlations would then be compared to the turbulent mixing times to determine the limiting rates of the reaction. The NASA Glenn GLSENS kinetics code calculates the reaction rates and rate constants for each species in a kinetic scheme for finite kinetic rates. These reaction rates are used to calculate the necessary chemical kinetic times. Chemical kinetic time equations for fuel, carbon monoxide and NOx are obtained for Jet-A fuel and methane with and without water injection to water mass loadings of 2/1 water to fuel. A similar correlation was also developed using data from NASA's Chemical Equilibrium Applications (CEA) code to determine the equilibrium concentrations of carbon monoxide and nitrogen oxide as functions of overall equivalence ratio, water to fuel mass ratio, pressure and temperature (T3). The temperature of the gas entering the turbine (T4) was also correlated as a function of the initial combustor temperature (T3), equivalence ratio, water to fuel mass ratio, and pressure.

Effect of deposition rate and NNN interactions on adatoms mobility in epitaxial growth

NASA Astrophysics Data System (ADS)

Hamouda, Ajmi B. H.; Mahjoub, B.; Blel, S.

2017-07-01

This paper provides a detailed analysis of the surface diffusion problem during epitaxial step-flow growth using a simple theoretical model for the diffusion equation of adatoms concentration. Within this framework, an analytical expression for the adatom mobility as a function of the deposition rate and the Next-Nearest-Neighbor (NNN) interactions is derived and compared with the effective mobility computed from kinetic Monte Carlo (kMC) simulations. As far as the 'small' step velocity or relatively weak deposition rate commonly used for copper growth is concerned, an excellent quantitative agreement with the theoretical prediction is found. The effective adatoms mobility is shown to exhibit an exponential decrease with NNN interactions strength and increases in roughly linear behavior versus deposition rate F. The effective step stiffness and the adatoms mobility are also shown to be closely related to the concentration of kinks.

A Flow Adhesion Assay to Study Leucocyte Recruitment to Human Hepatic Sinusoidal Endothelium Under Conditions of Shear Stress

PubMed Central

Shetty, Shishir; Weston, Christopher J.; Adams, David H.; Lalor, Patricia F.

2014-01-01

Leucocyte infiltration into human liver tissue is a common process in all adult inflammatory liver diseases. Chronic infiltration can drive the development of fibrosis and progression to cirrhosis. Understanding the molecular mechanisms that mediate leucocyte recruitment to the liver could identify important therapeutic targets for liver disease. The key interaction during leucocyte recruitment is that of inflammatory cells with endothelium under conditions of shear stress. Recruitment to the liver occurs within the low shear channels of the hepatic sinusoids which are lined by hepatic sinusoidal endothelial cells (HSEC). The conditions within the hepatic sinusoids can be recapitulated by perfusing leucocytes through channels lined by human HSEC monolayers at specific flow rates. In these conditions leucocytes undergo a brief tethering step followed by activation and firm adhesion, followed by a crawling step and subsequent transmigration across the endothelial layer. Using phase contrast microscopy, each step of this 'adhesion cascade' can be visualized and recorded followed by offline analysis. Endothelial cells or leucocytes can be pretreated with inhibitors to determine the role of specific molecules during this process. PMID:24686418

Step Permeability on the Pt(111) Surface

NASA Astrophysics Data System (ADS)

Altman, Michael

2005-03-01

Surface morphology will be affected, or even dictated, by kinetic limitations that may be present during growth. Asymmetric step attachment is recognized to be an important and possibly common cause of morphological growth instabilities. However, the impact of this kinetic limitation on growth morphology may be hindered by other factors such as the rate limiting step and step permeability. This strongly motivates experimental measurements of these quantities in real systems. Using low energy electron microscopy, we have measured step flow velocities in growth on the Pt(111) surface. The dependence of step velocity upon adjacent terrace width clearly shows evidence of asymmetric step attachment and step permeability. Step velocity is modeled by solving the diffusion equation simultaneously on several adjacent terraces subject to boundary conditions at intervening steps that include asymmetric step attachment and step permeability. This analysis allows a quantitative evaluation of step permeability and the kinetic length, which characterizes the rate limiting step continuously between diffusion and attachment-detachment limited regimes. This work provides information that is greatly needed to set physical bounds on the parameters that are used in theoretical treatments of growth. The observation that steps are permeable even on a simple metal surface should also stimulate more experimental measurements and theoretical treatments of this effect.

Permeability and kinetic coefficients for mesoscale BCF surface step dynamics: Discrete two-dimensional deposition-diffusion equation analysis

DOE PAGES

Zhao, Renjie; Evans, James W.; Oliveira, Tiago J.

2016-04-08

Here, a discrete version of deposition-diffusion equations appropriate for description of step flow on a vicinal surface is analyzed for a two-dimensional grid of adsorption sites representing the stepped surface and explicitly incorporating kinks along the step edges. Model energetics and kinetics appropriately account for binding of adatoms at steps and kinks, distinct terrace and edge diffusion rates, and possible additional barriers for attachment to steps. Analysis of adatom attachment fluxes as well as limiting values of adatom densities at step edges for nonuniform deposition scenarios allows determination of both permeability and kinetic coefficients. Behavior of these quantities is assessedmore » as a function of key system parameters including kink density, step attachment barriers, and the step edge diffusion rate.« less

Permeability and kinetic coefficients for mesoscale BCF surface step dynamics: Discrete two-dimensional deposition-diffusion equation analysis

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

Zhao, Renjie; Evans, James W.; Oliveira, Tiago J.

Here, a discrete version of deposition-diffusion equations appropriate for description of step flow on a vicinal surface is analyzed for a two-dimensional grid of adsorption sites representing the stepped surface and explicitly incorporating kinks along the step edges. Model energetics and kinetics appropriately account for binding of adatoms at steps and kinks, distinct terrace and edge diffusion rates, and possible additional barriers for attachment to steps. Analysis of adatom attachment fluxes as well as limiting values of adatom densities at step edges for nonuniform deposition scenarios allows determination of both permeability and kinetic coefficients. Behavior of these quantities is assessedmore » as a function of key system parameters including kink density, step attachment barriers, and the step edge diffusion rate.« less

Catalytic four-electron reduction of O2 via rate-determining proton-coupled electron transfer to a dinuclear cobalt-μ-1,2-peroxo complex.

PubMed

Fukuzumi, Shunichi; Mandal, Sukanta; Mase, Kentaro; Ohkubo, Kei; Park, Hyejin; Benet-Buchholz, Jordi; Nam, Wonwoo; Llobet, Antoni

2012-06-20

Four-electron reduction of O(2) by octamethylferrocene (Me(8)Fc) occurs efficiently with a dinuclear cobalt-μ-1,2-peroxo complex, 1, in the presence of trifluoroacetic acid in acetonitrile. Kinetic investigations of the overall catalytic reaction and each step in the catalytic cycle showed that proton-coupled electron transfer from Me(8)Fc to 1 is the rate-determining step in the catalytic cycle.

Comparative activity of TiO2 microspheres and P25 powder for organic degradation: Implicative importance of structural defects and organic adsorption

NASA Astrophysics Data System (ADS)

Wang, Chuan; Liu, Hong; Liu, Yuan; He, Guang'an; Jiang, Chengchun

2014-11-01

TiO2 microspheres have been employed as a promisingly new photocatalyst for water and wastewater treatment. P25 TiO2 is commonly employed and its properties are well established as photocatalyst. In this study, photocatalytic activities of the two TiO2 samples are compared by degrading sulfosalicylic acid (SSA), phenol, and 2,4-Dichlorophenoxyacetic acid (2,4-D) under 365 nm UV illumination in a suspension system at neutral pH and associated optimized TiO2 dosages. The results showed that the three organic compounds unexceptionally degraded more rapidly on P25 than on TiO2 microspheres in terms of the concentration-time curves and total organic carbon removals at 120 min. This might me attributed the presence of oxygen vacancies and Ti(III) defects already present on P25 as determined by electron paramagnetic resonance, implying that the defects played an important role for the enhancement of the charge transfer step as rate-determining step. The degradations of three organic compounds on P25 and TiO2 microspheres could be well described by the first-order rate equation, while the degradation kinetics of SSA on TiO2 microspheres was quite different. The difference was ascribed to the medium adsorption ability of SSA on the TiO2 surface.

Postprocessing Algorithm for Driving Conventional Scanning Tunneling Microscope at Fast Scan Rates.

PubMed

Zhang, Hao; Li, Xianqi; Chen, Yunmei; Park, Jewook; Li, An-Ping; Zhang, X-G

2017-01-01

We present an image postprocessing framework for Scanning Tunneling Microscope (STM) to reduce the strong spurious oscillations and scan line noise at fast scan rates and preserve the features, allowing an order of magnitude increase in the scan rate without upgrading the hardware. The proposed method consists of two steps for large scale images and four steps for atomic scale images. For large scale images, we first apply for each line an image registration method to align the forward and backward scans of the same line. In the second step we apply a "rubber band" model which is solved by a novel Constrained Adaptive and Iterative Filtering Algorithm (CIAFA). The numerical results on measurement from copper(111) surface indicate the processed images are comparable in accuracy to data obtained with a slow scan rate, but are free of the scan drift error commonly seen in slow scan data. For atomic scale images, an additional first step to remove line-by-line strong background fluctuations and a fourth step of replacing the postprocessed image by its ranking map as the final atomic resolution image are required. The resulting image restores the lattice image that is nearly undetectable in the original fast scan data.

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

PubMed

Bērziņš, Agris; Actiņš, Andris

2014-06-01

The dehydration kinetics of mildronate dihydrate [3-(1,1,1-trimethylhydrazin-1-ium-2-yl)propionate dihydrate] was analyzed in isothermal and nonisothermal modes. The particle size, sample preparation and storage, sample weight, nitrogen flow rate, relative humidity, and sample history were varied in order to evaluate the effect of these factors and to more accurately interpret the data obtained from such analysis. It was determined that comparable kinetic parameters can be obtained in both isothermal and nonisothermal mode. However, dehydration activation energy values obtained in nonisothermal mode showed variation with conversion degree because of different rate-limiting step energy at higher temperature. Moreover, carrying out experiments in this mode required consideration of additional experimental complications. Our study of the different sample and experimental factor effect revealed information about changes of the dehydration rate-limiting step energy, variable contribution from different rate limiting steps, as well as clarified the dehydration mechanism. Procedures for convenient and fast determination of dehydration kinetic parameters were offered. © 2014 Wiley Periodicals, Inc. and the American Pharmacists Association.

Differences in the catalytic mechanisms of mesophilic and thermophilic indole-3-glycerol phosphate synthase enzymes at their adaptive temperatures.

PubMed

Zaccardi, Margot J; Mannweiler, Olga; Boehr, David D

2012-02-10

Thermophilic enzymes tend to be less catalytically-active at lower temperatures relative to their mesophilic counterparts, despite having very similar crystal structures. An often cited hypothesis for this general observation is that thermostable enzymes have evolved a more rigid tertiary structure in order to cope with their more extreme, natural environment, but they are also less flexible at lower temperatures, leading to their lower catalytic activity under mesophilic conditions. An alternative hypothesis, however, is that complementary thermophilic-mesophilic enzyme pairs simply operate through different evolutionary-optimized catalytic mechanisms. In this communication, we present evidence that while the steps of the catalytic mechanisms for mesophilic and thermophilic indole-3-glycerol phosphate synthase (IGPS) enzymes are fundamentally similar, the identity of the rate-determining step changes as a function of temperature. Our findings indicate that while product release is rate-determining at 25°C for thermophilic IGPS, near its adaptive temperature (75°C), a proton transfer event, involving a general acid, becomes rate-determining. The rate-determining steps for thermophilic and mesophilic IGPS enzymes are also different at their respective, adaptive temperatures with the mesophilic IGPS-catalyzed reaction being rate-limited before irreversible CO2 release, and the thermophilic IGPS-catalyzed reaction being rate limited afterwards. Copyright © 2012 Elsevier Inc. All rights reserved.

Two types of rate-determining step in chemical and biochemical processes.

PubMed Central

Yagisawa, S

1989-01-01

Close examination of the concept of the rate-determining step (RDS) shows that there are two types of RDS depending on the definition of 'rate'. One is represented by the highest peak of the free-energy diagram of consecutive reactions and holds true where the rate is defined in terms of the concentration of the first reactant. The other is represented by the peak showing the maximum free-energy difference, where the free-energy difference is the height of a peak measured from the bottom of any preceding troughs, where the definition of the rate is in terms of the total reactant concentration including intermediates. There are no criteria a priori for selecting one of them. PMID:2597141

Analyzing the dependence of oxygen incorporation current density on overpotential and oxygen partial pressure in mixed conducting oxide electrodes.

PubMed

Guan, Zixuan; Chen, Di; Chueh, William C

2017-08-30

The oxygen incorporation reaction, which involves the transformation of an oxygen gas molecule to two lattice oxygen ions in a mixed ionic and electronic conducting solid, is a ubiquitous and fundamental reaction in solid-state electrochemistry. To understand the reaction pathway and to identify the rate-determining step, near-equilibrium measurements have been employed to quantify the exchange coefficients as a function of oxygen partial pressure and temperature. However, because the exchange coefficient contains contributions from both forward and reverse reaction rate constants and depends on both oxygen partial pressure and oxygen fugacity in the solid, unique and definitive mechanistic assessment has been challenging. In this work, we derive a current density equation as a function of both oxygen partial pressure and overpotential, and consider both near and far from equilibrium limits. Rather than considering specific reaction pathways, we generalize the multi-step oxygen incorporation reaction into the rate-determining step, preceding and following quasi-equilibrium steps, and consider the number of oxygen ions and electrons involved in each. By evaluating the dependence of current density on oxygen partial pressure and overpotential separately, one obtains the reaction orders for oxygen gas molecules and for solid-state species in the electrode. We simulated the oxygen incorporation current density-overpotential curves for praseodymium-doped ceria for various candidate rate-determining steps. This work highlights a promising method for studying the exchange kinetics far away from equilibrium.

Method of controlling a variable geometry type turbocharger

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

Hirabayashi, Y.

1988-08-23

This patent describes a method of controlling the supercharging pressure of a variable geometry type turbocharger having a bypass, comprising the following steps which are carried out successively: receiving signals from an engine speed sensor and from an engine knocking sensor; receiving a signal from a throttle valve sensor; judging whether or not an engine is being accelerated, and proceeding to step below if the engine is being accelerated and to step below if the engine is not being accelerated, i.e., if the engine is in a constant speed operation; determining a first correction value and proceeding to step below;more » judging whether or not the engine is knocking, and proceeding to step (d) if knocking is occurring and to step (f) below if no knocking is occurring; determining a second correction value and proceeding to step; receiving signals from the engine speed sensor and from an airflow meter which measures the quantity of airflow to be supplied to the engine; calculating an airflow rate per engine revolution; determining a duty valve according to the calculated airflow rate; transmitting the corrected duty value to control means for controlling the geometry of the variable geometry type turbocharger and the opening of bypass of the turbocharger, thereby controlling the supercharging pressure of the turbocharger.« less

Dynamic Modeling of the Main Blow in Basic Oxygen Steelmaking Using Measured Step Responses

NASA Astrophysics Data System (ADS)

Kattenbelt, Carolien; Roffel, B.

2008-10-01

In the control and optimization of basic oxygen steelmaking, it is important to have an understanding of the influence of control variables on the process. However, important process variables such as the composition of the steel and slag cannot be measured continuously. The decarburization rate and the accumulation rate of oxygen, which can be derived from the generally measured waste gas flow and composition, are an indication of changes in steel and slag composition. The influence of the control variables on the decarburization rate and the accumulation rate of oxygen can best be determined in the main blow period. In this article, the measured step responses of the decarburization rate and the accumulation rate of oxygen to step changes in the oxygen blowing rate, lance height, and the addition rate of iron ore during the main blow are presented. These measured step responses are subsequently used to develop a dynamic model for the main blow. The model consists of an iron oxide and a carbon balance and an additional equation describing the influence of the lance height and the oxygen blowing rate on the decarburization rate. With this simple dynamic model, the measured step responses can be explained satisfactorily.

An Interactive Classroom Activity Demonstrating Reaction Mechanisms and Rate-Determining Steps

ERIC Educational Resources Information Center

Jennings, Laura D.; Keller, Steven W.

2005-01-01

An interactive classroom activity that includes two-step reaction of unwrapping and eating chocolate candies is described which brings not only the reaction intermediate, but also the reactants and products into macroscopic view. The qualitative activation barriers of both steps can be adjusted independently.

Hydroxide as general base in the saponification of ethyl acetate.

PubMed

Mata-Segreda, Julio F

2002-03-13

The second-order rate constant for the saponification of ethyl acetate at 30.0 degrees C in H(2)O/D(2)O mixtures of deuterium atom fraction n (a proton inventory experiment) obeys the relation k(2)(n) = 0.122 s(-1) M(-1) (1 - n + 1.2n) (1 - n + 0.48n)/(1 - n + 1.4n) (1 - n + 0.68n)(3). This result is interpreted as a process where formation of the tetrahedral intermediate is the rate-determining step and the transition-state complex is formed via nucleophilic interaction of a water molecule with general-base assistance from hydroxide ion, opposite to the direct nucleophilic collision commonly accepted. This mechanistic picture agrees with previous heavy-atom kinetic isotope effect data of Marlier on the alkaline hydrolysis of methyl formate.

Characterization and multi-step transketolase-ω-transaminase bioconversions in an immobilized enzyme microreactor (IEMR) with packed tube.

PubMed

Halim, Amanatuzzakiah Abdul; Szita, Nicolas; Baganz, Frank

2013-12-01

The concept of de novo metabolic engineering through novel synthetic pathways offers new directions for multi-step enzymatic synthesis of complex molecules. This has been complemented by recent progress in performing enzymatic reactions using immobilized enzyme microreactors (IEMR). This work is concerned with the construction of de novo designed enzyme pathways in a microreactor synthesizing chiral molecules. An interesting compound, commonly used as the building block in several pharmaceutical syntheses, is a single diastereoisomer of 2-amino-1,3,4-butanetriol (ABT). This chiral amino alcohol can be synthesized from simple achiral substrates using two enzymes, transketolase (TK) and transaminase (TAm). Here we describe the development of an IEMR using His6-tagged TK and TAm immobilized onto Ni-NTA agarose beads and packed into tubes to enable multi-step enzyme reactions. The kinetic parameters of both enzymes were first determined using single IEMRs evaluated by a kinetic model developed for packed bed reactors. The Km(app) for both enzymes appeared to be flow rate dependent, while the turnover number kcat was reduced 3 fold compared to solution-phase TK and TAm reactions. For the multi-step enzyme reaction, single IEMRs were cascaded in series, whereby the first enzyme, TK, catalyzed a model reaction of lithium-hydroxypyruvate (HPA) and glycolaldehyde (GA) to L-erythrulose (ERY), and the second unit of the IEMR with immobilized TAm converted ERY into ABT using (S)-α-methylbenzylamine (MBA) as amine donor. With initial 60mM (HPA and GA each) and 6mM (MBA) substrate concentration mixture, the coupled reaction reached approximately 83% conversion in 20 min at the lowest flow rate. The ability to synthesize a chiral pharmaceutical intermediate, ABT in relatively short time proves this IEMR system as a powerful tool for construction and evaluation of de novo pathways as well as for determination of enzyme kinetics. Copyright © 2013 The Authors. Published by Elsevier B.V. All rights reserved.

Great Teaching

ERIC Educational Resources Information Center

Chetty, Raj; Friedman, John N.; Rockoff, Jonah E.

2012-01-01

In February 2012, the "New York Times" took the unusual step of publishing performance ratings for nearly 18,000 New York City teachers based on their students' test-score gains, commonly called value-added (VA) measures. This action, which followed a similar release of ratings in Los Angeles last year, drew new attention to the growing use of VA…

Blastocyst utilization rates after continuous culture in two commercial single-step media: a prospective randomized study with sibling oocytes.

PubMed

Sfontouris, Ioannis A; Kolibianakis, Efstratios M; Lainas, George T; Venetis, Christos A; Petsas, George K; Tarlatzis, Basil C; Lainas, Tryfon G

2017-10-01

The aim of this study is to determine whether blastocyst utilization rates are different after continuous culture in two different commercial single-step media. This is a paired randomized controlled trial with sibling oocytes conducted in infertility patients, aged ≤40 years with ≥10 oocytes retrieved assigned to blastocyst culture and transfer. Retrieved oocytes were randomly allocated to continuous culture in either Sage one-step medium (Origio) or Continuous Single Culture (CSC) medium (Irvine Scientific) without medium renewal up to day 5 post oocyte retrieval. Main outcome measure was the proportion of embryos suitable for clinical use (utilization rate). A total of 502 oocytes from 33 women were randomly allocated to continuous culture in either Sage one-step medium (n = 250) or CSC medium (n = 252). Fertilization was performed by either in vitro fertilization or intracytoplasmic sperm injection, and embryo transfers were performed on day 5. Two patients had all blastocysts frozen due to the occurrence of severe ovarian hyperstimulation syndrome. Fertilization and cleavage rates, as well as embryo quality on day 3, were similar in the two media. Blastocyst utilization rates (%, 95% CI) [55.4% (46.4-64.1) vs 54.7% (44.9-64.6), p = 0.717], blastocyst formation rates [53.6% (44.6-62.5) vs 51.9 (42.2-61.6), p = 0.755], and proportion of good quality blastocysts [36.8% (28.1-45.4) vs 36.1% (27.2-45.0), p = 0.850] were similar in Sage one-step and CSC media, respectively. Continuous culture of embryos in Sage one-step and CSC media is associated with similar blastocyst development and utilization rates. Both single-step media appear to provide adequate support during in vitro preimplantation embryo development. Whether these observations are also valid for other continuous single medium protocols remains to be determined. NCT02302638.

Problem-based learning outcomes: the glass half-full.

PubMed

Distlehorst, Linda H; Dawson, Elizabeth; Robbs, Randall S; Barrows, Howard S

2005-03-01

To compare the characteristics and outcome data of students from a single institution with a two-track, problem based learning (PBL) and standard (STND) curriculum. PBL and STND students from nine graduating classes at Southern Illinois University School of Medicine were compared using common medical school performance outcomes (USMLE Step 1, USMLE Step 2, clerkship mean ratings, number of clerkship honors and remediation designations, and the senior clinical competency exam), as well as common admission and demographic variables. PBL students were older, and the cohort had a higher proportion of women. The two tracks had similar USMLE Step 1 and 2 mean scores and pass rates. Performance differences were significant for PBL students in two clerkships as well as in the clerkship subcategories of clinical performance, knowledge and clinical reasoning, and noncognitive behaviors. In addition, the proportion of PBL students earning honors was greater. The traditional undergraduate educational outcomes for the PBL and STND students are very positive. In several of the clerkship performance measures, the PBL students performed significantly better, and in no circumstance did they perform worse than the STND students.

Homogeneous reactions of hydrocarbons, silane, and chlorosilanes in radiofrequency plasmas at low pressures

NASA Technical Reports Server (NTRS)

Avni, R.; Carmi, U.; Inspektor, A.; Rosenthal, I.

1984-01-01

The ion-molecule and radical-molecule mechanisms are responsible for the dissociation of hydrocarbon, silane, and chlorosilane monomers and the formation of polymerized species, respectively, in an RF plasma discharge. In a plasma containing a mixture of monomer and argon the rate-determining step for both dissociation and polymerization is governed by an ion-molecule type of interaction. Adding hydrogen or ammonia to the monomer-argon mixture transforms the rate-determining step from an ion-molecule interaction to a radical-molecule interaction for both monomer dissociation and polymerization.

Short‐term time step convergence in a climate model

PubMed Central

Rasch, Philip J.; Taylor, Mark A.; Jablonowski, Christiane

2015-01-01

Abstract This paper evaluates the numerical convergence of very short (1 h) simulations carried out with a spectral‐element (SE) configuration of the Community Atmosphere Model version 5 (CAM5). While the horizontal grid spacing is fixed at approximately 110 km, the process‐coupling time step is varied between 1800 and 1 s to reveal the convergence rate with respect to the temporal resolution. Special attention is paid to the behavior of the parameterized subgrid‐scale physics. First, a dynamical core test with reduced dynamics time steps is presented. The results demonstrate that the experimental setup is able to correctly assess the convergence rate of the discrete solutions to the adiabatic equations of atmospheric motion. Second, results from full‐physics CAM5 simulations with reduced physics and dynamics time steps are discussed. It is shown that the convergence rate is 0.4—considerably slower than the expected rate of 1.0. Sensitivity experiments indicate that, among the various subgrid‐scale physical parameterizations, the stratiform cloud schemes are associated with the largest time‐stepping errors, and are the primary cause of slow time step convergence. While the details of our findings are model specific, the general test procedure is applicable to any atmospheric general circulation model. The need for more accurate numerical treatments of physical parameterizations, especially the representation of stratiform clouds, is likely common in many models. The suggested test technique can help quantify the time‐stepping errors and identify the related model sensitivities. PMID:27660669

Modeling logistic performance in quantitative microbial risk assessment.

PubMed

Rijgersberg, Hajo; Tromp, Seth; Jacxsens, Liesbeth; Uyttendaele, Mieke

2010-01-01

In quantitative microbial risk assessment (QMRA), food safety in the food chain is modeled and simulated. In general, prevalences, concentrations, and numbers of microorganisms in media are investigated in the different steps from farm to fork. The underlying rates and conditions (such as storage times, temperatures, gas conditions, and their distributions) are determined. However, the logistic chain with its queues (storages, shelves) and mechanisms for ordering products is usually not taken into account. As a consequence, storage times-mutually dependent in successive steps in the chain-cannot be described adequately. This may have a great impact on the tails of risk distributions. Because food safety risks are generally very small, it is crucial to model the tails of (underlying) distributions as accurately as possible. Logistic performance can be modeled by describing the underlying planning and scheduling mechanisms in discrete-event modeling. This is common practice in operations research, specifically in supply chain management. In this article, we present the application of discrete-event modeling in the context of a QMRA for Listeria monocytogenes in fresh-cut iceberg lettuce. We show the potential value of discrete-event modeling in QMRA by calculating logistic interventions (modifications in the logistic chain) and determining their significance with respect to food safety.

Postprocessing Algorithm for Driving Conventional Scanning Tunneling Microscope at Fast Scan Rates

PubMed Central

Zhang, Hao; Li, Xianqi; Park, Jewook; Li, An-Ping

2017-01-01

We present an image postprocessing framework for Scanning Tunneling Microscope (STM) to reduce the strong spurious oscillations and scan line noise at fast scan rates and preserve the features, allowing an order of magnitude increase in the scan rate without upgrading the hardware. The proposed method consists of two steps for large scale images and four steps for atomic scale images. For large scale images, we first apply for each line an image registration method to align the forward and backward scans of the same line. In the second step we apply a “rubber band” model which is solved by a novel Constrained Adaptive and Iterative Filtering Algorithm (CIAFA). The numerical results on measurement from copper(111) surface indicate the processed images are comparable in accuracy to data obtained with a slow scan rate, but are free of the scan drift error commonly seen in slow scan data. For atomic scale images, an additional first step to remove line-by-line strong background fluctuations and a fourth step of replacing the postprocessed image by its ranking map as the final atomic resolution image are required. The resulting image restores the lattice image that is nearly undetectable in the original fast scan data. PMID:29362664

Determination of Biogenic Amines with HPLC-APCI-MS

USDA-ARS?s Scientific Manuscript database

Determination of biogenic amines in fish samples can be used as a quality attribute and are commonly performed using a derivatization step followed by high pressure liquid chromatography (HPLC) and UV detection. Over estimation and misidentification of biogenic amines can occur when interfering comp...

Single-molecule enzymology of steroid transforming enzymes: Transient kinetic studies and what they tell us.

PubMed

Penning, Trevor M

2016-07-01

Structure-function studies on steroid transforming enzymes often use site-directed mutagenesis to inform mechanisms of catalysis and effects on steroid binding, and data are reported in terms of changes in steady state kinetic parameters kcat, Km and kcat/Km. However, this dissection of function is limited since kcat is governed by the rate-determining step and Km is a complex macroscopic kinetic constant. Often site-directed mutagenesis can lead to a change in the rate-determining step which cannot be revealed by just reporting a decrease in kcat alone. These issues are made more complex when it is considered that many steroid transforming enzymes have more than one substrate and product. We present the case for using transient-kinetics performed with stopped-flow spectrometry to assign rate constants to discrete steps in these multi-substrate reactions and their use to interpret enzyme mechanism and the effects of disease and engineered mutations. We demonstrate that fluorescence kinetic transients can be used to measure ligand binding that may be accompanied by isomerization steps, revealing the existence of new enzyme intermediates. We also demonstrate that single-turnover reactions can provide a klim for the chemical step and Ks for steroid-substrate binding and that when coupled with kinetic isotope effect measurements can provide information on transition state intermediates. We also demonstrate how multiple turnover experiments can provide evidence for either "burst-phase" kinetics, which can reveal a slow product release step, or linear-phase kinetics, in which the chemical step can be rate-determining. With these assignments it becomes more straightforward to analyze the effects of mutations. We use examples from the hydroxysteroid dehydrogenases (AKR1Cs) and human steroid 5β-reductase (AKR1D1) to illustrate the utility of the approach, which are members of the aldo-keto reductase (AKR) superfamily. Copyright © 2015 Elsevier Ltd. All rights reserved.

Ab initio ONIOM-molecular dynamics (MD) study on the deamination reaction by cytidine deaminase.

PubMed

Matsubara, Toshiaki; Dupuis, Michel; Aida, Misako

2007-08-23

We applied the ONIOM-molecular dynamics (MD) method to the hydrolytic deamination of cytidine by cytidine deaminase, which is an essential step of the activation process of the anticancer drug inside the human body. The direct MD simulations were performed for the realistic model of cytidine deaminase by calculating the energy and its gradient by the ab initio ONIOM method on the fly. The ONIOM-MD calculations including the thermal motion show that the neighboring amino acid residue is an important factor of the environmental effects and significantly affects not only the geometry and energy of the substrate trapped in the pocket of the active site but also the elementary step of the catalytic reaction. We successfully simulate the second half of the catalytic cycle, which has been considered to involve the rate-determining step, and reveal that the rate-determining step is the release of the NH3 molecule.

New insight into the ZnO sulfidation reaction: mechanism and kinetics modeling of the ZnS outward growth.

PubMed

Neveux, Laure; Chiche, David; Pérez-Pellitero, Javier; Favergeon, Loïc; Gay, Anne-Sophie; Pijolat, Michèle

2013-02-07

Zinc oxide based materials are commonly used for the final desulfurization of synthesis gas in Fischer-Tropsch based XTL processes. Although the ZnO sulfidation reaction has been widely studied, little is known about the transformation at the crystal scale, its detailed mechanism and kinetics. A model ZnO material with well-determined characteristics (particle size and shape) has been synthesized to perform this study. Characterizations of sulfided samples (using XRD, TEM and electron diffraction) have shown the formation of oriented polycrystalline ZnS nanoparticles with a predominant hexagonal form (wurtzite phase). TEM observations also have evidenced an outward development of the ZnS phase, showing zinc and oxygen diffusion from the ZnO-ZnS internal interface to the surface of the ZnS particle. The kinetics of ZnO sulfidation by H(2)S has been investigated using isothermal and isobaric thermogravimetry. Kinetic tests have been performed that show that nucleation of ZnS is instantaneous compared to the growth process. A reaction mechanism composed of eight elementary steps has been proposed to account for these results, and various possible rate laws have been determined upon approximation of the rate-determining step. Thermogravimetry experiments performed in a wide range of H(2)S and H(2)O partial pressures have shown that the ZnO sulfidation reaction rate has a nonlinear variation with H(2)S partial pressure at the same time no significant influence of water vapor on reaction kinetics has been observed. From these observations, a mixed kinetics of external interface reaction with water desorption and oxygen diffusion has been determined to control the reaction kinetics and the proposed mechanism has been validated. However, the formation of voids at the ZnO-ZnS internal interface, characterized by TEM and electron tomography, strongly slows down the reaction rate. Therefore, the impact of the decreasing ZnO-ZnS internal interface on reaction kinetics has been taken into account in the reaction rate expression. In this way the void formation at the interface has been modeled considering a random nucleation followed by an isotropic growth of cavities. Very good agreement has been observed between both experimental and calculated rates after taking into account the decrease in the ZnO-ZnS internal interface.

An Empirical Method for Determining the Lunar Gravity Field. Ph.D. Thesis - George Washington Univ.

NASA Technical Reports Server (NTRS)

Ferrari, A. J.

1971-01-01

A method has been devised to determine the spherical harmonic coefficients of the lunar gravity field. This method consists of a two-step data reduction and estimation process. In the first step, a weighted least-squares empirical orbit determination scheme is applied to Doppler tracking data from lunar orbits to estimate long-period Kepler elements and rates. Each of the Kepler elements is represented by an independent function of time. The long-period perturbing effects of the earth, sun, and solar radiation are explicitly modeled in this scheme. Kepler element variations estimated by this empirical processor are ascribed to the non-central lunar gravitation features. Doppler data are reduced in this manner for as many orbits as are available. In the second step, the Kepler element rates are used as input to a second least-squares processor that estimates lunar gravity coefficients using the long-period Lagrange perturbation equations.

Understanding the hydrolysis mechanism of ethyl acetate catalyzed by an aqueous molybdocene: a computational chemistry investigation.

PubMed

Tílvez, Elkin; Cárdenas-Jirón, Gloria I; Menéndez, María I; López, Ramón

2015-02-16

A thoroughly mechanistic investigation on the [Cp2Mo(OH)(OH2)](+)-catalyzed hydrolysis of ethyl acetate has been performed using density functional theory methodology together with continuum and discrete-continuum solvation models. The use of explicit water molecules in the PCM-B3LYP/aug-cc-pVTZ (aug-cc-pVTZ-PP for Mo)//PCM-B3LYP/aug-cc-pVDZ (aug-cc-pVDZ-PP for Mo) computations is crucial to show that the intramolecular hydroxo ligand attack is the preferred mechanism in agreement with experimental suggestions. Besides, the most stable intermediate located along this mechanism is analogous to that experimentally reported for the norbornenyl acetate hydrolysis catalyzed by molybdocenes. The three most relevant steps are the formation and cleavage of the tetrahedral intermediate immediately formed after the hydroxo ligand attack and the acetic acid formation, with the second one being the rate-determining step with a Gibbs energy barrier of 36.7 kcal/mol. Among several functionals checked, B3LYP-D3 and M06 give the best agreement with experiment as the rate-determining Gibbs energy barrier obtained only differs 0.2 and 0.7 kcal/mol, respectively, from that derived from the experimental kinetic constant measured at 296.15 K. In both cases, the acetic acid elimination becomes now the rate-determining step of the overall process as it is 0.4 kcal/mol less stable than the tetrahedral intermediate cleavage. Apart from clarifying the identity of the cyclic intermediate and discarding the tetrahedral intermediate formation as the rate-determining step for the mechanism of the acetyl acetate hydrolysis catalyzed by molybdocenes, the small difference in the Gibbs energy barrier found between the acetic acid formation and the tetrahedral intermediate cleavage also uncovers that the rate-determining step could change when studying the reactivity of carboxylic esters other than ethyl acetate substrate specific toward molybdocenes or other transition metal complexes. Therefore, in general, the information reported here could be of interest in designing new catalysts and understanding the reaction mechanism of these and other metal-catalyzed hydrolysis reactions.

Universal dependence of hydrogen oxidation and evolution reaction activity of platinum-group metals on pH and hydrogen binding energy

PubMed Central

Zheng, Jie; Sheng, Wenchao; Zhuang, Zhongbin; Xu, Bingjun; Yan, Yushan

2016-01-01

Understanding how pH affects the activity of hydrogen oxidation reaction (HOR) and hydrogen evolution reaction (HER) is key to developing active, stable, and affordable HOR/HER catalysts for hydroxide exchange membrane fuel cells and electrolyzers. A common linear correlation between hydrogen binding energy (HBE) and pH is observed for four supported platinum-group metal catalysts (Pt/C, Ir/C, Pd/C, and Rh/C) over a broad pH range (0 to 13), suggesting that the pH dependence of HBE is metal-independent. A universal correlation between exchange current density and HBE is also observed on the four metals, indicating that they may share the same elementary steps and rate-determining steps and that the HBE is the dominant descriptor for HOR/HER activities. The onset potential of CO stripping on the four metals decreases with pH, indicating a stronger OH adsorption, which provides evidence against the promoting effect of adsorbed OH on HOR/HER. PMID:27034988

Universal dependence of hydrogen oxidation and evolution reaction activity of platinum-group metals on pH and hydrogen binding energy.

PubMed

Zheng, Jie; Sheng, Wenchao; Zhuang, Zhongbin; Xu, Bingjun; Yan, Yushan

2016-03-01

Understanding how pH affects the activity of hydrogen oxidation reaction (HOR) and hydrogen evolution reaction (HER) is key to developing active, stable, and affordable HOR/HER catalysts for hydroxide exchange membrane fuel cells and electrolyzers. A common linear correlation between hydrogen binding energy (HBE) and pH is observed for four supported platinum-group metal catalysts (Pt/C, Ir/C, Pd/C, and Rh/C) over a broad pH range (0 to 13), suggesting that the pH dependence of HBE is metal-independent. A universal correlation between exchange current density and HBE is also observed on the four metals, indicating that they may share the same elementary steps and rate-determining steps and that the HBE is the dominant descriptor for HOR/HER activities. The onset potential of CO stripping on the four metals decreases with pH, indicating a stronger OH adsorption, which provides evidence against the promoting effect of adsorbed OH on HOR/HER.

Optimum Particle Size for Gold-Catalyzed CO Oxidation

PubMed Central

2018-01-01

The structure sensitivity of gold-catalyzed CO oxidation is presented by analyzing in detail the dependence of CO oxidation rate on particle size. Clusters with less than 14 gold atoms adopt a planar structure, whereas larger ones adopt a three-dimensional structure. The CO and O2 adsorption properties depend strongly on particle structure and size. All of the reaction barriers relevant to CO oxidation display linear scaling relationships with CO and O2 binding strengths as main reactivity descriptors. Planar and three-dimensional gold clusters exhibit different linear scaling relationship due to different surface topologies and different coordination numbers of the surface atoms. On the basis of these linear scaling relationships, first-principles microkinetics simulations were conducted to determine CO oxidation rates and possible rate-determining step of Au particles. Planar Au9 and three-dimensional Au79 clusters present the highest CO oxidation rates for planar and three-dimensional clusters, respectively. The planar Au9 cluster is much more active than the optimum Au79 cluster. A common feature of optimum CO oxidation performance is the intermediate binding strengths of CO and O2, resulting in intermediate coverages of CO, O2, and O. Both these optimum particles present lower performance than maximum Sabatier performance, indicating that there is sufficient room for improvement of gold catalysts for CO oxidation. PMID:29707098

Effects of Foot Strike and Step Frequency on Achilles Tendon Stress During Running.

PubMed

Lyght, Michael; Nockerts, Matthew; Kernozek, Thomas W; Ragan, Robert

2016-08-01

Achilles tendon (AT) injuries are common in runners. The AT withstands high magnitudes of stress during running which may contribute to injury. Our purpose was to examine the effects of foot strike pattern and step frequency on AT stress and strain during running utilizing muscle forces based on a musculoskeletal model and subject-specific ultrasound-derived AT cross-sectional area. Nineteen female runners performed running trials under 6 conditions, including rearfoot strike and forefoot strike patterns at their preferred cadence, +5%, and -5% preferred cadence. Rearfoot strike patterns had less peak AT stress (P < .001), strain (P < .001), and strain rate (P < .001) compared with the forefoot strike pattern. A reduction in peak AT stress and strain were exhibited with a +5% preferred step frequency relative to the preferred condition using a rearfoot (P < .001) and forefoot (P=.005) strike pattern. Strain rate was not different (P > .05) between step frequencies within each foot strike condition. Our results suggest that a rearfoot pattern may reduce AT stress, strain, and strain rate. Increases in step frequency of 5% above preferred frequency, regardless of foot strike pattern, may also lower peak AT stress and strain.

Low Complexity Compression and Speed Enhancement for Optical Scanning Holography

PubMed Central

Tsang, P. W. M.; Poon, T.-C.; Liu, J.-P.; Kim, T.; Kim, Y. S.

2016-01-01

In this paper we report a low complexity compression method that is suitable for compact optical scanning holography (OSH) systems with different optical settings. Our proposed method can be divided into 2 major parts. First, an automatic decision maker is applied to select the rows of holographic pixels to be scanned. This process enhances the speed of acquiring a hologram, and also lowers the data rate. Second, each row of down-sampled pixels is converted into a one-bit representation with delta modulation (DM). Existing DM-based hologram compression techniques suffers from the disadvantage that a core parameter, commonly known as the step size, has to be determined in advance. However, the correct value of the step size for compressing each row of hologram is dependent on the dynamic range of the pixels, which could deviate significantly with the object scene, as well as OSH systems with different opical settings. We have overcome this problem by incorporating a dynamic step-size adjustment scheme. The proposed method is applied in the compression of holograms that are acquired with 2 different OSH systems, demonstrating a compression ratio of over two orders of magnitude, while preserving favorable fidelity on the reconstructed images. PMID:27708410

40 CFR 211.207 - Computation of the noise -reduction rating (NRR).

Code of Federal Regulations, 2012 CFR

2012-07-01

... mathematics to determine the combined value of protected ear levels (Step #8) which is used in Step #9 to exactly derive the NRR; or use the following table as a substitute for logarithmic mathematics to...

40 CFR 211.207 - Computation of the noise -reduction rating (NRR).

Code of Federal Regulations, 2014 CFR

2014-07-01

... mathematics to determine the combined value of protected ear levels (Step #8) which is used in Step #9 to exactly derive the NRR; or use the following table as a substitute for logarithmic mathematics to...

40 CFR 211.207 - Computation of the noise -reduction rating (NRR).

Code of Federal Regulations, 2013 CFR

2013-07-01

... mathematics to determine the combined value of protected ear levels (Step #8) which is used in Step #9 to exactly derive the NRR; or use the following table as a substitute for logarithmic mathematics to...

40 CFR 211.207 - Computation of the noise -reduction rating (NRR).

Code of Federal Regulations, 2010 CFR

2010-07-01

... mathematics to determine the combined value of protected ear levels (Step #8) which is used in Step #9 to exactly derive the NRR; or use the following table as a substitute for logarithmic mathematics to...

Laparoscopic Common Bile Duct Exploration in Patients With Gallstones and Choledocholithiasis

PubMed Central

Rodriguez, Omaira; Bellorín, Omar; Sánchez, Renata; Benítez, Gustavo

2010-01-01

Objectives: To compare the effectiveness of laparoscopic common bile duct exploration in patients with failed endoscopic retrograde cholangiopancreatography (ERCP). Methods: This is a descriptive, comparative study. Patients with an indication of common bile duct exploration between February 2005 and October 2008 were included. We studied 2 groups: Group A: patients with failed ERCP who underwent LCBDE plus LC. Group B: patients with common bile duct stones managed with the 1-step approach (LCBDE + LC) with no prior ERCP. Results: Twenty-five patients were included. Group A: 9 patients, group B: 16 patients. Success rate, operative time, and hospital stay were as follows: group A 66% vs group B 87.5%; group A 187 minutes vs 106 minutes; group A 4.5 days vs 2.3 days; respectively. Conclusion: Patients with failed ERCP should be considered as high-complex cases in which the laparoscopic procedure success rate decreases, and the conversion rate increases considerably. PMID:20932377

Tibial Acceleration and Spatiotemporal Mechanics in Distance Runners During Reduced-Body-Weight Conditions.

PubMed

Moran, Matthew F; Rickert, Brendan J; Greer, Beau K

2017-05-01

Treadmills that unload runners via a differential air-pressure (DAP) bladder (eg, AlterG Anti-Gravity Treadmill) are commonly used to reduce effective body weight (BW) in a clinical setting. However, the relationship between the level of unloading and tibial stress is currently unknown. To determine the relationship between tibial impact acceleration and level of BW unloading during running. Cross-sectional. University motion-analysis laboratory. 15 distance runners (9 male, 6 female; 20.4 ± 2.4 y, 60.1 ± 12.6 kg). Peak tibial acceleration and peak-to-peak tibial acceleration were measured via a uniaxial accelerometer attached to the tibia during a 37-min continuous treadmill run that simulated reduced-BW conditions via a DAP bladder. The trial began with a 10-min run at 100% BW followed by nine 3-min stages where BW was systematically reduced from 95% to 60% in 5% increments. There was no significant relationship between level of BW and either peak tibial acceleration or peak-to-peak tibial acceleration (P > .05). Both heart rate and step rate were significantly reduced with each 5% reduction in BW level (P < .01). Although ground-reaction forces are reduced when running in reduced-BW conditions on a DAP treadmill, tibial shock magnitudes are unchanged as an alteration in spatiotemporal running mechanics (eg, reduced step rate) and may nullify the unloading effect.

Temperature Requirements of Some Common Forensically Important Blow and Flesh Flies (Diptera) under Laboratory Conditions

PubMed Central

Shiravi, AH; Mostafavi, R; Akbarzadeh, K; Oshaghi, MA

2011-01-01

Background: The aim of his study was to determine development time and thermal requirements of three myiasis flies including Chrysomya albiceps, Lucilia sericata, and Sarcophaga sp. Methods: Rate of development (ROD) and accumulated degree day (ADD) of three important forensic flies in Iran, Chrysomya albiceps, Lucilia sericata, and Sarcophaga sp. by rearing individuals under a single constant temperature (28° C) was calculated using specific formula for four developmental events including egg hatching, larval stages, pupation, and eclosion. Results: Rates of development decreased step by step as the flies grew from egg to larvae and then to adult stage; however, this rate was bigger for blowflies (C. albiceps and L. sericata) in comparison with the flesh fly Sarcophaga sp. Egg hatching, larval stages, and pupation took about one fourth and half of the time of the total pre-adult development time for all of the three species. In general, the flesh fly Sarcophaga sp. required more heat for development than the blowflies. The thermal constants (K) were 130–195, 148–222, and 221–323 degree-days (DD) for egg hatching to adult stages of C. albiceps, L. sericata, and Sarcophaga sp., respectively. Conclusion: This is the first report on thermal requirement of three forensic flies in Iran. The data of this study provide preliminary information for forensic entomologist to establish PMI in the area of study. PMID:22808410

Person centered prediction of survival in population based screening program by an intelligent clinical decision support system.

PubMed

Safdari, Reza; Maserat, Elham; Asadzadeh Aghdaei, Hamid; Javan Amoli, Amir Hossein; Mohaghegh Shalmani, Hamid

2017-01-01

To survey person centered survival rate in population based screening program by an intelligent clinical decision support system. Colorectal cancer is the most common malignancy and major cause of morbidity and mortality throughout the world. Colorectal cancer is the sixth leading cause of cancer death in Iran. In this survey, we used cosine similarity as data mining technique and intelligent system for estimating survival of at risk groups in the screening plan. In the first step, we determined minimum data set (MDS). MDS was approved by experts and reviewing literatures. In the second step, MDS were coded by python language and matched with cosine similarity formula. Finally, survival rate by percent was illustrated in the user interface of national intelligent system. The national intelligent system was designed in PyCharm environment. Main data elements of intelligent system consist demographic information, age, referral type, risk group, recommendation and survival rate. Minimum data set related to survival comprise of clinical status, past medical history and socio-demographic information. Information of the covered population as a comprehensive database was connected to intelligent system and survival rate estimated for each patient. Mean range of survival of HNPCC patients and FAP patients were respectively 77.7% and 75.1%. Also, the mean range of the survival rate and other calculations have changed with the entry of new patients in the CRC registry by real-time. National intelligent system monitors the entire of risk group and reports survival rates by electronic guidelines and data mining technique and also operates according to the clinical process. This web base software has a critical role in the estimation survival rate in order to health care planning.

Trace contaminant adsorption and sorbent regeneration in closed ecological systems

NASA Technical Reports Server (NTRS)

Arnold, C. R.; Kersels, G. J.; Merrill, R. P.; Robell, A. J.; Wheeler, A.

1972-01-01

Correlation was obtained for determining sorptive capacity of carbon for pure and mixed contaminants under dry and humid conditions at various temperatures. Vacuum desorption rates were investigated for single particles and for sorbent beds. For sorbent beds, rate-determining step is Knudsen diffusion through interparticle voids.

Methods and apparatus for distributed resource discovery using examples

NASA Technical Reports Server (NTRS)

Chang, Yuan-Chi (Inventor); Li, Chung-Sheng (Inventor); Smith, John Richard (Inventor); Hill, Matthew L. (Inventor); Bergman, Lawrence David (Inventor); Castelli, Vittorio (Inventor)

2005-01-01

Distributed resource discovery is an essential step for information retrieval and/or providing information services. This step is usually used for determining the location of an information or data repository which has relevant information. The most fundamental challenge is the usual lack of semantic interoperability of the requested resource. In accordance with the invention, a method is disclosed where distributed repositories achieve semantic interoperability through the exchange of examples and, optionally, classifiers. The outcome of the inventive method can be used to determine whether common labels are referring to the same semantic meaning.

Comparison of step-down and binary search algorithms for determination of defibrillation threshold in humans.

PubMed

Shorofsky, Stephen R; Peters, Robert W; Rashba, Eric J; Gold, Michael R

2004-02-01

Determination of DFT is an integral part of ICD implantation. Two commonly used methods of DFT determination, the step-down method and the binary search method, were compared in 44 patients undergoing ICD testing for standard clinical indications. The step-down protocol used an initial shock of 18 J. The binary search method began with a shock energy of 9 J and successive shock energies were increased or decreased depending on the success of the previous shock. The DFT was defined as the lowest energy that successfully terminated ventricular fibrillation. The binary search method has the advantage of requiring a predetermined number of shocks, but some have questioned its accuracy. The study found that (mean) DFT obtained by the step-down method was 8.2 +/- 5.0, whereas by the binary search method DFT was 8.1 +/- 0.7 J, P = NS. DFT differed by no more than one step between methods in 32 (71%) of patients. The number of shocks required to determine DFT by the step-down method was 4.6 +/- 1.4, whereas by definition, the binary search method always required three shocks. In conclusion, the binary search method is preferable because it is of comparable efficacy and requires fewer shocks.

New Reduced Two-Time Step Method for Calculating Combustion and Emission Rates of Jet-A and Methane Fuel With and Without Water Injection

NASA Technical Reports Server (NTRS)

Molnar, Melissa; Marek, C. John

2004-01-01

A simplified kinetic scheme for Jet-A, and methane fuels with water injection was developed to be used in numerical combustion codes, such as the National Combustor Code (NCC) or even simple FORTRAN codes that are being developed at Glenn. The two time step method is either an initial time averaged value (step one) or an instantaneous value (step two). The switch is based on the water concentration in moles/cc of 1x10(exp -20). The results presented here results in a correlation that gives the chemical kinetic time as two separate functions. This two step method is used as opposed to a one step time averaged method previously developed to determine the chemical kinetic time with increased accuracy. The first time averaged step is used at the initial times for smaller water concentrations. This gives the average chemical kinetic time as a function of initial overall fuel air ratio, initial water to fuel mass ratio, temperature, and pressure. The second instantaneous step, to be used with higher water concentrations, gives the chemical kinetic time as a function of instantaneous fuel and water mole concentration, pressure and temperature (T4). The simple correlations would then be compared to the turbulent mixing times to determine the limiting properties of the reaction. The NASA Glenn GLSENS kinetics code calculates the reaction rates and rate constants for each species in a kinetic scheme for finite kinetic rates. These reaction rates were then used to calculate the necessary chemical kinetic times. Chemical kinetic time equations for fuel, carbon monoxide and NOx were obtained for Jet-A fuel and methane with and without water injection to water mass loadings of 2/1 water to fuel. A similar correlation was also developed using data from NASA's Chemical Equilibrium Applications (CEA) code to determine the equilibrium concentrations of carbon monoxide and nitrogen oxide as functions of overall equivalence ratio, water to fuel mass ratio, pressure and temperature (T3). The temperature of the gas entering the turbine (T4) was also correlated as a function of the initial combustor temperature (T3), equivalence ratio, water to fuel mass ratio, and pressure.

Generalization of improved step length symmetry from treadmill to overground walking in persons with stroke and hemiparesis†

PubMed Central

Savin, Douglas N.; Morton, Susanne M.; Whitall, Jill

2013-01-01

Objectives Determine whether adaptation to a swing phase perturbation during gait transferred from treadmill to overground walking, the rate of overground deadaptation, and whether overground aftereffects improved step length asymmetry in persons with hemiparetic stroke and gait asymmetry. Methods Ten participants with stroke and hemiparesis and 10 controls walked overground on an instrumented gait mat, adapted gait to a swing phase perturbation on a treadmill, then walked overground on the gait mat again. Outcome measures, primary: overground step length symmetry, rates of treadmill step length symmetry adaptation and overground step length symmetry deadaptation; secondary: overground gait velocity, stride length, and stride cycle duration. Results Step length symmetry aftereffects generalized to overground walking and adapted at a similar rate on the treadmill in both groups. Aftereffects decayed at a slower rate overground in participants with stroke and temporarily improved overground step length asymmetry. Both groups’ overground gait velocity increased post adaptation due to increased stride length and decreased stride duration. Conclusions Stroke and hemiparesis do not impair generalization of step length symmetry changes from adapted treadmill to overground walking, but prolong overground aftereffects. Significance Motor adaptation during treadmill walking may be an effective treatment for improving overground gait asymmetries post-stroke. PMID:24286858

Theoretical investigation of the mechanism of the baeyer-villiger reaction in nonpolar solvents.

PubMed

Okuno, Y

1997-02-01

The Baeyer-Villiger reaction of p-anisaldehyde with peroxyacetic acid in nonpolar solvents to give p-anisylformate was examined on the basis of ab initio molecular orbital calculations. To explain the experimental observations, the free-energy change was evaluated for each case in the absence and in the presence of an acid catalyst. It was found that, without catalysts, the rate-determining step corresponds to the carbonyl addition of peroxyacetic acid to p-anisaldehyde and the reaction hardly occurs. Acetic acid was found to catalyze the carbonyl addition and change the rate-determining step from the carbonyl addition to the migration of the carbonyl-adduct intermediate. Trifluoroacetic acid was observed to catalyze both the carbonyl addition and migration, and the carbonyl addition was demonstrated to be a rate-determining step. The results provided a convincing explanation of the complex kinetics seen experimentally. Further calculations were performed for the reaction of benzaldehyde with peroxyacetic acid to give phenylformate. Migratory aptitude was found to depend on the catalyst. Isotope effects were also investigated, and the exceptional isotope effect observed experimentally was shown to be due to the rate-determining carbonyl addition caused by autocatalysis. It is concluded that the mechanism of the reaction varies with catalysis or substituent effects. Copyright © 1997 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Dissolution of Fe(III) (hydr) oxides by metal-EDTA complexes

NASA Astrophysics Data System (ADS)

Ngwack, Bernd; Sigg, Laura

1997-03-01

The dissolution of Fe(III)(hydr)oxides (goethite and hydrous ferric oxide) by metal-EDTA complexes occurs by ligand-promoted dissolution. The process is initiated by the adsorption of metal-EDTA complexes to the surface and is followed by the dissociation of the complex at the surface and the release of Fe(III)EDTA into solution. The dissolution rate is decreased to a great extent if EDTA is complexed by metals in comparison to the uncomplexed EDTA. The rate decreases in the order EDTA CaEDTA ≫ PbEDTA > ZnEDTA > CuEDTA > Co(II)EDTA > NiEDTA. Two different rate-limiting steps determine the dissolution process: (1) detachment of Fe(III) from the oxide-structure and (2) dissociation of the metal-EDTA complexes. In the case of goethite, step 1 is slower than step 2 and the dissolution rates by various metals are similar. In the case of hydrous ferric oxide, step 2 is rate-limiting and the effect of the complexed metal is very pronounced.

Manipulating the Rate-Limiting Step in Water Oxidation Catalysis by Ruthenium Bipyridine–Dicarboxylate Complexes

DOE PAGES

Shaffer, David W.; Xie, Yan; Szalda, David J.; ...

2016-11-01

In order to gain a deeper mechanistic understanding of water oxidation by [(bda)Ru(L) 2] catalysts (bdaH 2 = [2,2'-bipyridine]-6,6'-dicarboxylic acid; L = pyridine-type ligand), a series of modified catalysts with one and two trifluoromethyl groups in the 4 position of the bda 2– ligand was synthesized and studied using stopped-flow kinetics. The additional $-$CF 3 groups increased the oxidation potentials for the catalysts and enhanced the rate of electrocatalytic water oxidation at low pH. Stopped-flow measurements of cerium(IV)-driven water oxidation at pH 1 revealed two distinct kinetic regimes depending on catalyst concentration. At relatively high catalyst concentration (ca. ≥10 –4more » M), the rate-determining step (RDS) was a proton-coupled oxidation of the catalyst by cerium(IV) with direct kinetic isotope effects (KIE > 1). At low catalyst concentration (ca. ≤10 –6 M), the RDS was a bimolecular step with k H/k D ≈ 0.8. The results support a catalytic mechanism involving coupling of two catalyst molecules. The rate constants for both RDSs were determined for all six catalysts studied. The presence of $-$CF 3 groups had inverse effects on the two steps, with the oxidation step being fastest for the unsubstituted complexes and the bimolecular step being faster for the most electron-deficient complexes. Finally, though the axial ligands studied here did not significantly affect the oxidation potentials of the catalysts, the nature of the ligand was found to be important not only in the bimolecular step but also in facilitating electron transfer from the metal center to the sacrificial oxidant.« less

Determining when to conduct a violence risk assessment: Development and initial validation of the Fordham Risk Screening Tool (FRST).

PubMed

Rosenfeld, Barry; Foellmi, Melodie; Khadivi, Ali; Wijetunga, Charity; Howe, Jacqueline; Nijdam-Jones, Alicia; Grover, Shana; Rotter, Merrill

2017-08-01

Techniques to assess violence risk are increasingly common, but no systematic approach exists to help clinicians decide which psychiatric patients are most in need of a violence risk assessment. The Fordham Risk Screening Tool (FRST) was designed to fill this void, providing a structured, systematic approach to screening psychiatric patients and determining the need for further, more thorough violence risk assessment. The FRST was administered to a sample of 210 consecutive admissions to the civil psychiatric units of an urban medical center, 159 of whom were subsequently evaluated using the Historical Clinical Risk Management-20, version 3, to determine violence risk. The FRST showed a high degree of sensitivity (93%) in identifying patients subsequently deemed to be at high risk for violence (based on the Case Prioritization risk rating). The FRST also identified all of the patients (100%) rated high in potential for severe violence (based on the Serious Physical Harm Historical Clinical Risk Management-20, version 3, summary risk rating). Sensitivity was more modest when individuals rated as moderate risk were included as the criterion (rather than only those identified as high risk). Specificity was also moderate, screening out approximately half of all participants as not needing further risk assessment. A systematic approach to risk screening is clearly needed to prioritize psychiatric admissions for thorough risk assessment, and the FRST appears to be a potentially valuable step in that process. (PsycINFO Database Record (c) 2017 APA, all rights reserved).

Enhanced performance of wearable piezoelectric nanogenerator fabricated by two-step hydrothermal process

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

Qiu, Yu; Lei, Jixue; Yin, Bing

2014-03-17

A simple two-step hydrothermal process was proposed for enhancing the performance of the nanogenerator on flexible and wearable terylene-fabric substrate. With this method, a significant enhancement in output voltage of the nanogenerator from ∼10 mV to 7 V was achieved, comparing with the one by conventional one-step process. In addition, another advantage with the devices synthesized by two-step hydrothermal process was that their output voltages are only sensitive to strain rather than strain rate. The devices with a high output voltage have the ability to power common electric devices and will have important applications in flexible electronics and wearable devices.

The mechanism of transition-metal (Cu or Pd)-catalyzed synthesis of benzimidazoles from amidines: theoretical investigation.

PubMed

Li, Juan; Gu, Honghong; Wu, Caihong; Du, Lijuan

2014-11-28

In this study, the Cu(OAc)2- and [PdCl2(PhCN)2]-catalyzed syntheses of benzimidazoles from amidines were theoretically investigated using density functional theory calculations. For the Cu-catalyzed system, our calculations supported a four-step-pathway involving C-H activation of an arene with Cu(II) via concerted metalation-deprotonation (CMD), followed by oxidation of the Cu(II) intermediate and deprotonation of the imino group by Cu(III), and finally reductive elimination from Cu(III). In our calculations, the barriers for the CMD step and the oxidation step are the same. The results are different from the ones reported by Fu et al. in which the whole reaction mechanism includes three steps and the CMD step is rate determining. On the basis of the calculation results for the [PdCl2(PhCN)2]-catalyzed system, C-H bond breaking by CMD occurs first, followed by the rate-determining C-N bond formation and N-H deprotonation. Pd(III) species is not involved in the [PdCl2(PhCN)2]-catalyzed syntheses of benzimidazoles from amidines.

Endoclip Magnetic Resonance Imaging Screening: A Local Practice Review.

PubMed

Accorsi, Fabio; Lalonde, Alain; Leswick, David A

2018-05-01

Not all endoscopically placed clips (endoclips) are magnetic resonance imaging (MRI) compatible. At many institutions, endoclip screening is part of the pre-MRI screening process. Our objective is to determine the contribution of each step of this endoclip screening protocol in determining a patient's endoclip status at our institution. A retrospective review of patients' endoscopic histories on general MRI screening forms for patients scanned during a 40-day period was performed to assess the percentage of patients that require endoclip screening at our institution. Following this, a prospective evaluation of 614 patients' endoclip screening determined the percentage of these patients ultimately exposed to each step in the protocol (exposure), and the percentage of patients whose endoclip status was determined with reasonable certainty by each step (determination). Exposure and determination values for each step were calculated as follows (exposure, determination): verbal interview (100%, 86%), review of past available imaging (14%, 36%), review of endoscopy report (9%, 57%), and new abdominal radiograph (4%, 96%), or CT (0.2%, 100%) for evaluation of potential endoclips. Only 1 patient did not receive MRI because of screening (in situ gastrointestinal endoclip identified). Verbal interview is invaluable to endoclip screening, clearing 86% of patients with minimal monetary and time investment. Conversely, the limited availability of endoscopy reports and relevant past imaging somewhat restricts the determination rates of these. New imaging (radiograph or computed tomography) is required <5% of the time, and although costly and associated with patient irradiation, has excellent determination rates (above 96%) when needed. Copyright © 2017 Canadian Association of Radiologists. Published by Elsevier Inc. All rights reserved.

Is a multivariate consensus representation of genetic relationships among populations always meaningful?

PubMed Central

Moazami-Goudarzi, K; Laloë, D

2002-01-01

To determine the relationships among closely related populations or species, two methods are commonly used in the literature: phylogenetic reconstruction or multivariate analysis. The aim of this article is to assess the reliability of multivariate analysis. We describe a method that is based on principal component analysis and Mantel correlations, using a two-step process: The first step consists of a single-marker analysis and the second step tests if each marker reveals the same typology concerning population differentiation. We conclude that if single markers are not congruent, the compromise structure is not meaningful. Our model is not based on any particular mutation process and it can be applied to most of the commonly used genetic markers. This method is also useful to determine the contribution of each marker to the typology of populations. We test whether our method is efficient with two real data sets based on microsatellite markers. Our analysis suggests that for closely related populations, it is not always possible to accept the hypothesis that an increase in the number of markers will increase the reliability of the typology analysis. PMID:12242255

Physiological and biomechanical responses to walking underwater on a non-motorised treadmill: effects of different exercise intensities and depths in middle-aged healthy women.

PubMed

Benelli, Piero; Colasanti, Franca; Ditroilo, Massimiliano; Cuesta-Vargas, Antonio; Gatta, Giorgio; Giacomini, Francesco; Lucertini, Francesco

2014-01-01

Non-motorised underwater treadmills are commonly used in fitness activities. However, no studies have examined physiological and biomechanical responses of walking on non-motorised treadmills at different intensities and depths. Fifteen middle-aged healthy women underwent two underwater walking tests at two different depths, immersed either up to the xiphoid process (deep water) or the iliac crest (shallow water), at 100, 110, 120, 130 step-per-minute (spm). Oxygen consumption (VO2), heart rate (HR), blood lactate concentration, perceived exertion and step length were determined. Compared to deep water, walking in shallow water exhibited, at all intensities, significantly higher VO2 (+13.5%, on average) and HR (+8.1%, on average) responses. Water depth did not influence lactate concentration, whereas perceived exertion was higher in shallow compared to deep water, solely at 120 (+40%) and 130 (+39.4%) spm. Average step length was reduced as the intensity increased (from 100 to 130 spm), irrespective of water depth. Expressed as a percentage of maximum, average VO2 and HR were: 64-76% of peak VO2 and 71-90% of maximum HR, respectively at both water depths. Accordingly, this form of exercise can be included in the "vigorous" range of exercise intensity, at any of the step frequencies used in this study.

Obesity does not increase External Mechanical Work per kilogram body mass during Walking

PubMed Central

Browning, Raymond C.; McGowan, Craig P.; Kram, Rodger

2009-01-01

Walking is the most common type of physical activity prescribed for the treatment of obesity. The net metabolic rate during level walking (Watts/kg) is ~10% greater in obese vs. normal weight adults. External mechanical work (Wext) is one of the primary determinants of the metabolic cost of walking, but the effects of obesity on Wext have not been clearly established. The purpose of this study was to compare Wext between obese and normal weight adults across a range of walking speeds. We hypothesized that Wext (J/step) would be greater in obese adults but Wext normalized to body mass would be similar in obese and normal weight adults. We collected right leg three-dimensional ground reaction forces (GRF) while twenty adults (10 obese, BMI=35.6 kg/m2 and 10 normal weight, BMI=22.1 kg/m2) walked on a level, dual-belt force measuring treadmill at six speeds (0.50–1.75 m/s). We used the individual limb method (ILM) to calculate external work done on the center of mass. Absolute Wext (J/step) was greater in obese vs. normal weight adults at each walking speed, but relative Wext (J/step/kg) was similar between the groups. Step frequencies were not different. These results suggest that Wext is not responsible for the greater metabolic cost of walking (W/kg) in moderately obese adults. PMID:19646701

Determination of Glucose Utilization Rates in Cultured Astrocytes and Neurons with [14C]deoxyglucose: Progress, Pitfalls, and Discovery of Intracellular Glucose Compartmentation.

PubMed

Dienel, Gerald A; Cruz, Nancy F; Sokoloff, Louis; Driscoll, Bernard F

2017-01-01

2-Deoxy-D-[ 14 C]glucose ([ 14 C]DG) is commonly used to determine local glucose utilization rates (CMR glc ) in living brain and to estimate CMR glc in cultured brain cells as rates of [ 14 C]DG phosphorylation. Phosphorylation rates of [ 14 C]DG and its metabolizable fluorescent analog, 2-(N-(7-nitrobenz-2-oxa-1,3-diazol-4-yl)amino)-2-deoxyglucose (2-NBDG), however, do not take into account differences in the kinetics of transport and metabolism of [ 14 C]DG or 2-NBDG and glucose in neuronal and astrocytic cells in cultures or in single cells in brain tissue, and conclusions drawn from these data may, therefore, not be correct. As a first step toward the goal of quantitative determination of CMR glc in astrocytes and neurons in cultures, the steady-state intracellular-to-extracellular concentration ratios (distribution spaces) for glucose and [ 14 C]DG were determined in cultured striatal neurons and astrocytes as functions of extracellular glucose concentration. Unexpectedly, the glucose distribution spaces rose during extreme hypoglycemia, exceeding 1.0 in astrocytes, whereas the [ 14 C]DG distribution space fell at the lowest glucose levels. Calculated CMR glc was greatly overestimated in hypoglycemic and normoglycemic cells because the intracellular glucose concentrations were too high. Determination of the distribution space for [ 14 C]glucose revealed compartmentation of intracellular glucose in astrocytes, and probably, also in neurons. A smaller metabolic pool is readily accessible to hexokinase and communicates with extracellular glucose, whereas the larger pool is sequestered from hexokinase activity. A new experimental approach using double-labeled assays with DG and glucose is suggested to avoid the limitations imposed by glucose compartmentation on metabolic assays.

Impact of Pitot tube calibration on the uncertainty of water flow rate measurement

NASA Astrophysics Data System (ADS)

de Oliveira Buscarini, Icaro; Costa Barsaglini, Andre; Saiz Jabardo, Paulo Jose; Massami Taira, Nilson; Nader, Gilder

2015-10-01

Water utility companies often use Cole type Pitot tubes to map velocity profiles and thus measure flow rate. Frequent monitoring and measurement of flow rate is an important step in identifying leaks and other types of losses. In Brazil losses as high as 42% are common and in some places even higher values are found. When using Cole type Pitot tubes to measure the flow rate, the uncertainty of the calibration coefficient (Cd) is a major component of the overall flow rate measurement uncertainty. A common practice is to employ the usual value Cd = 0.869, in use since Cole proposed his Pitot tube in 1896. Analysis of 414 calibrations of Cole type Pitot tubes show that Cd varies considerably and values as high 0.020 for the expanded uncertainty are common. Combined with other uncertainty sources, the overall velocity measurement uncertainty is 0.02, increasing flowrate measurement uncertainty by 1.5% which, for the Sao Paulo metropolitan area (Brazil) corresponds to 3.5 × 107 m3/year.

Building a common pipeline for rule-based document classification.

PubMed

Patterson, Olga V; Ginter, Thomas; DuVall, Scott L

2013-01-01

Instance-based classification of clinical text is a widely used natural language processing task employed as a step for patient classification, document retrieval, or information extraction. Rule-based approaches rely on concept identification and context analysis in order to determine the appropriate class. We propose a five-step process that enables even small research teams to develop simple but powerful rule-based NLP systems by taking advantage of a common UIMA AS based pipeline for classification. Our proposed methodology coupled with the general-purpose solution provides researchers with access to the data locked in clinical text in cases of limited human resources and compact timelines.

Radical molecule and ion-molecule mechanisms in the polymerization of hydrocarbons and chlorosilanes in R.F. plasmas at low pressures (below 1.0 Torr)

NASA Technical Reports Server (NTRS)

Avni, R.; Carmi, U.; Inspektor, A.; Rosenthal, I.

1984-01-01

The ion-molecule and the radical-molecule mechanisms are responsible for the dissociation of hydrocarbons, and chlorosilane monomers and the formation of polymerized species, respectively, in the plasma state of a RF discharge. In the plasma, of a mixture of monomer with Ar, the rate determining step for both dissociation and polymerization is governed by an ion-molecular type interaction. Additions of H2 or NH3 to the monomer Ar(+) mixture transforms the rate determining step from an ion-molecular interaction to a radical-molecule type interaction for both monomer dissociation and polymerization processes.

Radical and ion molecule mechanisms in the polymerization of hydrocarbons and chlorosilanes in RF plasmas at low pressures ( 1.0 torr)

NASA Technical Reports Server (NTRS)

Avni, R.; Carmi, U.; Inspektor, A.; Rosenthal, I.

1984-01-01

The ion-molecule and the radical-molecule mechanisms are responsible for the dissociation of hydrocarbons, and chlorosilane monomers and the formation of polymerized species, respectively, in the plasma state of a RF discharge. In the plasma, of a mixture of monomer with Ar, the rate determining step for both dissociation and polymerization is governed by an ion-molecular type interaction. Additions of H2 or NH3 to the monomer Ar(+) mixture transforms the rate determining step from an ion-molecular interaction to a radical-molecule type interaction for both monomer dissociation and polymerization processes.

Status of Cancer | Did You Know?

Cancer.gov

The Status of Cancer is an update on the rate of new cancer cases, deaths, and the most common cancers in the United States. Data from 1975 to 2012 provide trends in cancer rates among people from all racial and ethnic backgrounds combined. Watch this video to find out which cancers have declined, which have increased, and what steps can be taken to reduce the risk.

Sociodemographic determinants of pedometer-determined physical activity among Japanese adults.

PubMed

Inoue, Shigeru; Ohya, Yumiko; Odagiri, Yuko; Takamiya, Tomoko; Suijo, Kenichi; Kamada, Masamitsu; Okada, Shinpei; Tudor-Locke, Catrine; Shimomitsu, Teruichi

2011-05-01

Although previous studies have reported physical activity and its sociodemographic determinants using self-report measures, there have been few studies using pedometers. To ascertain pedometer-determined physical activity and its sociodemographic determinants among community residents living in four Japanese cities. A cross-sectional mail survey was conducted from February 2007 to January 2008 with a sample of 4000 residents (aged 20-69 years and 50% male) who were randomly selected from the registry of residential addresses. Complete responses for both questionnaire and pedometer were obtained from 790 residents (48.3±13.7 years, 46.7% male). Associations of 11 sociodemographic variables with steps per day were examined using multiple logistic regression analyses. Data were analyzed in 2010. Men averaged 8763±3497 steps/day and women averaged 8242±3277 steps/day. Further, 29.0% of men and 27.8% of women walked ≥10,000 steps/day. City of residence, good self-rated health, low educational attainment, and not owning a car were associated with taking ≥10,000 steps/day in men, whereas employed status and dog ownership were associated with walking ≥10,000 steps/day in women. The results contribute to understanding of step-defined physical activity and its sociodemographic determinants. A diversity of step counts by sociodemographic variables clarifies specific populations among Japanese who are in need of intervention to promote physical activity. Copyright © 2011 American Journal of Preventive Medicine. Published by Elsevier Inc. All rights reserved.

Uncovering the Atomistic Mechanism for Calcite Step Growth

DOE PAGES

De La Pierre, Marco; Raiteri, Paolo; Stack, Andrew G.; ...

2017-04-13

Determining a complete atomic-level picture of how minerals grow from aqueous solution remains a challenge as macroscopic rates can be a convolution of many reactions. For the case of calcite (CaCO 3) in water, computer simulations have been used in this paper to map the complex thermodynamic landscape leading to growth of the two distinct steps, acute and obtuse, on the basal surface. The carbonate ion is found to preferentially adsorb at the upper edge of acute steps while Ca 2+ only adsorbs after CO 3 2-. In contrast to the conventional picture, ion pairs prefer to bind at themore » upper edge of the step with only one ion, at most, coordinated to the step and lower terrace. Finally, migration of the first carbonate ion to a growth site is found to be rate-limiting for kink nucleation, with this process having a lower activation energy on the obtuse step.« less

Probing the mechanism of proton coupled electron transfer to dioxygen: the oxidative half-reaction of bovine serum amine oxidase.

PubMed

Su, Q; Klinman, J P

1998-09-08

Bovine serum amine oxidase (BSAO) catalyzes the oxidative deamination of primary amines, concomitant with the reduction of molecular oxygen to hydrogen peroxide via a ping-pong mechanism. A protocol has been developed for an analysis of chemical and kinetic mechanisms in the conversion of dioxygen to hydrogen peroxide. Steady-state kinetics show that two groups need to be deprotonated to facilitate the oxidative half-reaction. The pH dependence of Vmax/Km(O2) reveals pKa's of 6.2 +/- 0.3 and 7.0 +/- 0.2, respectively. A pKa of 7.2 +/- 0.1 has been obtained from a titration of anaerobically reduced BSAO using UV-vis spectrophotometry. The near identity of the pKa obtained from the reduced enzyme titration with the second pKa from steady-state kinetics suggests that this second pKa arises from the reduced cofactor. The assignment of pKa is supported by the observed pH dependence for formation of the cofactor semiquinone signal, detected by EPR spectroscopy under anaerobic conditions. To address the nature of rate-limiting steps in the oxidative half-reaction, the solvent isotope effect, viscosity effect, and O-18 isotope effect on Vmax/Km(O2) have been determined. The solvent isotope effect is indistinguishable from unity, ruling out a proton transfer as a rate-determining step. Use of glucose as a solvent viscosogen shows no viscosity effect, indicating that binding of oxygen is not in the rate-determining step. The O-18 kinetic isotope effect is independent of pH with an average value of 18(V/K) = 1.0097 +/- 0. 0010. This has been compared to calculated equilibrium O-18 isotope effects for various dioxygen intermediate species [Tian and Klinman (1993) J. Am. Chem. Soc. 115, 8891], leading to the conclusion that either the first electron transfer to dioxygen or the desorption of product peroxide from a Cu(II)-OOH complex could be the rate-limiting step. The distribution of steady-state enzyme species was, therefore, analyzed through a combination of stopped-flow experiments and analysis of DV and D(V/K) for benzylamine oxidation. We conclude that the major species accumulating in the steady state are the oxidized cofactor-substrate Schiff base complex and the reduced, aminoquinol form of cofactor. These data rule out a slow release of product hydroperoxide from the aminoquinone form of enzyme, leading to the conclusion that the first electron transfer from substrate-reduced cofactor to dioxygen is the rate-determining step in the oxidative half-reaction. This step is also estimated to be 40% rate-limiting in kcat. An important mechanistic conclusion from this study is that dioxygen binding is a separate step from the rate-limiting electron-transfer step to form superoxide. On the basis of a recently determined X-ray structure for the active form of a yeast amine oxidase from Hansenula polymorpha [Li et al. (1998) Structure 6, 293], a hydrophobic space has been identified near the O-2 position of reduced cofactor as the putative dioxygen binding site. Movement of superoxide from this site onto the Cu(II) at the active site may occur prior to further electron transfer from cofactor to superoxide.

Pathway and rate-limiting step of glyphosate degradation by Aspergillus oryzae A-F02.

PubMed

Fu, Gui-Ming; Chen, Yan; Li, Ru-Yi; Yuan, Xiao-Qiang; Liu, Cheng-Mei; Li, Bin; Wan, Yin

2017-09-14

Aspergillus oryzae A-F02, a glyphosate-degrading fungus, was isolated from an aeration tank in a pesticide factory. The pathway and rate-limiting step of glyphosate (GP) degradation were investigated through metabolite analysis. GP, aminomethylphosphonic acid (AMPA), and methylamine were detected in the fermentation liquid of A. oryzae A-F02, whereas sarcosine and glycine were not. The pathway of GP degradation in A. oryzae A-F02 was revealed: GP was first degraded into AMPA, which was then degraded into methylamine. Finally, methylamine was further degraded into other products. Investigating the effects of the exogenous addition of substrates and metabolites showed that the degradation of GP to AMPA is the rate-limiting step of GP degradation by A. oryzae A-F02. In addition, the accumulation of AMPA and methylamine did not cause feedback inhibition in GP degradation. Results showed that degrading GP to AMPA was a crucial step in the degradation of GP, which determines the degradation rate of GP by A. oryzae A-F02.

Fluoroscopy guided percutaneous renal access in prone position

PubMed Central

Sharma, Gyanendra R; Maheshwari, Pankaj N; Sharma, Anshu G; Maheshwari, Reeta P; Heda, Ritwik S; Maheshwari, Sakshi P

2015-01-01

Percutaneous nephrolithotomy is a very commonly done procedure for management of renal calculus disease. Establishing a good access is the first and probably the most crucial step of this procedure. A proper access is the gateway to success. However, this crucial step has the steepest learning curve for, in a fluoroscopy guided access, it involves visualizing a three dimensional anatomy on a two dimensional fluoroscopy screen. This review describes the anatomical basis of the renal access. It provides a literature review of all aspects of percutaneous renal access along with the advances that have taken place in this field over the years. The article describes a technique to determine the site of skin puncture, the angle and depth of puncture using a simple mathematical principle. It also reviews the common problems faced during the process of puncture and dilatation and describes the ways to overcome them. The aim of this article is to provide the reader a step by step guide for percutaneous renal access. PMID:25789297

COMPARISON OF FIELD AEROBIC BIODEGRADATION RATES TO LABORATORY

EPA Science Inventory

It is common to use bioventing as a polishing step for soil vapor extraction. It was originally planned to use soil vapor extraction and bioventing at a former landfill site in Delaware but laboratory scale biodegradation studies indicated that most of the volatile organic compou...

Is impaired control of reactive stepping related to falls during inpatient stroke rehabilitation?

PubMed

Mansfield, Avril; Inness, Elizabeth L; Wong, Jennifer S; Fraser, Julia E; McIlroy, William E

2013-01-01

Individuals with stroke fall more often than age-matched controls. Although many focus on the multifactorial nature of falls, the fundamental problem is likely the ability for an individual to generate reactions to recover from a loss of balance. Stepping reactions to recover balance are particularly important to balance recovery, and individuals with stroke have difficulty executing these responses to prevent a fall following a loss of balance. The purpose of this study is to determine if characteristics of balance recovery steps are related to falls during inpatient stroke rehabilitation. We conducted a retrospective review of individuals with stroke attending inpatient rehabilitation (n = 136). Details of falls experienced during inpatient rehabilitation were obtained from incident reports, nursing notes, and patient interviews. Stepping reactions were evoked using a "release-from-lean" postural perturbation. Poisson regression was used to determine characteristics of stepping reactions that were related to increased fall frequency relative to length of stay. In all, 20 individuals experienced 29 falls during inpatient rehabilitation. The characteristics of stepping reactions significantly related to increased fall rates were increased frequency of external assistance to prevent a fall to the floor, increased frequency of no-step responses, increased frequency of step responses with inadequate foot clearance, and delayed time to initiate stepping responses. Impaired control of balance recovery steps is related to increased fall rates during inpatient stroke rehabilitation. This study informs the specific features of stepping reactions that can be targeted with physiotherapy intervention during inpatient rehabilitation to improve dynamic stability control and potentially prevent falls.

Dynamic Histogram Analysis To Determine Free Energies and Rates from Biased Simulations.

PubMed

Stelzl, Lukas S; Kells, Adam; Rosta, Edina; Hummer, Gerhard

2017-12-12

We present an algorithm to calculate free energies and rates from molecular simulations on biased potential energy surfaces. As input, it uses the accumulated times spent in each state or bin of a histogram and counts of transitions between them. Optimal unbiased equilibrium free energies for each of the states/bins are then obtained by maximizing the likelihood of a master equation (i.e., first-order kinetic rate model). The resulting free energies also determine the optimal rate coefficients for transitions between the states or bins on the biased potentials. Unbiased rates can be estimated, e.g., by imposing a linear free energy condition in the likelihood maximization. The resulting "dynamic histogram analysis method extended to detailed balance" (DHAMed) builds on the DHAM method. It is also closely related to the transition-based reweighting analysis method (TRAM) and the discrete TRAM (dTRAM). However, in the continuous-time formulation of DHAMed, the detailed balance constraints are more easily accounted for, resulting in compact expressions amenable to efficient numerical treatment. DHAMed produces accurate free energies in cases where the common weighted-histogram analysis method (WHAM) for umbrella sampling fails because of slow dynamics within the windows. Even in the limit of completely uncorrelated data, where WHAM is optimal in the maximum-likelihood sense, DHAMed results are nearly indistinguishable. We illustrate DHAMed with applications to ion channel conduction, RNA duplex formation, α-helix folding, and rate calculations from accelerated molecular dynamics. DHAMed can also be used to construct Markov state models from biased or replica-exchange molecular dynamics simulations. By using binless WHAM formulated as a numerical minimization problem, the bias factors for the individual states can be determined efficiently in a preprocessing step and, if needed, optimized globally afterward.

The effect of genome-wide association scan quality control on imputation outcome for common variants.

PubMed

Southam, Lorraine; Panoutsopoulou, Kalliope; Rayner, N William; Chapman, Kay; Durrant, Caroline; Ferreira, Teresa; Arden, Nigel; Carr, Andrew; Deloukas, Panos; Doherty, Michael; Loughlin, John; McCaskie, Andrew; Ollier, William E R; Ralston, Stuart; Spector, Timothy D; Valdes, Ana M; Wallis, Gillian A; Wilkinson, J Mark; Marchini, Jonathan; Zeggini, Eleftheria

2011-05-01

Imputation is an extremely valuable tool in conducting and synthesising genome-wide association studies (GWASs). Directly typed SNP quality control (QC) is thought to affect imputation quality. It is, therefore, common practise to use quality-controlled (QCed) data as an input for imputing genotypes. This study aims to determine the effect of commonly applied QC steps on imputation outcomes. We performed several iterations of imputing SNPs across chromosome 22 in a dataset consisting of 3177 samples with Illumina 610 k (Illumina, San Diego, CA, USA) GWAS data, applying different QC steps each time. The imputed genotypes were compared with the directly typed genotypes. In addition, we investigated the correlation between alternatively QCed data. We also applied a series of post-imputation QC steps balancing elimination of poorly imputed SNPs and information loss. We found that the difference between the unQCed data and the fully QCed data on imputation outcome was minimal. Our study shows that imputation of common variants is generally very accurate and robust to GWAS QC, which is not a major factor affecting imputation outcome. A minority of common-frequency SNPs with particular properties cannot be accurately imputed regardless of QC stringency. These findings may not generalise to the imputation of low frequency and rare variants.

A Heckman selection model for the safety analysis of signalized intersections

PubMed Central

Wong, S. C.; Zhu, Feng; Pei, Xin; Huang, Helai; Liu, Youjun

2017-01-01

Purpose The objective of this paper is to provide a new method for estimating crash rate and severity simultaneously. Methods This study explores a Heckman selection model of the crash rate and severity simultaneously at different levels and a two-step procedure is used to investigate the crash rate and severity levels. The first step uses a probit regression model to determine the sample selection process, and the second step develops a multiple regression model to simultaneously evaluate the crash rate and severity for slight injury/kill or serious injury (KSI), respectively. The model uses 555 observations from 262 signalized intersections in the Hong Kong metropolitan area, integrated with information on the traffic flow, geometric road design, road environment, traffic control and any crashes that occurred during two years. Results The results of the proposed two-step Heckman selection model illustrate the necessity of different crash rates for different crash severity levels. Conclusions A comparison with the existing approaches suggests that the Heckman selection model offers an efficient and convenient alternative method for evaluating the safety performance at signalized intersections. PMID:28732050

Increased walking variability in elderly persons with congestive heart failure

NASA Technical Reports Server (NTRS)

Hausdorff, J. M.; Forman, D. E.; Ladin, Z.; Goldberger, A. L.; Rigney, D. R.; Wei, J. Y.

1994-01-01

OBJECTIVES: To determine the effects of congestive heart failure on a person's ability to walk at a steady pace while ambulating at a self-determined rate. SETTING: Beth Israel Hospital, Boston, a primary and tertiary teaching hospital, and a social activity center for elderly adults living in the community. PARTICIPANTS: Eleven elderly subjects (aged 70-93 years) with well compensated congestive heart failure (NY Heart Association class I or II), seven elderly subjects (aged 70-79 years) without congestive heart failure, and 10 healthy young adult subjects (aged 20-30 years). MEASUREMENTS: Subjects walked for 8 minutes on level ground at their own selected walking rate. Footswitches were used to measure the time between steps. Step rate (steps/minute) and step rate variability were calculated for the entire walking period, for 30 seconds during the first minute of the walk, for 30 seconds during the last minute of the walk, and for the 30-second period when each subject's step rate variability was minimal. Group means and 5% and 95% confidence intervals were computed. MAIN RESULTS: All measures of walking variability were significantly increased in the elderly subjects with congestive heart failure, intermediate in the elderly controls, and lowest in the young subjects. There was no overlap between the three groups using the minimal 30-second variability (elderly CHF vs elderly controls: P < 0.001, elderly controls vs young: P < 0.001), and no overlap between elderly subjects with and without congestive heart failure when using the overall variability. For all four measures, there was no overlap in any of the confidence intervals, and all group means were significantly different (P < 0.05).

Crystallization kinetics of the borax decahydrate

NASA Astrophysics Data System (ADS)

Ceyhan, A. A.; Sahin, Ö.; Bulutcu, A. N.

2007-03-01

The growth and dissolution rates of borax decahydrate have been measured as a function of supersaturation for various particle sizes at different temperature ranges of 13 and 50 °C in a laboratory-scale fluidized bed crystallizer. The values of mass transfer coefficient, K, reaction rate constant, kr and reaction rate order, r were determined. The relative importances of diffusion and integration resistance were described by new terms named integration and diffusion concentration fraction. It was found that the overall growth rate of borax decahydrate is mainly controlled by integration (reaction) steps. It was also estimated that the dissolution region of borax decahydrate, apart from other materials, is controlled by diffusion and surface reaction. Increasing the temperature and particle size cause an increase in the values of kinetic parameters ( Kg, kr and K). The activation energies of overall, reaction and mass transfer steps were determined as 18.07, 18.79 and 8.26 kJmol -1, respectively.

Power ultrasound irradiation during the alkaline etching process of the 2024 aluminum alloy

NASA Astrophysics Data System (ADS)

Moutarlier, V.; Viennet, R.; Rolet, J.; Gigandet, M. P.; Hihn, J. Y.

2015-11-01

Prior to any surface treatment on an aluminum alloy, a surface preparation is necessary. This commonly consists in performing an alkaline etching followed by acid deoxidizing. In this work, the use of power ultrasound irradiation during the etching step on the 2024 aluminum alloy was studied. The etching rate was estimated by weight loss, and the alkaline film formed during the etching step was characterized by glow discharge optical emission spectrometry (GDOES) and scanning electron microscope (SEM). The benefit of power ultrasound during the etching step was confirmed by pitting potential measurement in NaCl solution after a post-treatment (anodizing).

The Correlates of Body Composition with Heart Rate Recovery after Step Test: An Exploratory Study of Malaysian Adolescents

PubMed Central

Abu Hanifah, Redzal; Mohamed, Mohd. Nahar Azmi; Jaafar, Zulkarnain; Abdul Mohsein, Nabilla Al-Sadat; Jalaludin, Muhammad Yazid; Abdul Majid, Hazreen; Murray, Liam; Cantwell, Marie; Su, Tin Tin

2013-01-01

Background In adults, heart rate recovery is a predictor of mortality, while in adolescents it is associated with cardio-metabolic risk factors. The aim of this study was to examine the relationship between body composition measures and heart rate recovery (HRR) after step test in Malaysian secondary school students. Methods In the Malaysian Health and Adolescents Longitudinal Research Team (MyHEART) study, 1071 healthy secondary school students, aged 13 years old, participated in the step test. Parameters for body composition measures were body mass index z-score, body fat percentage, waist circumference, and waist height ratio. The step test was conducted by using a modified Harvard step test. Heart rate recovery of 1 minute (HRR1min) and heart rate recovery of 2 minutes (HRR2min) were calculated by the difference between the peak pulse rate during exercise and the resting pulse rate at 1 and 2 minutes, respectively. Analysis was done separately based on gender. Pearson correlation analysis was used to determine the association between the HRR parameters with body composition measures, while multiple regression analysis was used to determine which body composition measures was the strongest predictor for HRR. Results For both gender groups, all body composition measures were inversely correlated with HRR1min. In girls, all body composition measures were inversely correlated with HRR2min, while in boys all body composition measures, except BMI z-score, were associated with HRR2min. In multiple regression, only waist circumference was inversely associated with HRR2min (p=0.024) in boys, while in girls it was body fat percentage for HRR2min (p=0.008). Conclusion There was an inverse association between body composition measurements and HRR among apparently healthy adolescents. Therefore, it is important to identify cardio-metabolic risk factors in adolescent as an early prevention of consequent adulthood morbidity. This reiterates the importance of healthy living which should start from young. PMID:24349388

Practical, transparent prospective risk analysis for the clinical laboratory.

PubMed

Janssens, Pim Mw

2014-11-01

Prospective risk analysis (PRA) is an essential element in quality assurance for clinical laboratories. Practical approaches to conducting PRA in laboratories, however, are scarce. On the basis of the classical Failure Mode and Effect Analysis method, an approach to PRA was developed for application to key laboratory processes. First, the separate, major steps of the process under investigation are identified. Scores are then given for the Probability (P) and Consequence (C) of predefined types of failures and the chances of Detecting (D) these failures. Based on the P and C scores (on a 10-point scale), an overall Risk score (R) is calculated. The scores for each process were recorded in a matrix table. Based on predetermined criteria for R and D, it was determined whether a more detailed analysis was required for potential failures and, ultimately, where risk-reducing measures were necessary, if any. As an illustration, this paper presents the results of the application of PRA to our pre-analytical and analytical activities. The highest R scores were obtained in the stat processes, the most common failure type in the collective process steps was 'delayed processing or analysis', the failure type with the highest mean R score was 'inappropriate analysis' and the failure type most frequently rated as suboptimal was 'identification error'. The PRA designed is a useful semi-objective tool to identify process steps with potential failures rated as risky. Its systematic design and convenient output in matrix tables makes it easy to perform, practical and transparent. © The Author(s) 2014 Reprints and permissions: sagepub.co.uk/journalsPermissions.nav.

Individual, social and environmental determinants of sleep among women: Protocol for a systematic review and meta-analysis

USDA-ARS?s Scientific Manuscript database

Sleep is important to promote optimal health and avoid negative health outcomes. Short-duration and low-quality sleep may be more common and more detrimental among women compared with men. Identifying the determinants of behaviour is one of the first steps in designing effective interventions. To ou...

Compliance With WHO/UNICEF BFHI Standards in Croatia After Implementation of the BFHI.

PubMed

Zakarija-Grković, Irena; Boban, Marija; Janković, Sunčana; Ćuže, Anamarija; Burmaz, Tea

2018-02-01

The primary goal of the Baby-Friendly Hospital Initiative (BFHI) is to create conditions in maternity facilities that enable women to initiate and sustain the practice of breastfeeding exclusively. Research aim: This study aimed to determine hospital practices and breastfeeding rates before and after BFHI implementation and assess compliance with UNICEF/World Health Organization (WHO) standards for seven of the BFHI's Ten Steps to Successful Breastfeeding ( Ten Steps). Mothers of healthy, term infants ( N = 1,115) were recruited from the postnatal ward of the University Hospital of Split, Croatia, between February 2008 and July 2011 and followed for 12 months in a repeated-measures, prospective, longitudinal, three-group, nonequivalent, cohort study. Breastfeeding rates, hospital practices-including seven of the Ten Steps-and maternal sociodemographic data were collected. Parts of all seven Ten Steps that were assessed improved significantly post-BFHI. Step 3 ("antenatal education") showed the least improvement, whereas Step 7 ("rooming-in"; 2.6% pre-BFHI vs. 98.5% post-BFHI) and Step 9 ("no pacifiers/teats"; 21.8% pre-BFHI vs. 99.4% post-BFHI) showed the greatest improvement. Six months after Baby-Friendly designation, only Steps 7 and 9 were in full compliance with UNICEF/WHO standards. In-hospital, exclusive-breastfeeding rates rose markedly ( p < .001), but no change occurred in breastfeeding rates at 3, 6, or 12 months. Full implementation of the BFHI was associated with significant improvement in hospital practices and in-hospital, exclusive-breastfeeding rates, but it did not affect breastfeeding rates postdischarge, emphasizing the vital role of community support. Baby-Friendly Hospital Initiative standards declined rapidly post-hospital designation, indicating the need for regular monitoring and reassessment as well as ongoing, effective training for hospital staff.

Daily Steps in Midlife and Older Adults: Relationship with Demographic, Self-Rated Health, and Self-Reported Physical Activity

ERIC Educational Resources Information Center

Payn, Tamara; Pfeiffer, Karin A.; Hutto, Brent; Vena, John E.; LaMonte, Michael J.; Blair, Steven N.; Hooker, Steven P.

2008-01-01

The relationship between average daily step counts and age, body mass index (BMI), self-reported physical activity (PA) level, and perceived health was determined in 85 middle-aged and older adults who wore a pedometer for 7 consecutive days. Average daily steps were significantly (p less than 0.05) correlated with BMI (r = -0.26), age (r = -0.44)…

What makes a visualization memorable?

PubMed

Borkin, Michelle A; Vo, Azalea A; Bylinskii, Zoya; Isola, Phillip; Sunkavalli, Shashank; Oliva, Aude; Pfister, Hanspeter

2013-12-01

An ongoing debate in the Visualization community concerns the role that visualization types play in data understanding. In human cognition, understanding and memorability are intertwined. As a first step towards being able to ask questions about impact and effectiveness, here we ask: 'What makes a visualization memorable?' We ran the largest scale visualization study to date using 2,070 single-panel visualizations, categorized with visualization type (e.g., bar chart, line graph, etc.), collected from news media sites, government reports, scientific journals, and infographic sources. Each visualization was annotated with additional attributes, including ratings for data-ink ratios and visual densities. Using Amazon's Mechanical Turk, we collected memorability scores for hundreds of these visualizations, and discovered that observers are consistent in which visualizations they find memorable and forgettable. We find intuitive results (e.g., attributes like color and the inclusion of a human recognizable object enhance memorability) and less intuitive results (e.g., common graphs are less memorable than unique visualization types). Altogether our findings suggest that quantifying memorability is a general metric of the utility of information, an essential step towards determining how to design effective visualizations.

"What Is a Step?" Differences in How a Step Is Detected among Three Popular Activity Monitors That Have Impacted Physical Activity Research.

PubMed

John, Dinesh; Morton, Alvin; Arguello, Diego; Lyden, Kate; Bassett, David

2018-04-15

(1) Background: This study compared manually-counted treadmill walking steps from the hip-worn DigiwalkerSW200 and OmronHJ720ITC, and hip and wrist-worn ActiGraph GT3X+ and GT9X; determined brand-specific acceleration amplitude (g) and/or frequency (Hz) step-detection thresholds; and quantified key features of the acceleration signal during walking. (2) Methods: Twenty participants (Age: 26.7 ± 4.9 years) performed treadmill walking between 0.89-to-1.79 m/s (2-4 mph) while wearing a hip-worn DigiwalkerSW200, OmronHJ720ITC, GT3X+ and GT9X, and a wrist-worn GT3X+ and GT9X. A DigiwalkerSW200 and OmronHJ720ITC underwent shaker testing to determine device-specific frequency and amplitude step-detection thresholds. Simulated signal testing was used to determine thresholds for the ActiGraph step algorithm. Steps during human testing were compared using bias and confidence intervals. (3) Results: The OmronHJ720ITC was most accurate during treadmill walking. Hip and wrist-worn ActiGraph outputs were significantly different from the criterion. The DigiwalkerSW200 records steps for movements with a total acceleration of ≥1.21 g. The OmronHJ720ITC detects a step when movement has an acceleration ≥0.10 g with a dominant frequency of ≥1 Hz. The step-threshold for the ActiLife algorithm is variable based on signal frequency. Acceleration signals at the hip and wrist have distinctive patterns during treadmill walking. (4) Conclusions: Three common research-grade physical activity monitors employ different step-detection strategies, which causes variability in step output.

“What Is a Step?” Differences in How a Step Is Detected among Three Popular Activity Monitors That Have Impacted Physical Activity Research

PubMed Central

John, Dinesh; Arguello, Diego; Lyden, Kate; Bassett, David

2018-01-01

(1) Background: This study compared manually-counted treadmill walking steps from the hip-worn DigiwalkerSW200 and OmronHJ720ITC, and hip and wrist-worn ActiGraph GT3X+ and GT9X; determined brand-specific acceleration amplitude (g) and/or frequency (Hz) step-detection thresholds; and quantified key features of the acceleration signal during walking. (2) Methods: Twenty participants (Age: 26.7 ± 4.9 years) performed treadmill walking between 0.89-to-1.79 m/s (2–4 mph) while wearing a hip-worn DigiwalkerSW200, OmronHJ720ITC, GT3X+ and GT9X, and a wrist-worn GT3X+ and GT9X. A DigiwalkerSW200 and OmronHJ720ITC underwent shaker testing to determine device-specific frequency and amplitude step-detection thresholds. Simulated signal testing was used to determine thresholds for the ActiGraph step algorithm. Steps during human testing were compared using bias and confidence intervals. (3) Results: The OmronHJ720ITC was most accurate during treadmill walking. Hip and wrist-worn ActiGraph outputs were significantly different from the criterion. The DigiwalkerSW200 records steps for movements with a total acceleration of ≥1.21 g. The OmronHJ720ITC detects a step when movement has an acceleration ≥0.10 g with a dominant frequency of ≥1 Hz. The step-threshold for the ActiLife algorithm is variable based on signal frequency. Acceleration signals at the hip and wrist have distinctive patterns during treadmill walking. (4) Conclusions: Three common research-grade physical activity monitors employ different step-detection strategies, which causes variability in step output. PMID:29662048

Mechanism and the origins of stereospecificity in copper-catalyzed ring expansion of vinyl oxiranes: a traceless dual transition-metal-mediated process.

PubMed

Mustard, Thomas J L; Mack, Daniel J; Njardarson, Jon T; Cheong, Paul Ha-Yeon

2013-01-30

Density functional theory computations of the Cu-catalyzed ring expansion of vinyloxiranes is mediated by a traceless dual Cu(I)-catalyst mechanism. Overall, the reaction involves a monomeric Cu(I)-catalyst, but a single key step, the Cu migration, requires two Cu(I)-catalysts for the transformation. This dual-Cu step is found to be a true double Cu(I) transition state rather than a single Cu(I) transition state in the presence of an adventitious, spectator Cu(I). Both Cu(I) catalysts are involved in the bond forming and breaking process. The single Cu(I) transition state is not a stationary point on the potential energy surface. Interestingly, the reductive elimination is rate-determining for the major diastereomeric product, while the Cu(I) migration step is rate-determining for the minor. Thus, while the reaction requires dual Cu(I) activation to proceed, kinetically, the presence of the dual-Cu(I) step is untraceable. The diastereospecificity of this reaction is controlled by the Cu migration step. Suprafacial migration is favored over antarafacial migration due to the distorted Cu π-allyl in the latter.

Effects of age and step length on joint kinetics during stepping task.

PubMed

Bieryla, Kathleen A; Buffinton, Christine

2015-07-16

Following a balance perturbation, a stepping response is commonly used to regain support, and the distance of the recovery step can vary. To date, no other studies have examined joint kinetics in young and old adults during increasing step distances, when participants are required to bring their rear foot forward. Therefore, the purpose of this study was to examine age-related differences in joint kinetics with increasing step distance. Twenty young and 20 old adults completed the study. Participants completed a step starting from double support, at an initial distance equal to the individual's average step length. The distance was increased by 10% body height until an unsuccessful attempt. A one-way, repeated measures ANOVA was used to determine the effects of age on joint kinetics during the maximum step distance. A two-way, repeated measures, mixed model ANOVA was used to determine the effects of age, step distance, and their interaction on joint kinetics during the first three step distances for all participants. Young adults completed a significantly longer step than old adults. During the maximum step, in general, kinetic measures were greater in the young than in the old. As step distance increased, all but one kinetic measure increased for both young and old adults. This study has shown the ability to discriminate between young and old adults, and could potentially be used in the future to distinguish between fallers and non-fallers. Copyright © 2015 Elsevier Ltd. All rights reserved.

Rate-determining Step of Flap Endonuclease 1 (FEN1) Reflects a Kinetic Bias against Long Flaps and Trinucleotide Repeat Sequences.

PubMed

Tarantino, Mary E; Bilotti, Katharina; Huang, Ji; Delaney, Sarah

2015-08-21

Flap endonuclease 1 (FEN1) is a structure-specific nuclease responsible for removing 5'-flaps formed during Okazaki fragment maturation and long patch base excision repair. In this work, we use rapid quench flow techniques to examine the rates of 5'-flap removal on DNA substrates of varying length and sequence. Of particular interest are flaps containing trinucleotide repeats (TNR), which have been proposed to affect FEN1 activity and cause genetic instability. We report that FEN1 processes substrates containing flaps of 30 nucleotides or fewer at comparable single-turnover rates. However, for flaps longer than 30 nucleotides, FEN1 kinetically discriminates substrates based on flap length and flap sequence. In particular, FEN1 removes flaps containing TNR sequences at a rate slower than mixed sequence flaps of the same length. Furthermore, multiple-turnover kinetic analysis reveals that the rate-determining step of FEN1 switches as a function of flap length from product release to chemistry (or a step prior to chemistry). These results provide a kinetic perspective on the role of FEN1 in DNA replication and repair and contribute to our understanding of FEN1 in mediating genetic instability of TNR sequences. © 2015 by The American Society for Biochemistry and Molecular Biology, Inc.

Step edge sputtering yield at grazing incidence ion bombardment.

PubMed

Hansen, Henri; Polop, Celia; Michely, Thomas; Friedrich, Andreas; Urbassek, Herbert M

2004-06-18

The surface morphology of Pt(111) was investigated by scanning tunneling microscopy after 5 keV Ar+ ion bombardment at grazing incidence in dependence of the ion fluence and in the temperature range between 625 and 720 K. The average erosion rate was found to be strongly dependent on the ion fluence and the substrate temperature during bombardment. This dependence is traced back to the variation of step concentration with temperature and fluence. We develop a simple model allowing us to determine separately the constant sputtering yields for terraces and for impact area stripes in front of ascending steps. The experimentally determined yield of these stripes--the step-edge sputtering yield--is in excellent agreement with our molecular dynamics simulations performed for the experimental situation.

Oxygen Reduction Reaction on PtCo Nanocatalyst: (Bi)sulfate Anion Poisoning

NASA Astrophysics Data System (ADS)

Liu, Jie; Huang, Yan

2018-05-01

Pt alloy electrocatalysts are susceptible to anion adsorption in the working environment of fuel cells. In this work, the unavoidable bisulfate and sulfate ((bi)sulfate) poisoning of the oxygen reduction reaction (ORR) on a common PtCo nanocatalyst was studied by the rotating disk electrode (RDE) technique, for the first time to the best of our knowledge. The specific activity decreases linearly with the logarithm of (bi)sulfate concentration under various high potentials. This demonstrates that the (bi)sulfate adsorption does not affect the free energy of ORR activation at a given potential. Moreover, it is speculated that these two conditions, the adsorption of one O2 molecule onto two Pt sites and this adsorption as a rate-determining step of ORR reaction, are unlikely to exist simultaneously.

Erosion of stereochemical control with increasing nucleophilicity: O-glycosylation at the diffusion limit.

PubMed

Beaver, Matthew G; Woerpel, K A

2010-02-19

Nucleophilic substitution reactions of 2-deoxyglycosyl donors indicated that the reactivity of the oxygen nucleophile has a significant impact on stereoselectivity. Employing ethanol as the nucleophile resulted in a 1:1 (alpha:beta) ratio of diastereomers under S(N)1-like reaction conditions. Stereoselective formation of the 2-deoxy-alpha-O-glycoside was only observed when weaker nucleophiles, such as trifluoroethanol, were employed. The lack of stereoselectivity observed in reactions of common oxygen nucleophiles can be attributed to reaction rates of the stereochemistry-determining step that approach the diffusion limit. In this scenario, both faces of the prochiral oxocarbenium ion are subject to nucleophilic addition to afford a statistical mixture of diastereomeric products. Control experiments confirmed that all nucleophilic substitution reactions were performed under kinetic control.

Correlation between Gas Bubble Formation and Hydrogen Evolution Reaction Kinetics at Nanoelectrodes.

PubMed

Chen, Qianjin; Luo, Long

2018-04-17

We report the correlation between H 2 gas bubble formation potential and hydrogen evolution reaction (HER) activity for Au and Pt nanodisk electrodes (NEs). Microkinetic models were formulated to obtain the HER kinetic information for individual Au and Pt NEs. We found that the rate-determining steps for the HER at Au and Pt NEs were the Volmer step and the Heyrovsky step, respectively. More interestingly, the standard rate constant ( k 0 ) of the rate-determining step was found to vary over 2 orders of magnitude for the same type of NEs. The observed variations indicate the HER activity heterogeneity at the nanoscale. Furthermore, we discovered a linear relationship between bubble formation potential ( E bubble ) and log( k 0 ) with a slope of 125 mV/decade for both Au and Pt NEs. As log ( k 0 ) increases, E bubble shifts linearly to more positive potentials, meaning NEs with higher HER activities form H 2 bubbles at less negative potentials. Our theoretical model suggests that such linear relationship is caused by the similar critical bubble formation condition for Au and Pt NEs with varied sizes. Our results have potential implications for using gas bubble formation to evaluate the HER activity distribution of nanoparticles in an ensemble.

Inorganic Halogen Oxidizer Research.

DTIC Science & Technology

1978-01-25

depend on the rate of exchange. Finally, in our experiments we were dealing RI/RD78-125 B-4 -5- with polymeric solid AsF 5 or BF3 phases which on...well be a heterogeneous diffusion controlled reaction and step (5) might be the rate determining step in the above mechanism. It was shown that at...temperatures above -196*C, where a given NF+ salt is still stable in the absence of light, uv irradiation causes a rapid decay RI/RD78-125 B-5 -6- decay of

Rhenium/Oxygen Interactions at Elevated Temperatures

NASA Technical Reports Server (NTRS)

Jacobson, Nathan; Myers, Dwight; Zhu, Dong-Ming; Humphrey, Donald

2000-01-01

The oxidation of pure rhenium is examined from 600-1400 C in oxygen/argon mixtures. Linear weight loss kinetics are observed. Gas pressures, flow rates, and temperatures are methodically varied to determine the rate controlling steps. The reaction at 600 and 800 C appears to be controlled by a chemical reaction step at the surface; whereas the higher temperature reactions appear to be controlled by gas phase diffusion of oxygen to the rhenium surface. Attack of the rhenium appears to be along grain boundaries and crystallographic planes.

Cardiovascular responses to aerobic step dance sessions with and without appendicular overload.

PubMed

La Torre, A; Impellizzeri, F M; Rampinini, E; Casanova, F; Alberti, G; Marcora, S M

2005-09-01

Several studies showed that exercise intensity during aerobic step dance can be modified varying stepping rate, bench height and manipulating body mass using hand held or adding loads to the torso. The aim of this study was to determine the cardiovascular responses during aerobic step dance using an overload strategy not yet investigated: appendicular overload. Ten healthy and moderately trained women (mean+/-SD: age 27+/-3.4 years, height 167.8+/-4.6 cm, body mass 55.7+/-4.7 kg, body mass index 19.8+/-1.6, VO2max44.4+/-6.1 mLxkg-1xmin-1) performed an incremental treadmill test to determine VO2peak, the VO2-heart rate (HR) and rating of perceived exertion (RPE)-HR relationships. Within 1 week from the laboratory test, the subjects performed two identical aerobic step dance routines: one using a track suit with loads placed in pockets close to the legs and arms and another without overload. The appendicular overload (10% of body mass) significantly increased the exercise intensity from 84.5% to 89.8% of HRmax corresponding to 68.9% and 78.3% of VO2peak, respectively (P<0.01). Similarly, RPE increased from 12.1 to 15.7 (P<0.001). The estimated VO2 and the caloric expenditure rose from 30.3 to 34.7 mLxkg-1xmin-1 and from 251 to 288 kcal, respectively. This study shows that the use of appendicular overload significantly increases the energy cost of aerobic step session similarly to other overload strategies already reported in the literature.

Simplified Two-Time Step Method for Calculating Combustion Rates and Nitrogen Oxide Emissions for Hydrogen/Air and Hydorgen/Oxygen

NASA Technical Reports Server (NTRS)

Molnar, Melissa; Marek, C. John

2005-01-01

A simplified single rate expression for hydrogen combustion and nitrogen oxide production was developed. Detailed kinetics are predicted for the chemical kinetic times using the complete chemical mechanism over the entire operating space. These times are then correlated to the reactor conditions using an exponential fit. Simple first order reaction expressions are then used to find the conversion in the reactor. The method uses a two-time step kinetic scheme. The first time averaged step is used at the initial times with smaller water concentrations. This gives the average chemical kinetic time as a function of initial overall fuel air ratio, temperature, and pressure. The second instantaneous step is used at higher water concentrations (> 1 x 10(exp -20) moles/cc) in the mixture which gives the chemical kinetic time as a function of the instantaneous fuel and water mole concentrations, pressure and temperature (T4). The simple correlations are then compared to the turbulent mixing times to determine the limiting properties of the reaction. The NASA Glenn GLSENS kinetics code calculates the reaction rates and rate constants for each species in a kinetic scheme for finite kinetic rates. These reaction rates are used to calculate the necessary chemical kinetic times. This time is regressed over the complete initial conditions using the Excel regression routine. Chemical kinetic time equations for H2 and NOx are obtained for H2/air fuel and for the H2/O2. A similar correlation is also developed using data from NASA s Chemical Equilibrium Applications (CEA) code to determine the equilibrium temperature (T4) as a function of overall fuel/air ratio, pressure and initial temperature (T3). High values of the regression coefficient R2 are obtained.

Summary of Simplified Two Time Step Method for Calculating Combustion Rates and Nitrogen Oxide Emissions for Hydrogen/Air and Hydrogen/Oxygen

NASA Technical Reports Server (NTRS)

Marek, C. John; Molnar, Melissa

2005-01-01

A simplified single rate expression for hydrogen combustion and nitrogen oxide production was developed. Detailed kinetics are predicted for the chemical kinetic times using the complete chemical mechanism over the entire operating space. These times are then correlated to the reactor conditions using an exponential fit. Simple first order reaction expressions are then used to find the conversion in the reactor. The method uses a two time step kinetic scheme. The first time averaged step is used at the initial times with smaller water concentrations. This gives the average chemical kinetic time as a function of initial overall fuel air ratio, temperature, and pressure. The second instantaneous step is used at higher water concentrations (greater than l x 10(exp -20)) moles per cc) in the mixture which gives the chemical kinetic time as a function of the instantaneous fuel and water mole concentrations, pressure and temperature (T(sub 4)). The simple correlations are then compared to the turbulent mixing times to determine the limiting properties of the reaction. The NASA Glenn GLSENS kinetics code calculates the reaction rates and rate constants for each species in a kinetic scheme for finite kinetic rates. These reaction rates are used to calculate the necessary chemical kinetic times. This time is regressed over the complete initial conditions using the Excel regression routine. Chemical kinetic time equations for H2 and NOx are obtained for H2/Air fuel and for H2/O2. A similar correlation is also developed using data from NASA's Chemical Equilibrium Applications (CEA) code to determine the equilibrium temperature (T(sub 4)) as a function of overall fuel/air ratio, pressure and initial temperature (T(sub 3)). High values of the regression coefficient R squared are obtained.

Torque Generation Mechanism of F1-ATPase upon NTP Binding

PubMed Central

Arai, Hidenobu C.; Yukawa, Ayako; Iwatate, Ryu John; Kamiya, Mako; Watanabe, Rikiya; Urano, Yasuteru; Noji, Hiroyuki

2014-01-01

Molecular machines fueled by NTP play pivotal roles in a wide range of cellular activities. One common feature among NTP-driven molecular machines is that NTP binding is a major force-generating step among the elementary reaction steps comprising NTP hydrolysis. To understand the mechanism in detail,in this study, we conducted a single-molecule rotation assay of the ATP-driven rotary motor protein F1-ATPase using uridine triphosphate (UTP) and a base-free nucleotide (ribose triphosphate) to investigate the impact of a pyrimidine base or base depletion on kinetics and force generation. Although the binding rates of UTP and ribose triphosphate were 103 and 106 times, respectively, slower than that of ATP, they supported rotation, generating torque comparable to that generated by ATP. Affinity change of F1 to UTP coupled with rotation was determined, and the results again were comparable to those for ATP, suggesting that F1 exerts torque upon the affinity change to UTP via rotation similar to ATP-driven rotation. Thus, the adenine-ring significantly enhances the binding rate, although it is not directly involved in force generation. Taking into account the findings from another study on F1 with mutated phosphate-binding residues, it was proposed that progressive bond formation between the phosphate region and catalytic residues is responsible for the rotation-coupled change in affinity. PMID:24988350

Method and system for measuring multiphase flow using multiple pressure differentials

DOEpatents

Fincke, James R.

2001-01-01

An improved method and system for measuring a multiphase flow in a pressure flow meter. An extended throat venturi is used and pressure of the multiphase flow is measured at three or more positions in the venturi, which define two or more pressure differentials in the flow conduit. The differential pressures are then used to calculate the mass flow of the gas phase, the total mass flow, and the liquid phase. The method for determining the mass flow of the high void fraction fluid flow and the gas flow includes certain steps. The first step is calculating a gas density for the gas flow. The next two steps are finding a normalized gas mass flow rate through the venturi and computing a gas mass flow rate. The following step is estimating the gas velocity in the venturi tube throat. The next step is calculating the pressure drop experienced by the gas-phase due to work performed by the gas phase in accelerating the liquid phase between the upstream pressure measuring point and the pressure measuring point in the venturi throat. Another step is estimating the liquid velocity in the venturi throat using the calculated pressure drop experienced by the gas-phase due to work performed by the gas phase. Then the friction is computed between the liquid phase and a wall in the venturi tube. Finally, the total mass flow rate based on measured pressure in the venturi throat is calculated, and the mass flow rate of the liquid phase is calculated from the difference of the total mass flow rate and the gas mass flow rate.

Line width determination using a biomimetic fly eye vision system.

PubMed

Benson, John B; Wright, Cameron H G; Barrett, Steven F

2007-01-01

Developing a new vision system based on the vision of the common house fly, Musca domestica, has created many interesting design challenges. One of those problems is line width determination, which is the topic of this paper. It has been discovered that line width can be determined with a single sensor as long as either the sensor, or the object in question, has a constant, known velocity. This is an important first step for determining the width of any arbitrary object, with unknown velocity.

Cathodic Potential Dependence of Electrochemical Reduction of SiO2 Granules in Molten CaCl2

NASA Astrophysics Data System (ADS)

Yang, Xiao; Yasuda, Kouji; Nohira, Toshiyuki; Hagiwara, Rika; Homma, Takayuki

2016-09-01

As part of an ongoing fundamental study to develop a new process for producing solar-grade silicon, this paper examines the effects of cathodic potential on reduction kinetics, current efficiency, morphology, and purity of Si product during electrolysis of SiO2 granules in molten CaCl2 at 1123 K (850 °C). SiO2 granules were electrolyzed potentiostatically at different cathodic potentials (0.6, 0.8, 1.0, and 1.2 V vs Ca2+/Ca). The reduction kinetics was evaluated based on the growth of the reduced Si layer and the current behavior during electrolysis. The results suggest that a more negative cathodic potential is favorable for faster reduction. Current efficiencies in 60 minutes are greater than 65 pct at all the potentials examined. Si wires with sub-micron diameters are formed, and their morphologies show little dependence on the cathodic potential. The impurities in the Si product can be controlled at low level. The rate-determining step for the electrochemical reduction of SiO2 granules in molten CaCl2 changes with time. At the initial stage of electrolysis, the electron transfer is the rate-determining step. At the later stage, the diffusion of O2- ions is the rate-determining step. The major cause of the decrease in reduction rate with increasing electrolysis time is the potential drop from the current collector to the reaction front due to the increased contact resistance among the reduced Si particles.

Advanced oxidation of acridine orange by aqueous alkaline iodine.

PubMed

Azmat, Rafia; Qamar, Noshab; Naz, Raheela; Khursheed, Anum

2016-11-01

The advanced oxidation process is certainly used for the dye waste water treatment. In this continuation a new advanced oxidation via aqueous alkaline iodine was developed for the oxidation of acridine orange (AO) {3, 6 -bis (dimethylamino) acridine zinc chloride double salt}. Oxidation Kinetics of AO by alkaline solution of iodine was investigated spectrophotometrically at λ max 491 nm. The reaction was monitored at various operational parameters like several concentrations of dye and iodine, pH, salt electrolyte and temperature. The initial steps of oxidation kinetics followed fractional order reaction with respect to the dye while depend upon the incremental amount of iodine to certain extent whereas maximum oxidation of AO was achieved at high pH. Decline in the reaction rate in the presence of salt electrolyte suggested the presence of oppositely charged species in the rate determining step. Kinetic data revealed that the de-colorization mechanism involves triodate (I 3 - ) species, instead of hypoidate (OI - ) and hypiodous acid (HOI), in alkaline medium during the photo-excitation of hydrolyzed AO. Alleviated concentration of alkali result in decreasing of rate of reaction, clearly indicate that the iodine species are active oxidizing species instead of OH radical. Activation parameters at elevated temperatures were determined which revealed that highly solvated state of dye complex existed into solution. Reaction mixture was subjected to UV/Visible and GC mass spectrum analysis that proves the secondary consecutive reaction was operative in rate determining step and finally dye complex end into smaller fragments.

Time-dependence of the alpha to epsilon phase transformation in iron

DOE PAGES

Smith, R. F.; Eggert, J. H.; Swift, D. C.; ...

2013-12-11

Here, iron was ramp-compressed over timescales of 3 ≤ t(ns) ≤ 300 to study the time-dependence of the α→ε (bcc→hcp) phase transformation. Onset stresses (σ α→ε) for the transformation ~14.8-38.4 GPa were determined through laser and magnetic ramp-compression techniques where the transition strain-rate was varied between 10 6 ≤more » $$\\dot{μ}$$ α→ε(s ₋1) ≤ 5×10 8. We find σ α→ε= 10.8 + 0.55 ln($$\\dot{μ}$$ α→ε) for $$\\dot{μ}$$ α→ε < 10 6/s and σ α→ε= 1.15($$\\dot{μ}$$ α→ε) 0.18 for $$\\dot{μ}$$ α→ε > 10 6/s. This $$\\dot{μ}$$ response is quite similar to recent results on incipient plasticity in Fe suggesting that under high rate ramp compression the α→ε phase transition and plastic deformation occur through similar mechanisms, e.g., the rate limiting step for $$\\dot{μ}$$ > 10 6/s is due to phonon scattering from defects moving to relieve strain. We show that over-pressurization of equilibrium phase boundaries is a common feature exhibited under high strain-rate compression of many materials encompassing many orders of magnitude of strain-rate.« less

Trigger loop folding determines transcription rate of Escherichia coli’s RNA polymerase

DOE PAGES

Mejia, Yara X.; Nudler, Evgeny; Bustamante, Carlos

2014-12-31

Two components of the RNA polymerase (RNAP) catalytic center, the bridge helix and the trigger loop (TL), have been linked with changes in elongation rate and pausing. Here, single molecule experiments with the WT and two TL-tip mutants of the Escherichia coli enzyme reveal that tip mutations modulate RNAP’s pause-free velocity, identifying TL conformational changes as one of two rate-determining steps in elongation. Consistent with this observation, we find a direct correlation between helix propensity of the modified amino acid and pause-free velocity. Moreover, nucleotide analogs affect transcription rate, suggesting that their binding energy also influences TL folding. A kineticmore » model in which elongation occurs in two steps, TL folding on nucleoside triphosphate (NTP) binding followed by NTP incorporation/pyrophosphate release, quantitatively accounts for these results. The TL plays no role in pause recovery remaining unfolded during a pause. The model suggests a finely tuned mechanism that balances transcription speed and fidelity.« less

How to locate & hire clinical/biomedical engineers, supervisors, managers & biomedical equipment technicians.

PubMed

Pacela, A F; Brush, L C

1993-01-01

This article has described the process and the resources available for locating and hiring clinical/biomedical engineers, supervisors, managers, and biomedical equipment technicians. First, the employer must determine the qualifications for the position, including job titles, descriptions, pay scales, and certification requirements. Next, the employer must find qualified applicants. The most common way to do this is to use "outside" contacts, such as help-wanted advertising, specialized job placement agencies, schools and colleges, military resources, regional biomedical societies, and nationwide societies. An "inside" search involves limited internal advertising of the position and using personal referrals for candidates. Finally, the employer must screen the applicants. The position description is the obvious first step in this process, but there are other pre-screening techniques, such as employment testing. Interviewing is the most common way to hire for job positions, but the interviewer needs to know about the position and ask the right questions. Post-interview screening is a final step to help determine the best job-person match.

Pre-Steady State Studies of Phosphite Dehydrogenase Demonstrate that Hydride Transfer is Fully Rate-Limiting†

PubMed Central

Fogle, Emily J.

2008-01-01

Phosphite dehydrogenase (PTDH)1 is a unique NAD-dependent enzyme that catalyzes the oxidation of inorganic phosphite to phosphate. The enzyme has great potential for cofactor regeneration and mechanistic studies have provided some insight into the residues that are important for catalysis. In this investigation, pre-steady state studies were performed on the His6-tagged wild type (WT) enzyme, several active site mutants, a thermostable mutant (12X-PTDH), and a thermostable mutant with dual cofactor specificity (NADP-12X-PTDH). Stopped-flow kinetic experiments indicate that slow steps after hydride transfer do not significantly limit the rate of reaction for WT, the active site mutants, or the thermostable mutant. Pre-steady state kinetic isotope effects (KIEs) and single turn-over experiments further confirm that slow steps after the chemical step do not significantly limit the rate of reaction for any of these proteins. Collectively, these results suggest that the hydride transfer step is fully rate determining in PTDH and that the observed KIE on kcat is the intrinsic effect in WT PTDH and the mutants examined. In contrast, a slow step after catalysis may partially limit the rate of phosphite oxidation by NADP-12X-PTDH with NADP as cofactor. Finally, site directed mutagenesis of Asp79 indicates that this residue is important in orienting Arg237 for proper interaction with phosphite. PMID:17949110

Design of a catalyst through Fe doping of the boron cage B10H14 for CO2 hydrogenation and investigation of the catalytic character of iron hydride (Fe-H).

PubMed

Qian, Lei; Ma, Kai-Yang; Zhou, Zhong-Jun; Ma, Fang

2017-12-13

The innovative catalyst Fe@B 10 H 14 is designed through Fe doping of the boron cage B 10 H 14 and is employed to catalyze CO 2 hydrogenation using a quantum mechanical method. First, the structure of the Fe@B 10 H 14 complex is characterized through calculated 11 B NMR chemical shifts and Raman spectra, and the interactions between Fe and the four H atoms of the opening in the cage are analyzed, which show that various iron hydride (Fe-H) characteristics exist. Subsequently, the potential of Fe@B 10 H 14 as a catalyst for the hydrogenative reduction of CO 2 in the gas phase is computationally evaluated. We find that an equivalent of Fe@B 10 H 14 can consecutively reduce double CO 2 to obtain the double product HCOOH through a two-step reduction, and Fe@B 10 H 12 and Fe@B 10 H 10 are successively obtained. The Fe presents single-atom character in the reduction of CO 2 , which is different from the common iron(ii) catalyzed CO 2 reduction. The calculated total free energy barrier of the first CO 2 reduction is only 8.79 kcal mol -1 , and that of the second CO 2 reduction is 25.71 kcal mol -1 . Every reduction reaction undergoes two key transition states TSC-H and TSO-H. Moreover, the transition state of the C-H bond formation TSC-H is the rate-determining step, where the interaction between π C[double bond, length as m-dash]O * and the weak σ Fe-H bond plays an important role. Furthermore, the hydrogenations of Fe@B 10 H 12 and Fe@B 10 H 10 are investigated, which aim at determining the ability of Fe-H circulation in the Fe doped decaborane complex. We find that the hydrogenation of Fe@B 10 H 10 undergoes a one-step H 2 -adsorbed transition state TSH-adsorb with an energy barrier of 6.42 kcal mol -1 from Fe@B 10 H 12 . Comparing with the hydrogenation of Fe@B 10 H 10 , it is slightly more difficult for the hydrogenation of Fe@B 10 H 12 , where the rate-determining step is the H 2 -cleaved transition state TS2H-H with an energy barrier of 17.38 kcal mol -1 .

Drilling of CFRP and GFRP composite laminates using one shot solid carbide step drill K44

NASA Astrophysics Data System (ADS)

Nagaraja, R.; Rangaswamy, T.

2018-04-01

Drilling is a very common machining operation to install fasteners for assembly of laminates Drilling of Carbon Fiber Reinforced Plastic (CFRP) and Glass Fiber Reinforced Plastic (GFRP) composite laminate materials are different from that of convention materials that causes excessive tool wear and edge delamination. This paper reports on the tool geometry, cutting speed and feed rate. In this work two composite materials CFRP-G926 and Glass-7781 composite materials of varying thickness are drilled to investigate the effect of feed rate, and cutting speed. The study mainly focused on drilling laminates specimen of varying thickness 9 mm, 9.6 mm and 12 mm by using a single shot solid carbide step drill K44. The drilling is performed from lower to higher feed rate and cutting speed to investigate the hole quality, bottom top edge delamination, fiber breakages and local cracks. The work performed shows that a proper combination of tool geometry, cutting speed and feed rate can help to reduce the occurrence of delamination.

10 CFR 431.264 - Uniform test method for the measurement of flow rate for commercial prerinse spray valves.

Code of Federal Regulations, 2010 CFR

2010-01-01

..., the water consumption flow rate of commercial prerinse spray valves. (b) Testing and Calculations. The test procedure to determine the water consumption flow rate for prerinse spray valves, expressed in... the previous step. Round the final water consumption value to one decimal place as follows: (1) A...

2-Step scalar deadzone quantization for bitplane image coding.

PubMed

Auli-Llinas, Francesc

2013-12-01

Modern lossy image coding systems generate a quality progressive codestream that, truncated at increasing rates, produces an image with decreasing distortion. Quality progressivity is commonly provided by an embedded quantizer that employs uniform scalar deadzone quantization (USDQ) together with a bitplane coding strategy. This paper introduces a 2-step scalar deadzone quantization (2SDQ) scheme that achieves same coding performance as that of USDQ while reducing the coding passes and the emitted symbols of the bitplane coding engine. This serves to reduce the computational costs of the codec and/or to code high dynamic range images. The main insights behind 2SDQ are the use of two quantization step sizes that approximate wavelet coefficients with more or less precision depending on their density, and a rate-distortion optimization technique that adjusts the distortion decreases produced when coding 2SDQ indexes. The integration of 2SDQ in current codecs is straightforward. The applicability and efficiency of 2SDQ are demonstrated within the framework of JPEG2000.

The learning curve: Implications of a quantitative analysis

PubMed Central

Gallistel, Charles R.; Fairhurst, Stephen; Balsam, Peter

2004-01-01

The negatively accelerated, gradually increasing learning curve is an artifact of group averaging in several commonly used basic learning paradigms (pigeon autoshaping, delay- and trace-eye-blink conditioning in the rabbit and rat, autoshaped hopper entry in the rat, plus maze performance in the rat, and water maze performance in the mouse). The learning curves for individual subjects show an abrupt, often step-like increase from the untrained level of responding to the level seen in the well trained subject. The rise is at least as abrupt as that commonly seen in psychometric functions in stimulus detection experiments. It may indicate that the appearance of conditioned behavior is mediated by an evidence-based decision process, as in stimulus detection experiments. If the appearance of conditioned behavior is taken instead to reflect the increase in an underlying associative strength, then a negligible portion of the function relating associative strength to amount of experience is behaviorally visible. Consequently, rate of learning cannot be estimated from the group-average curve; the best measure is latency to the onset of responding, determined for each subject individually. PMID:15331782

The learning curve: implications of a quantitative analysis.

PubMed

Gallistel, Charles R; Fairhurst, Stephen; Balsam, Peter

2004-09-07

The negatively accelerated, gradually increasing learning curve is an artifact of group averaging in several commonly used basic learning paradigms (pigeon autoshaping, delay- and trace-eye-blink conditioning in the rabbit and rat, autoshaped hopper entry in the rat, plus maze performance in the rat, and water maze performance in the mouse). The learning curves for individual subjects show an abrupt, often step-like increase from the untrained level of responding to the level seen in the well trained subject. The rise is at least as abrupt as that commonly seen in psychometric functions in stimulus detection experiments. It may indicate that the appearance of conditioned behavior is mediated by an evidence-based decision process, as in stimulus detection experiments. If the appearance of conditioned behavior is taken instead to reflect the increase in an underlying associative strength, then a negligible portion of the function relating associative strength to amount of experience is behaviorally visible. Consequently, rate of learning cannot be estimated from the group-average curve; the best measure is latency to the onset of responding, determined for each subject individually.

QM/MM simulations identify the determinants of catalytic activity differences between type II dehydroquinase enzymes.

PubMed

Lence, Emilio; van der Kamp, Marc W; González-Bello, Concepción; Mulholland, Adrian J

2018-05-16

Type II dehydroquinase enzymes (DHQ2), recognized targets for antibiotic drug discovery, show significantly different activities dependent on the species: DHQ2 from Mycobacterium tuberculosis (MtDHQ2) and Helicobacter pylori (HpDHQ2) show a 50-fold difference in catalytic efficiency. Revealing the determinants of this activity difference is important for our understanding of biological catalysis and further offers the potential to contribute to tailoring specificity in drug design. Molecular dynamics simulations using a quantum mechanics/molecular mechanics potential, with correlated ab initio single point corrections, identify and quantify the subtle determinants of the experimentally observed difference in efficiency. The rate-determining step involves the formation of an enolate intermediate: more efficient stabilization of the enolate and transition state of the key step in MtDHQ2, mainly by the essential residues Tyr24 and Arg19, makes it more efficient than HpDHQ2. Further, a water molecule, which is absent in MtDHQ2 but involved in generation of the catalytic Tyr22 tyrosinate in HpDHQ2, was found to destabilize both the transition state and the enolate intermediate. The quantification of the contribution of key residues and water molecules in the rate-determining step of the mechanism also leads to improved understanding of higher potencies and specificity of known inhibitors, which should aid ongoing inhibitor design.

A New Microscopic Model of the Rate- and State- Friction Evolution

NASA Astrophysics Data System (ADS)

Li, T.; Rubin, A. M.

2016-12-01

The Slip (Ruina) law and the Aging (Dieterich) law are the two most common descriptions of the evolution of "state" in rate- and state-dependent friction, behind which are the ideas of slip-dependent and time-dependent fault healing, respectively. Since the mid-1990's, friction experiments have been interpreted as demonstrating that fault healing in rock is primarily time-dependent, and that frictional strength is proportional to contact area (Dieterich and Kilgore, 1994; Beeler et al., 1994). However, a recent re-examination of the data of Beeler et al. (1994) suggests that the evidence for time-dependent healing is equivocal, while large step velocity decreases provide unequivocal evidence of slip-dependent healing (Bhattacharya et al., AGU 2016). Nonetheless, unlike the Aging law, for which see-through experiments showing growing contacts could serve as a physical model, there has been no corresponding physical picture for the Slip law. In this study, we develop a new microscopic model of friction in which each asperity has a heterogeneous strength, with individual portions "remembering" the velocity at which they came into existence. Such a scenario could arise via processes that are more efficient at the margin of a contact than within the interior (e.g., chemical diffusion). A numerical kernel for friction evolution is developed for arbitrary slip histories and an exponential distribution of asperity sizes. For velocity steps we derive an analytical expression that is essentially the Slip law. Numerical inversions show that this model performs as well as the Slip law when fitting velocity step data, but (unfortunately) without improving much the fit to slide-hold-slide data. Because "state" as defined by the Aging law has traditionally been interpreted as contact age, we also use our model to determine whether the "Aging law" actually tracks contact age for general velocity histories. As is traditional, we assume that strength increases logarithmically with age. For reasonable definitions of "age" we obtain results significantly different from the Aging law for velocity step increases. Interestingly, we can obtain an analytical solution for velocity steps that is very close to the Aging law if we adopt a definition of age that we consider to be non-physical.

Development of a kinetic model of hydrogen absorption and desorption in magnesium and analysis of the rate-determining step

NASA Astrophysics Data System (ADS)

Kitagawa, Yuta; Tanabe, Katsuaki

2018-05-01

Mg is promising as a new light-weight and low-cost hydrogen-storage material. We construct a numerical model to represent the hydrogen dynamics on Mg, comprising dissociative adsorption, desorption, bulk diffusion, and chemical reaction. Our calculation shows a good agreement with experimental data for hydrogen absorption and desorption on Mg. Our model clarifies the evolution of the rate-determining processes as absorption and desorption proceed. Furthermore, we investigate the optimal condition and materials design for efficient hydrogen storage in Mg. By properly understanding the rate-determining processes using our model, one can determine the design principle for high-performance hydrogen-storage systems.

Effect of strain on actomyosin kinetics in isometric muscle fibers.

PubMed

Siththanandan, V B; Donnelly, J L; Ferenczi, M A

2006-05-15

Investigations were conducted into the biochemical and mechanical states of cross-bridges during isometric muscle contraction. Rapid length steps (3 or 6 nm hs(-1)) were applied to rabbit psoas fibers, permeabilized and isometric, at either 12 degrees C or 20 degrees C. Fibers were activated by photolysis of P(3)-1-(2-nitrophenyl)-ethyl ester of ATP infused into rigor fibers at saturating Ca(2+). Sarcomere length, tension, and phosphate release were recorded-the latter using the MDCC-PBP fluorescent probe. A reduction in strain, induced by a rapid release step, produced a short-lived acceleration of phosphate release. Rates of the phosphate transient and that of phases 3 and 4 of tension recovery were unaffected by step size but were elevated at higher temperatures. In contrast the amplitude of the phosphate transient was smaller at 20 degrees C than 12 degrees C. The presence of 0.5 or 1.0 mM added ADP during a release step reduced both the rate of tension recovery and the poststep isometric tension. A kinetic scheme is presented to simulate the observed data and to precisely determine the rate constants for the elementary steps of the ATPase cycle.

Kinetics of protein–ligand unbinding: Predicting pathways, rates, and rate-limiting steps

PubMed Central

Tiwary, Pratyush; Limongelli, Vittorio; Salvalaglio, Matteo; Parrinello, Michele

2015-01-01

The ability to predict the mechanisms and the associated rate constants of protein–ligand unbinding is of great practical importance in drug design. In this work we demonstrate how a recently introduced metadynamics-based approach allows exploration of the unbinding pathways, estimation of the rates, and determination of the rate-limiting steps in the paradigmatic case of the trypsin–benzamidine system. Protein, ligand, and solvent are described with full atomic resolution. Using metadynamics, multiple unbinding trajectories that start with the ligand in the crystallographic binding pose and end with the ligand in the fully solvated state are generated. The unbinding rate koff is computed from the mean residence time of the ligand. Using our previously computed binding affinity we also obtain the binding rate kon. Both rates are in agreement with reported experimental values. We uncover the complex pathways of unbinding trajectories and describe the critical rate-limiting steps with unprecedented detail. Our findings illuminate the role played by the coupling between subtle protein backbone fluctuations and the solvation by water molecules that enter the binding pocket and assist in the breaking of the shielded hydrogen bonds. We expect our approach to be useful in calculating rates for general protein–ligand systems and a valid support for drug design. PMID:25605901

Interaction of abiotic and microbial processes in hexachloroethane reduction in groundwater

USGS Publications Warehouse

Roberts, A. Lynn; Gschwend, Philip M.

1994-01-01

In order to gain insight into mechanisms of hexachloroethane reduction, hexa- and pentachloroethane transformation rates were measured in anaerobic groundwater samples. For samples spiked with pentachloroethane, disappearance of pentachloroethane was accompanied by tetrachloroethylene production. Transformation rates were similar in unpoisoned and in HgCl2-poisoned samples, and rates were within ±20% of predictions based on measured pH and second-order dehydrochlorination rate constants determined in clean laboratory systems, indicating that the fate of pentachloroethane in this system is dominated by abiotic reactions. No hexachloroethane transformation was observed in HgCl2-poisoned samples, whereas in unpoisoned samples, hexachloroethane disappearance was accompanied by production of tetrachloroethylene as well as traces of pentachloroethane. Although only minor amounts of pentachloroethane accumulated, as much as 30% of the hexachloroethane transformation pathway proceeds via a pentachloroethane intermediate. This suggests that the microbial reduction of hexachloroethane proceeds at least in part through a free-radical mechanism. To the extent that hexachloroethane reduction to tetrachloroethylene occurs through a pentachloroethane intermediate, the first step in the sequence, the microbially-mediated step, is the slow step; the subsequent abiotic dehydrohalogenation step occurs much more rapidly.

Experimental study of combustion in a turbulent free shear layer formed at a rearward facing step

NASA Technical Reports Server (NTRS)

Pitz, R. W.; Daily, J. W.

1981-01-01

A premixed propane-air flame is stabilized in a turbulent free shear layer formed at a rearward facing step. The mean and rms averages of the turbulent velocity flow field are determined by LDV for both reacting (equivalence ratio 0.57) and nonreacting flows (Reynolds number 15,000-37,000 based on step height). The effect of combustion is to shift the layer toward the recirculation zone and reduce the flame spread. For reacting flow, the growth rate is unchanged except very near the step. The probability density function of the velocity is bimodial near the origin of the reacting layer and single-peaked but often skewed elsewhere. Large-scale structures dominate the reacting shear layer. Measurements of their passing frequency from LDV are consistent with high-speed Schlieren movies of the reacting layer and indicate that the coalescence rate of the eddies in the shear layer is reduced by combustion.

Beyond Composite Scores and Cronbach's Alpha: Advancing Methodological Rigor in Recreation Research

ERIC Educational Resources Information Center

Gagnon, Ryan J.; Stone, Garrett A.; Garst, Barry A.

2017-01-01

Critically examining common statistical approaches and their strengths and weaknesses is an important step in advancing recreation and leisure sciences. To continue this critical examination and to inform methodological decision making, this study compared three approaches to determine how alternative approaches may result in contradictory…

Evaluation of an early step-down strategy from intravenous anidulafungin to oral azole therapy for the treatment of candidemia and other forms of invasive candidiasis: results from an open-label trial.

PubMed

Vazquez, Jose; Reboli, Annette C; Pappas, Peter G; Patterson, Thomas F; Reinhardt, John; Chin-Hong, Peter; Tobin, Ellis; Kett, Daniel H; Biswas, Pinaki; Swanson, Robert

2014-02-21

Hospitalized patients are at increased risk for candidemia and invasive candidiasis (C/IC). Improved therapeutic regimens with enhanced clinical and pharmacoeconomic outcomes utilizing existing antifungal agents are still needed. An open-label, non-comparative study evaluated an intravenous (i.v.) to oral step-down strategy. Patients with C/IC were treated with i.v. anidulafungin and after 5 days of i.v. therapy had the option to step-down to oral azole therapy (fluconazole or voriconazole) if they met prespecified criteria. The primary endpoint was the global response rate (clinical + microbiological) at end of treatment (EOT) in the modified intent-to-treat (MITT) population (at least one dose of anidulafungin plus positive Candida within 96 hours of study entry). Secondary endpoints included efficacy at other time points and in predefined patient subpopulations. Patients who stepped down early (≤ 7 days' anidulafungin) were identified as the "early switch" subpopulation. In total, 282 patients were enrolled, of whom 250 were included in the MITT population. The MITT global response rate at EOT was 83.7% (95% confidence interval, 78.7-88.8). Global response rates at all time points were generally similar in the early switch subpopulation compared with the MITT population. Global response rates were also similar across multiple Candida species, including C. albicans, C. glabrata, and C. parapsilosis. The most common treatment-related adverse events were nausea and vomiting (four patients each). A short course of i.v. anidulafungin, followed by early step-down to oral azole therapy, is an effective and well-tolerated approach for the treatment of C/IC. ClinicalTrials.gov: NCT00496197.

Evaluation of an early step-down strategy from intravenous anidulafungin to oral azole therapy for the treatment of candidemia and other forms of invasive candidiasis: results from an open-label trial

PubMed Central

2014-01-01

Background Hospitalized patients are at increased risk for candidemia and invasive candidiasis (C/IC). Improved therapeutic regimens with enhanced clinical and pharmacoeconomic outcomes utilizing existing antifungal agents are still needed. Methods An open-label, non-comparative study evaluated an intravenous (IV) to oral step-down strategy. Patients with C/IC were treated with IV anidulafungin and after 5 days of IV therapy had the option to step-down to oral azole therapy (fluconazole or voriconazole) if they met prespecified criteria. The primary endpoint was the global response rate (clinical + microbiological) at end of treatment (EOT) in the modified intent-to-treat (MITT) population (at least one dose of anidulafungin plus positive Candida within 96 hours of study entry). Secondary endpoints included efficacy at other time points and in predefined patient subpopulations. Patients who stepped down early (≤ 7 days’ anidulafungin) were identified as the "early switch" subpopulation. Results In total, 282 patients were enrolled, of whom 250 were included in the MITT population. The MITT global response rate at EOT was 83.7% (95% confidence interval, 78.7–88.8). Global response rates at all time points were generally similar in the early switch subpopulation compared with the MITT population. Global response rates were also similar across multiple Candida species, including C. albicans, C. glabrata, and C. parapsilosis. The most common treatment-related adverse events were nausea and vomiting (four patients each). Conclusions A short course of IV anidulafungin, followed by early step-down to oral azole therapy, is an effective and well-tolerated approach for the treatment of C/IC. Trial registration ClinicalTrials.gov: NCT00496197 PMID:24559321

Back-exchange: a novel approach to quantifying oxygen diffusion and surface exchange in ambient atmospheres.

PubMed

Cooper, Samuel J; Niania, Mathew; Hoffmann, Franca; Kilner, John A

2017-05-17

A novel two-step Isotopic Exchange (IE) technique has been developed to investigate the influence of oxygen containing components of ambient air (such as H 2 O and CO 2 ) on the effective surface exchange coefficient (k*) of a common mixed ionic electronic conductor material. The two step 'back-exchange' technique was used to introduce a tracer diffusion profile, which was subsequently measured using Time-of-Flight Secondary Ion Mass Spectrometry (ToF-SIMS). The isotopic fraction of oxygen in a dense sample as a function of distance from the surface, before and after the second exchange step, could then be used to determine the surface exchange coefficient in each atmosphere. A new analytical solution was found to the diffusion equation in a semi-infinite domain with a variable surface exchange boundary, for the special case where D* and k* are constant for all exchange steps. This solution validated the results of a numerical, Crank-Nicolson type finite-difference simulation, which was used to extract the parameters from the experimental data. When modelling electrodes, D* and k* are important input parameters, which significantly impact performance. In this study La 0.6 Sr 0.4 Co 0.2 Fe 0.8 O 3-δ (LSCF6428) was investigated and it was found that the rate of exchange was increased by around 250% in ambient air compared to high purity oxygen at the same pO 2 . The three experiments performed in this study were used to validate the back-exchange approach and show its utility.

An investigation using atomic force microscopy nanoindentation of dental enamel demineralization as a function of undissociated acid concentration and differential buffer capacity

NASA Astrophysics Data System (ADS)

Barbour, Michele E.; Shellis, R. Peter

2007-02-01

Acidic drinks and foodstuffs can demineralize dental hard tissues, leading to a pathological condition known as dental erosion, which is of increasing clinical concern. The first step in enamel dissolution is a demineralization of the outer few micrometres of tissue, which results in a softening of the structure. The primary determinant of dissolution rate is pH, but the concentration of undissociated acid, which is related to buffer capacity, also appears to be important. In this study, atomic force microscopy nanoindentation was used to measure the first initial demineralization (softening) induced within 1 min by exposure to solutions with a range of undissociated acid concentration and natural pH of 3.3 or with an undissociated acid concentration of 10 mmol l-1 and pH adjusted to 3.3. The results indicate that differential buffering capacity is a better determinant of softening than undissociated acid concentration. Under the conditions of these experiments, a buffer capacity of >3 mmol l-1 pH-1 does not have any further effect on dissolution rate. These results imply that differential buffering capacity should be used for preference over undissociated acid concentration or titratable acidity, which are more commonly employed in the literature.

A comparison of the flow of iodine 125 through three different intestinal anastomoses: standard, Gambee, and stapler

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

Wheeless, C.R. Jr.; Smith, J.J.

1983-10-01

Angiogenesis determines blood supply, and it is postulated that after surgery, the healing of a wound is directly related to the blood supplied to the surrounding tissues. As a first step in evaluating the process of flow through different surgical anastomoses, the flow rate of /sup 125/I through three different types of anastomoses in the intestines of dogs was determined. When the results were compared, the flow rate through the stapler anastomosis was significantly higher than the flow rate through the standard and Gambee anastomoses.

Development, reliability, and validity testing of Toddler NutriSTEP: a nutrition risk screening questionnaire for children 18-35 months of age.

PubMed

Randall Simpson, Janis; Gumbley, Jillian; Whyte, Kylie; Lac, Jane; Morra, Crystal; Rysdale, Lee; Turfryer, Mary; McGibbon, Kim; Beyers, Joanne; Keller, Heather

2015-09-01

Nutrition is vital for optimal growth and development of young children. Nutrition risk screening can facilitate early intervention when followed by nutritional assessment and treatment. NutriSTEP (Nutrition Screening Tool for Every Preschooler) is a valid and reliable nutrition risk screening questionnaire for preschoolers (aged 3-5 years). A need was identified for a similar questionnaire for toddlers (aged 18-35 months). The purpose was to develop a reliable and valid Toddler NutriSTEP. Toddler NutriSTEP was developed in 4 phases. Content and face validity were determined with a literature review, parent focus groups (n = 6; 48 participants), and experts (n = 13) (phase A). A draft questionnaire was refined with key intercept interviews of 107 parents/caregivers (phase B). Test-retest reliability (phase C), based on intra-class correlations (ICC), Kappa (κ) statistics, and Wilcoxon tests was assessed with 133 parents/caregivers. Criterion validity (phase D) was assessed using Receiver Operating Characteristic (ROC) curves by comparing scores on the Toddler NutriSTEP to a comprehensive nutritional assessment of 200 toddlers with a registered dietitian (RD). The Toddler NutriSTEP was reliable between 2 administrations (ICC = 0.951, F = 20.53, p < 0.001); most questions had moderate (κ ≥ 0.6) or excellent (κ ≥ 0.8) agreement. Scores on the RD nutrition risk rating and the Toddler NutriSTEP were correlated (r = 0.67, p < 0.000). The area under the ROC curve for moderate and high RD risk ratings were 84.6% and 82.7%, respectively. Cut-points of ≥21 (sensitivity 86%; specificity 61%) (moderate risk) and ≥26 (sensitivity 95%; specificity 63%) (high risk) were determined. The Toddler NutriSTEP questionnaire is both reliable and valid for screening for nutritional risk in toddlers.

Remifentanil for the insertion and removal of long-term central venous access during monitored anesthesia care.

PubMed

Burlacu, Crina L; McKeating, Kevin; McShane, Alan J

2011-06-01

To determine the analgesic efficacy of three different rates of remifentanil infusion in patients undergoing insertion or removal of long-term central venous access devices during monitored anesthesia care and local anesthetic field infiltration. Double-blinded, randomized, controlled study. Operating theatre of an University hospital. 44 unpremedicated, ASA physical status 1 and 2 patients, aged 18-65 years, undergoing insertion or removal of a Port-a-Cath or Hickman catheter. Patients sedated with a propofol target-controlled infusion were randomly allocated to three groups: Group R25 (n = 14), Group R50 (n = 15), and Group R75 (n = 15), to receive remifentanil 0.025, 0.05, and 0.075 μg/kg/min, respectively. Rescue remifentanil 0.5 μg/kg was administered for pain scores > 3. The remifentanil infusion rate was maintained constant unless respiratory and/or cardiovascular unwanted events occurred, whereupon the rate was adjusted in 0.01 μg/kg/min decrements as necessary. Pain scores (primary outcome), sedation, and movement scores (secondary outcomes) were assessed during local anesthetic infiltration of the anterior chest wall and 5 other procedural steps. All infusion rates had equal analgesic efficacy, as shown by comparable pain scores, number of rescue boluses, and number of patients requiring rescue analgesia. Excessive sedation was associated with the highest remifentanil rate such that Group R75 patients were significantly more sedated than Groups R25 or R50 at selective procedural steps (P < 0.05). More Group R75 patients (6/15) required remifentanil rate reduction than did patients from Group R50 (1/15) or Group R25 (0/14), P < 0.01, most commonly because of respiratory depression. For the insertion or removal of long-term central venous access devices, all three remifentanil infusion rates proved to be equally analgesic-efficient. However, the excessive sedation and tendency to respiratory and cardiovascular events associated with the highest remifentanil infusion rate renders such a rate less desirable for this purpose. Copyright © 2011 Elsevier Inc. All rights reserved.

Mild Aromatic Palladium-Catalyzed Protodecarboxylation: Kinetic Assessment of the Decarboxylative Palladation and the Protodepalladation Steps

PubMed Central

Dickstein, Joshua S.; Curto, John M.; Gutierrez, Osvaldo; Mulrooney, Carol A.; Kozlowski, Marisa C.

2013-01-01

Mechanism studies of a mild palladium catalyzed decarboxylation of aromatic carboxylic acids are described. In particular, reaction orders and activation parameters for the two stages of the transformation were determined. These studies guided development of a catalytic system capable of turnover. Further evidence reinforces that the second stage, protonation of the aryl palladium intermediate, is the rate-determining step of the reaction. The first step, decarboxylative palladation is proposed to occur through an intramolecular electrophilic palladation pathway, which is supported by computational and mechansim studies. In contrast to the reverse reaction (C-H insertion), the data support an electrophilic aromatic substitution mechanism involving a stepwise intramolecular protonation sequence for the protodepalladation portion of the reaction. PMID:23590518

Common cold outbreaks: A network theory approach

NASA Astrophysics Data System (ADS)

Vishkaie, Faranak Rajabi; Bakouie, Fatemeh; Gharibzadeh, Shahriar

2014-11-01

In this study, at first we evaluated the network structure in social encounters by which respiratory diseases can spread. We considered common-cold and recorded a sample of human population and actual encounters between them. Our results show that the database structure presents a great value of clustering. In the second step, we evaluated dynamics of disease spread with SIR model by assigning a function to each node of the structural network. The rate of disease spread in networks was observed to be inversely correlated with characteristic path length. Therefore, the shortcuts have a significant role in increasing spread rate. We conclude that the dynamics of social encounters' network stands between the random and the lattice in network spectrum. Although in this study we considered the period of common-cold disease for network dynamics, it seems that similar approaches may be useful for other airborne diseases such as SARS.

Responder Status Criterion for Stepped Care Trauma-Focused Cognitive Behavioral Therapy for Young Children

PubMed Central

Salloum, Alison; Scheeringa, Michael S.; Cohen, Judith A.; Storch, Eric A.

2014-01-01

Background In order to develop Stepped Care Trauma-Focused Cognitive Behavioral Therapy (TF-CBT), a definition of early response/non-response is needed to guide decisions about the need for subsequent treatment. Objective The purpose of this article is to (1) establish criterion for defining an early indicator of response/nonresponse to the first step within Stepped Care TF-CBT, and (2) to explore the preliminary clinical utility of the early response/non-response criterion. Method Data from two studies were used: (1) treatment outcome data from a clinical trial in which 17 young children (ages 3 to 6 years) received therapist-directed CBT for children with PTSS were examined to empirically establish the number of posttraumatic stress symptoms to define early treatment response/non-response; and (2) three case examples with young children in Stepped Care TF-CBT were used to explore the utility of the treatment response criterion. Results For defining the responder status criterion, an algorithm of either 3 or fewer PTSS on a clinician-rated measure or being below the clinical cutoff score on a parent-rated measure of childhood PTSS, and being rated as improved, much improved or free of symptoms functioned well for determining whether or not to step up to more intensive treatment. Case examples demonstrated how the criterion were used to guide subsequent treatment, and that responder status criterion after Step One may or may not be aligned with parent preference. Conclusion Although further investigation is needed, the responder status criterion for young children used after Step One of Stepped Care TF-CBT appears promising. PMID:25663796

Thermal denaturation of β-glucosidase B from Paenibacillus polymyxa proceeds through a Lumry-Eyring mechanism.

PubMed

Camarillo-Cadena, Menandro; Garza-Ramos, Georgina; Peimbert, Mariana; Pérez-Hernández, Gerardo; Zubillaga, Rafael A

2011-06-01

β-glucosidase B (BglB), 1,4-β-D: -glucanohydrolase, is an enzyme with various technological applications for which some thermostable mutants have been obtained. Because BglB denatures irreversibly with heating, the stabilities of these mutants are assessed kinetically. It, therefore, becomes relevant to determine whether the measured rate constants reflect one or several elementary kinetic steps. We have analyzed the kinetics of heat denaturation of BglB from Paenibacillus polymyxa under various conditions by following the loss of secondary structure and enzymatic activity. The denaturation is accompanied by aggregation and an initial reversible step at low temperatures. At T ≥ T ( m ), the process follows a two-state irreversible mechanism for which the kinetics does not depend on the enzyme concentration. This behavior can be explained by a Lumry-Eyring model in which the difference between the rates of the irreversible and the renaturation steps increases with temperature. Accordingly, at high scan rates (≥1 °C min(-1)) or temperatures (T ≥ T ( m )), the measurable activation energy involves only the elementary step of denaturation.

40 CFR 75.16 - Special provisions for monitoring emissions from common, bypass, and multiple stacks for SO2...

Code of Federal Regulations, 2011 CFR

2011-07-01

... emissions from common, bypass, and multiple stacks for SO2 emissions and heat input determinations. 75.16... emissions from common, bypass, and multiple stacks for SO2 emissions and heat input determinations. (a... by the Administrator, such that these emissions are not underestimated. (e) Heat input rate. The...

40 CFR 75.16 - Special provisions for monitoring emissions from common, bypass, and multiple stacks for SO 2...

Code of Federal Regulations, 2013 CFR

2013-07-01

... emissions from common, bypass, and multiple stacks for SO 2 emissions and heat input determinations. 75.16... emissions from common, bypass, and multiple stacks for SO 2 emissions and heat input determinations. (a... by the Administrator, such that these emissions are not underestimated. (e) Heat input rate. The...

40 CFR 75.16 - Special provisions for monitoring emissions from common, bypass, and multiple stacks for SO2...

Code of Federal Regulations, 2012 CFR

2012-07-01

... emissions from common, bypass, and multiple stacks for SO2 emissions and heat input determinations. 75.16... emissions from common, bypass, and multiple stacks for SO2 emissions and heat input determinations. (a... by the Administrator, such that these emissions are not underestimated. (e) Heat input rate. The...

40 CFR 75.16 - Special provisions for monitoring emissions from common, bypass, and multiple stacks for SO 2...

Code of Federal Regulations, 2014 CFR

2014-07-01

... emissions from common, bypass, and multiple stacks for SO 2 emissions and heat input determinations. 75.16... emissions from common, bypass, and multiple stacks for SO 2 emissions and heat input determinations. (a... by the Administrator, such that these emissions are not underestimated. (e) Heat input rate. The...

40 CFR 75.72 - Determination of NOX mass emissions for common stack and multiple stack configurations.

Code of Federal Regulations, 2010 CFR

2010-07-01

... the hourly stack flow rate (in scfh). Only one methodology for determining NOX mass emissions shall be...-diluent continuous emissions monitoring system and a flow monitoring system in the common stack, record... maintain a flow monitoring system and diluent monitor in the duct to the common stack from each unit; or...

A single determinant dominates the rate of yeast protein evolution.

PubMed

Drummond, D Allan; Raval, Alpan; Wilke, Claus O

2006-02-01

A gene's rate of sequence evolution is among the most fundamental evolutionary quantities in common use, but what determines evolutionary rates has remained unclear. Here, we carry out the first combined analysis of seven predictors (gene expression level, dispensability, protein abundance, codon adaptation index, gene length, number of protein-protein interactions, and the gene's centrality in the interaction network) previously reported to have independent influences on protein evolutionary rates. Strikingly, our analysis reveals a single dominant variable linked to the number of translation events which explains 40-fold more variation in evolutionary rate than any other, suggesting that protein evolutionary rate has a single major determinant among the seven predictors. The dominant variable explains nearly half the variation in the rate of synonymous and protein evolution. We show that the two most commonly used methods to disentangle the determinants of evolutionary rate, partial correlation analysis and ordinary multivariate regression, produce misleading or spurious results when applied to noisy biological data. We overcome these difficulties by employing principal component regression, a multivariate regression of evolutionary rate against the principal components of the predictor variables. Our results support the hypothesis that translational selection governs the rate of synonymous and protein sequence evolution in yeast.

Crystallization of Membrane Proteins by Vapor Diffusion

PubMed Central

Delmar, Jared A.; Bolla, Jani Reddy; Su, Chih-Chia; Yu, Edward W.

2016-01-01

X-ray crystallography remains the most robust method to determine protein structure at the atomic level. However, the bottlenecks of protein expression and purification often discourage further study. In this chapter, we address the most common problems encountered at these stages. Based on our experiences in expressing and purifying antimicrobial efflux proteins, we explain how a pure and homogenous protein sample can be successfully crystallized by the vapor diffusion method. We present our current protocols and methodologies for this technique. Case studies show step-by-step how we have overcome problems related to expression and diffraction, eventually producing high quality membrane protein crystals for structural determinations. It is our hope that a rational approach can be made of the often anecdotal process of membrane protein crystallization. PMID:25950974

Measurement of 1323 and 1487 keV resonances in 15N(α ,γ )19F with the recoil separator ERNA

NASA Astrophysics Data System (ADS)

Di Leva, A.; Imbriani, G.; Buompane, R.; Gialanella, L.; Best, A.; Cristallo, S.; De Cesare, M.; D'Onofrio, A.; Duarte, J. G.; Gasques, L. R.; Morales-Gallegos, L.; Pezzella, A.; Porzio, G.; Rapagnani, D.; Roca, V.; Romoli, M.; Schürmann, D.; Straniero, O.; Terrasi, F.; ERNA Collaboration

2017-04-01

Background: The origin of fluorine is a widely debated issue. Nevertheless, the 15N(α ,γ )19F reaction is a common feature among the various production channels so far proposed. Its reaction rate at relevant temperatures is determined by a number of narrow resonances together with the direct capture and the tails of the two broad resonances at Ec .m .=1323 and 1487 keV. Purpose: The broad resonances widths, Γγ and Γα, have to be measured with adequate precision in order to better determine their contribution to the 15N(α ,γ )19F stellar reaction rate. Methods: Measurement through the direct detection of the 19F recoil ions with the European Recoil separator for Nuclear Astrophysics (ERNA) were performed. The reaction was initiated by a 15N beam impinging onto a 4He windowless gas target. The observed yield of the resonances at Ec .m .=1323 and 1487 keV is used to determine their widths in the α and γ channels. Results: We show that a direct measurement of the cross section of the 15N(α ,γ )19F reaction can be successfully obtained with the recoil separator ERNA, and the widths Γγ and Γα of the two broad resonances have been determined. While a fair agreement is found with earlier determination of the widths of the 1487 keV resonance, a significant difference is found for the 1323 keV resonance Γα. Conclusions: The revision of the widths of the two more relevant broad resonances in the 15N(α ,γ )19F reaction presented in this work is the first step toward a more firm determination of the reaction rate. At present, the residual uncertainty at the temperatures of the 19F stellar nucleosynthesis is dominated by the uncertainties affecting the direct capture component and the 364 keV narrow resonance, both so far investigated only through indirect experiments.

Development of a Training Model for Laparoscopic Common Bile Duct Exploration

PubMed Central

Rodríguez, Omaira; Benítez, Gustavo; Sánchez, Renata; De la Fuente, Liliana

2010-01-01

Background: Training and experience of the surgical team are fundamental for the safety and success of complex surgical procedures, such as laparoscopic common bile duct exploration. Methods: We describe an inert, simple, very low-cost, and readily available training model. Created using a “black box” and basic medical and surgical material, it allows training in the fundamental steps necessary for laparoscopic biliary tract surgery, namely, (1) intraoperative cholangiography, (2) transcystic exploration, and (3) laparoscopic choledochotomy, and t-tube insertion. Results: The proposed model has allowed for the development of the skills necessary for partaking in said procedures, contributing to its development and diminishing surgery time as the trainee advances down the learning curve. Further studies are directed towards objectively determining the impact of the model on skill acquisition. Conclusion: The described model is simple and readily available allowing for accurate reproduction of the main steps and maneuvers that take place during laparoscopic common bile duct exploration, with the purpose of reducing failure and complications. PMID:20529526

The Determination of Rate-Limiting Steps during Soot Formation

DTIC Science & Technology

1990-06-08

and a CH3N precursor of acetonitrile such as 2H-aziridine although other intermediates of lower energy such as ketenimine have been identified on the...precursor of acetonitrile such as 2H-aziridine or ketenimine . Experimentally it was found that the overall rate of disappearance of pyrrole is first order

Foot and Ankle Kinematics During Descent From Varying Step Heights.

PubMed

Gerstle, Emily E; O'Connor, Kristian; Keenan, Kevin G; Cobb, Stephen C

2017-12-01

In the general population, one-third of incidences during step negotiation occur during the transition to level walking. Furthermore, falls during curb negotiation are a common cause of injury in older adults. Distal foot kinematics may be an important factor in determining injury risk associated with transition step negotiation. The purpose of this study was to identify foot and ankle kinematics of uninjured individuals during descent from varying step heights. A 7-segment foot model was used to quantify kinematics as participants walked on a level walkway, stepped down a single step (heights: 5 cm, 15 cm, 25 cm), and continued walking. As step height increased, landing strategy transitioned from the rearfoot to the forefoot, and the rearfoot, lateral and medial midfoot, and medial forefoot became more plantar flexed. During weight acceptance, sagittal plane range of motion of the rearfoot, lateral midfoot, and medial and lateral forefoot increased as step height increased. The changes in landing strategy and distal foot function suggest a less stable ankle position at initial contact and increased demand on the distal foot at initial contact and through the weight acceptance phase of transition step negotiation as step height increases.

Kinetic aspects of chain growth in Fischer-Tropsch synthesis.

PubMed

Filot, Ivo A W; Zijlstra, Bart; Broos, Robin J P; Chen, Wei; Pestman, Robert; Hensen, Emiel J M

2017-04-28

Microkinetics simulations are used to investigate the elementary reaction steps that control chain growth in the Fischer-Tropsch reaction. Chain growth in the FT reaction on stepped Ru surfaces proceeds via coupling of CH and CR surface intermediates. Essential to the growth mechanism are C-H dehydrogenation and C hydrogenation steps, whose kinetic consequences have been examined by formulating two novel kinetic concepts, the degree of chain-growth probability control and the thermodynamic degree of chain-growth probability control. For Ru the CO conversion rate is controlled by the removal of O atoms from the catalytic surface. The temperature of maximum CO conversion rate is higher than the temperature to obtain maximum chain-growth probability. Both maxima are determined by Sabatier behavior, but the steps that control chain-growth probability are different from those that control the overall rate. Below the optimum for obtaining long hydrocarbon chains, the reaction is limited by the high total surface coverage: in the absence of sufficient vacancies the CHCHR → CCHR + H reaction is slowed down. Beyond the optimum in chain-growth probability, CHCR + H → CHCHR and OH + H → H 2 O limit the chain-growth process. The thermodynamic degree of chain-growth probability control emphasizes the critical role of the H and free-site coverage and shows that at high temperature, chain depolymerization contributes to the decreased chain-growth probability. That is to say, during the FT reaction chain growth is much faster than chain depolymerization, which ensures high chain-growth probability. The chain-growth rate is also fast compared to chain-growth termination and the steps that control the overall CO conversion rate, which are O removal steps for Ru.

Rhenium-Oxygen Interactions at High Temperatures

NASA Technical Reports Server (NTRS)

Jacobson, Nathan S.; Myers, Dwight L.; Zhu, Dongming; Humphrey, Donald

2000-01-01

The reaction of pure rhenium metal with dilute oxygen/argon mixtures was studied from 600 to 1400 C. Temperature, oxygen pressure, and flow rates were systematically varied to determine the rate-controlling steps. At lower temperatures the oxygen/rhenium chemical reaction is rate limiting; at higher temperatures gas-phase diffusion of oxygen through the static boundary layer is rate limiting. At all temperatures post-reaction microstructures indicate preferential attack along certain crystallographic planes and defects.

Kinetic study of the oxidation of 3-hydroxyanisole catalysed by tyrosinase.

PubMed

Fenoll, L G; Rodríguez-López, J N; Varón, R; García-Ruiz, P A; García-Cánovas, F; Tudela, J

2000-02-14

Tyrosinase hydroxylates 3-hydroxyanisole in the 4-position. The reaction product accumulates in the reaction medium with a lag time (tau) which diminishes with increasing concentrations of enzyme and lengthens with increasing concentrations of substrate, thus fulfilling all the predictions of the mechanism proposed by us for 4-hydroxyphenols. The kinetic constants obtained, kcatM = (46.87 +/- 2.06) s-1 and KmM = (5.40 +/- 0.60) mM, are different from those obtained with 4-hydroxyanisole, kcatM = (184.20 +/- 6.1) s-1 and KmM = (0.08 +/- 0.004) mM. The catalytic efficiency, kcatM/KmM is, therefore, 265.3 times greater with 4-hydroxyanisole. The possible rate-determining steps for the reaction mechanism of tyrosinase on 3- and 4-hydroxyanisole, based on the NMR spectra of both monophenols, are discussed. These possible rate-determining steps are the nucleophilic attack of hydroxyl's oxygen on the copper and the electrophilic attack of the peroxide on the aromatic ring. Both steps may be of similar magnitude, i.e. take place in the same time scale.

Determining Annealing Temperatures for Polymerase Chain Reaction

ERIC Educational Resources Information Center

Porta, Angela R.; Enners, Edward

2012-01-01

The polymerase chain reaction (PCR) is a common technique used in high school and undergraduate science teaching. Students often do not fully comprehend the underlying principles of the technique and how optimization of the protocol affects the outcome and analysis. In this molecular biology laboratory, students learn the steps of PCR with an…

Equilibrium Moisture Content of Common Fine Fuels in Southeastern Forests

Treesearch

W.H. Blackmarr

1971-01-01

Nine different kinds of forest litter found in ground fuel complexes of southeastern forests were subjected to step-wise changes in relative humidity to determine their equilibrium moisture content (EMC) at different levels of relative humidity. The adsorption and desorption EMC curves for these fuels exhibited the typical hysteresis loop...

Energy dispersive-EXAFS of Pd nucleation at a liquid/liquid interface

NASA Astrophysics Data System (ADS)

Chang, S.-Y.; Booth, S. G.; Uehara, A.; Mosselmans, J. F. W.; Cibin, G.; Pham, V.-T.; Nataf, L.; Dryfe, R. A. W.; Schroeder, S. L. M.

2016-05-01

Energy dispersive extended X-ray absorption fine structure (EDE) has been applied to Pd nanoparticle nucleation at a liquid/liquid interface under control over the interfacial potential and thereby the driving force for nucleation. Preliminary analysis focusing on Pd K edge-step height determination shows that under supersaturated conditions the concentration of Pd near the interface fluctuate over a period of several hours, likely due to the continuous formation and dissolution of sub-critical nuclei. Open circuit potential measurements conducted ex-situ in a liquid/liquid electrochemical cell support this view, showing that the fluctuations in Pd concentration are also visible as variations in potential across the liquid/liquid interface. By decreasing the interfacial potential through inclusion of a common ion (tetraethylammonium, TEA+) the Pd nanoparticle growth rate could be slowed down, resulting in a smooth nucleation process. Eventually, when the TEA+ ions reached an equilibrium potential, Pd nucleation and particle growth were inhibited.

Practices for Identifying and Rejecting Hemolyzed Specimens Are Highly Variable in Clinical Laboratories.

PubMed

Howanitz, Peter J; Lehman, Christopher M; Jones, Bruce A; Meier, Frederick A; Horowitz, Gary L

2015-08-01

Hemolysis is an important clinical laboratory quality attribute that influences result reliability. To determine hemolysis identification and rejection practices occurring in clinical laboratories. We used the College of American Pathologists Survey program to distribute a Q-Probes-type questionnaire about hemolysis practices to Chemistry Survey participants. Of 3495 participants sent the questionnaire, 846 (24%) responded. In 71% of 772 laboratories, the hemolysis rate was less than 3.0%, whereas in 5%, it was 6.0% or greater. A visual scale, an instrument scale, and combination of visual and instrument scales were used to identify hemolysis in 48%, 11%, and 41% of laboratories, respectively. A picture of the hemolysis level was used as an aid to technologists' visual interpretation of hemolysis levels in 40% of laboratories. In 7.0% of laboratories, all hemolyzed specimens were rejected; in 4% of laboratories, no hemolyzed specimens were rejected; and in 88% of laboratories, some specimens were rejected depending on hemolysis levels. Participants used 69 different terms to describe hemolysis scales, with 21 terms used in more than 10 laboratories. Slight and moderate were the terms used most commonly. Of 16 different cutoffs used to reject hemolyzed specimens, moderate was the most common, occurring in 30% of laboratories. For whole blood electrolyte measurements performed in 86 laboratories, 57% did not evaluate the presence of hemolysis, but for those that did, the most common practice in 21 laboratories (24%) was centrifuging and visually determining the presence of hemolysis in all specimens. Hemolysis practices vary widely. Standard assessment and consistent reporting are the first steps in reducing interlaboratory variability among results.

A direct numerical simulation-based re-examination of coefficients in the pressure-strain models in second-moment closures

NASA Astrophysics Data System (ADS)

Jakirlić, S.; Hanjalić, K.

2013-10-01

The most challenging task in closing the Reynolds-averaged Navier-Stokes equations at the second-moment closure (SMC) level is to model the pressure-rate-of-strain correlation in the transport equation for the Reynolds-stress tensor. The accurate modelling of this term, commonly denoted as Φij, is the key prerequisite for the correct capturing of the stress anisotropy, which potentially gives SMCs a decisive advantage over the ‘anisotropy-blind’ eddy-viscosity models. A variety of models for Φij proposed in the literature can all be expressed as a function of the stress-anisotropy-, rate-of-strain- and rate-of-rotation second-rank tensors, so that the modelling task is reduced to determining the model coefficients. It is, thus, the coefficients, associated with various terms in the expression, which differ from one model to another. The model coefficients have been traditionally determined with reference to the available data for sets of generic flows while being forced to satisfying the known values at flow boundaries. We evaluated the coefficients up to the second-order terms (in stress-anisotropy aij) directly from the DNS database for Φij and the turbulence variables involved in its modelling. The variations of the coefficients across the flow in a plane channel over a range of Reynolds numbers are compared with several popular models. The analysis provided a reasonable support for the common tensor-expansion representation of both the slow and rapid terms. Apart from the near-wall region and the channel centre, most coefficients for higher Re numbers showed themselves to be reasonably uniform, with the values closest to those proposed by Sarkar et al (1991 J. Fluid Mech. 227 245-72). An illustration of the coefficient variation for the ‘quasi-linear’ model is also presented for flow over a backward-facing step.

Mechanism insight into the cyanide-catalyzed benzoin condensation: a density functional theory study.

PubMed

He, Yunqing; Xue, Ying

2010-09-02

The reaction mechanism of the cyanide-catalyzed benzoin condensation without protonic solvent assistance has been studied computationally for the first time employing the density functional theory (B3LYP) method in conjunction with 6-31+G(d,p) basis set. Four possible pathways have been investigated. A new proposed pathway on the basis of the Lapworth mechanism is determined to be the dominant pathway in aprotic solvent, in which the formation of the Lapworth's cyanohydrin intermediate is a sequence including three steps assisted by benzaldehyde, clearly manifesting that the reaction can take place in aprotic solvents such as DMSO. In this favorable pathway with six possible transition states located along the potential energy surface, the reaction of the cyanide/benzaldehyde complex with another benzaldehyde to afford an alpha-hydroxy ether is the rate-determining dynamically with the activation free energy barrier of 26.9 kcal/mol, and the step to form cyanohydrin intermediate from alpha-hydroxy ether is partially rate-determining for its relatively significant barrier 20.0 kcal/mol.

Growth Anomalies in Supramolecular Networks: 4,4'-Biphenyldicarboxylic Acid on Cu(001)

NASA Astrophysics Data System (ADS)

Schwarz, Daniel; van Gastel, Raoul; Zandvliet, Harold J. W.; Poelsema, Bene

2013-02-01

We have used low energy electron microscopy to demonstrate how the interaction of 4,4'-biphenyldicarboxylic acid (BDA) molecules with (steps on) the Cu(001) surface determines the structure of supramolecular BDA networks on a mesoscopic length scale. Our in situ real time observations reveal that steps are permeable to individual molecules but that the change in crystal registry between different layers of the Cu substrate causes them to be completely impermeable to condensed BDA domains. The resulting growth instabilities determine the evolution of the domain shape and include a novel Mullins-Sekerka-type growth instability that is characterized by high growth rates along, instead of perpendicular to, the Cu steps. This growth instability is responsible for the majority of residual defects in the BDA networks.

Dissolution of quartz in aqueous basic solution, 106-236 C - Surface kinetics of 'perfect' crystallographic faces

NASA Technical Reports Server (NTRS)

Gratz, Andrew J.; Bird, Peter; Quiro, Glenn B.

1990-01-01

A highly accurate method, called the negative crystal method, for determining the rate of dissolution on specific crystallographic faces of crystals was developed, in which the dissolution rates of nominally perfect crystal faces are obtained by measuring the size of individual negative crystals during a sequence of dissolution steps. The method was applied to determine the apparent activation energy and rate constants for the dissolution of quartz in 0.01 M KOH solutions at temperatures from 106 to 236 C. Also investigated were the effects of hydroxyl activity and ionic strength. The apparent activation energies for the dissolution of the prism and of the rhomb were determined.

The Relaxation of Vicinal (001) with ZigZag [110] Steps

NASA Astrophysics Data System (ADS)

Hawkins, Micah; Hamouda, Ajmi Bh; González-Cabrera, Diego Luis; Einstein, Theodore L.

2012-02-01

This talk presents a kinetic Monte Carlo study of the relaxation dynamics of [110] steps on a vicinal (001) simple cubic surface. This system is interesting because [110] steps have different elementary excitation energetics and favor step diffusion more than close-packed [100] steps. In this talk we show how this leads to relaxation dynamics showing greater fluctuations on a shorter time scale for [110] steps as well as 2-bond breaking processes being rate determining in contrast to 3-bond breaking processes for [100] steps. The existence of a steady state is shown via the convergence of terrace width distributions at times much longer than the relaxation time. In this time regime excellent fits to the modified generalized Wigner distribution (as well as to the Berry-Robnik model when steps can overlap) were obtained. Also, step-position correlation function data show diffusion-limited increase for small distances along the step as well as greater average step displacement for zigzag steps compared to straight steps for somewhat longer distances along the step. Work supported by NSF-MRSEC Grant DMR 05-20471 as well as a DOE-CMCSN Grant.

Processes and kinetics of Cd2+ sorption by a calcareous aquifer sand

USGS Publications Warehouse

Fuller, C.C.; Davis, J.A.

1987-01-01

The rate of Cd2+ sorption by a calcareous aquifer sand was characterized by two reaction steps, with the first step reaching completion in 24 hours. The second step proceeded at a slow and nearly constant rate for at least seven days. The first step includes a fast adsorption reaction which is followed by diffusive transport into either a disordered surface film of hydrated calcium carbonate or into pore spaces. After 24 hours the rate of Cd2+ sorption was constant and controlled by the rate of surface coprecipitation, as a solid solution of CdCO3 in CaCO3 formed in recrystallizing material. Desorption of Cd2+ from the sand was slow. Clean grains of primary minerals, e.g. quartz and aluminosilicates. sorbed much less Cd2+ than grains which had surface patches of secondary minerals, e.g. carbonates, iron and manganese oxides. Calcite grains sorbed the greatest amount of Cd2+ on a weight-normalized basis despite the greater abundance of quartz. A method is illustrated for determining empirical binding constants for trace metals at in situ pH values without introducing the experimental problem of supersaturation. The binding constants are useful for solute transport models which include a computation of aqueous speciation. ?? 1987.

Kinetics of the sorption of triterpene saponin by hypercrosslinked polystyrene

NASA Astrophysics Data System (ADS)

Mironenko, N. V.; Brezhneva, T. A.; Selemenev, V. F.

2013-03-01

The kinetics of sorption of triterpene saponin by the polymer sorbent NM-200 is considered. The influence of the surface activity of glycoside on the rate of formation and structure of the adsorption layer on the sorbent's surface is established. The rate-determining step of sorption is found to be diffusion into the sorbent grain. The value of the activation energy demonstrates the determining role of dispersion forces in the interaction between triterpene saponin and the polymer sorbent MN-200.

Criteria for software modularization

NASA Technical Reports Server (NTRS)

Card, David N.; Page, Gerald T.; Mcgarry, Frank E.

1985-01-01

A central issue in programming practice involves determining the appropriate size and information content of a software module. This study attempted to determine the effectiveness of two widely used criteria for software modularization, strength and size, in reducing fault rate and development cost. Data from 453 FORTRAN modules developed by professional programmers were analyzed. The results indicated that module strength is a good criterion with respect to fault rate, whereas arbitrary module size limitations inhibit programmer productivity. This analysis is a first step toward defining empirically based standards for software modularization.

A method for generating reduced-order combustion mechanisms that satisfy the differential entropy inequality

NASA Astrophysics Data System (ADS)

Ream, Allen E.; Slattery, John C.; Cizmas, Paul G. A.

2018-04-01

This paper presents a new method for determining the Arrhenius parameters of a reduced chemical mechanism such that it satisfies the second law of thermodynamics. The strategy is to approximate the progress of each reaction in the reduced mechanism from the species production rates of a detailed mechanism by using a linear least squares method. A series of non-linear least squares curve fittings are then carried out to find the optimal Arrhenius parameters for each reaction. At this step, the molar rates of production are written such that they comply with a theorem that provides the sufficient conditions for satisfying the second law of thermodynamics. This methodology was used to modify the Arrhenius parameters for the Westbrook and Dryer two-step mechanism and the Peters and Williams three-step mechanism for methane combustion. Both optimized mechanisms showed good agreement with the detailed mechanism for species mole fractions and production rates of most major species. Both optimized mechanisms showed significant improvement over previous mechanisms in minor species production rate prediction. Both optimized mechanisms produced no violations of the second law of thermodynamics.

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.

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

Lobo, R.; Revah, S.; Viveros-Garcia, T.

An analysis of the local processes occurring in a trickle-bed bioreactor (TBB) with a first-order bioreaction shows that the identification of the TBB operating regime requires knowledge of the substrate concentration in the liquid phase. If the substrate liquid concentration is close to 0, the rate-controlling step is mass transfer at the gas-liquid interface; when it is close to the value in equilibrium with the gas phase, the controlling step is the phenomena occurring in the biofilm, CS{sub 2} removal rate data obtained in a TBB with a Thiobacilii consortia biofilm are analyzed to obtain the mass transfer and kineticmore » parameters, and to show that the bioreactor operates in a regime mainly controlled by mass transfer. A TBB model with two experimentally determined parameters is developed and used to show how the bioreactor size depends on the rate-limiting step, the absorption factor, the substrate fractional conversion, and on the gas and liquid contact pattern. Under certain conditions, the TBB size is independent of the flowing phases` contact pattern. The model effectively describes substrate gas and liquid concentration data for mass transfer and biodegradation rate controlled processes.« less

Determination of the apparent transfer coefficient for CO oxidation on Pt(poly), Pt(111), Pt(665) and Pt(332) using a potential modulation technique.

PubMed

Wang, Han-Chun; Ernst, Siegfried; Baltruschat, Helmut

2010-03-07

The apparent transfer coefficient, which gives the magnitude of the potential dependence of the electrochemical reaction rates, is the key quantity for the elucidation of electrochemical reaction mechanisms. We introduce the application of an ac method to determine the apparent transfer coefficient alpha' for the oxidation of pre-adsorbed CO at polycrystalline and single-crystalline Pt electrodes in sulfuric acid. The method allows to record alpha' quasi continuously as a function of potential (and time) in cyclic voltammetry or at a fixed potential, with the reaction rate varying with time. At all surfaces (Pt(poly), Pt(111), Pt(665), and Pt(332)) we clearly observed a transition of the apparent transfer coefficient from values around 1.5 at low potentials to values around 0.5 at higher potentials. Changes of the apparent transfer coefficients for the CO oxidation with potential were observed previously, but only from around 0.7 to values as low as 0.2. In contrast, our experimental findings completely agree with the simulation by Koper et al., J. Chem. Phys., 1998, 109, 6051-6062. They can be understood in the framework of a Langmuir-Hinshelwood mechanism. The transition occurs when the sum of the rate constants for the forward reaction (first step: potential dependent OH adsorption, second step: potential dependent oxidation of CO(ad) with OH(ad)) exceeds the rate constant for the back-reaction of the first step. We expect that the ac method for the determination of the apparent transfer coefficient, which we used here, will be of great help also in many other cases, especially under steady conditions, where the major limitations of the method are avoided.

Development of Acetic Acid Removal Technology for the UREX+Process

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

Robert M. Counce; Jack S. Watson

2009-06-30

It is imperative that acetic acid is removed from a waste stream in the UREX+process so that nitric acid can be recycled and possible interference with downstreatm steps can be avoidec. Acetic acid arises from acetohydrozamic acid (AHA), and is used to suppress plutonium in the first step of the UREX+process. Later, it is hydrolyzed into hydroxyl amine nitrate and acetic acid. Many common separation technologies were examined, and solvent extraction was determined to be the best choice under process conditions. Solvents already used in the UREX+ process were then tested to determine if they would be sufficient for themore » removal of acetic acid. The tributyl phosphage (TBP)-dodecane diluent, used in both UREX and NPEX, was determined to be a solvent system that gave sufficient distribution coefficients for acetic acid in addition to a high separation factor from nitric acid.« less

47 CFR 54.607 - Determining the rural rate.

Code of Federal Regulations, 2010 CFR

2010-10-01

....607 Telecommunication FEDERAL COMMUNICATIONS COMMISSION (CONTINUED) COMMON CARRIER SERVICES (CONTINUED) UNIVERSAL SERVICE Universal Service Support for Health Care Providers § 54.607 Determining the rural rate..., other than health care providers, for identical or similar services provided by the telecommunications...

Complex Impedance, DSC and Lithium-7 NMR Studies of Poly(propylene oxide) Complexed with LiN(SO2CF3)2 and with LiAsF6

DTIC Science & Technology

1994-01-01

re- plexes. This feature is commonly observed when the moved by room temperature evaporation under par- heating rate is different from previous cooling...It is apparent from fig. 1 that some shallow teflon dishes. Prior to use, the acetonitrile overshoot (an apparent endotherm ) is observed just was...or tial vacuum ( - 20 mm) and the final preparation heating rates that the material has experienced. Con- step consisted of heating the samples to

In situ nanoscale observations of gypsum dissolution by digital holographic microscopy.

PubMed

Feng, Pan; Brand, Alexander S; Chen, Lei; Bullard, Jeffrey W

2017-06-01

Recent topography measurements of gypsum dissolution have not reported the absolute dissolution rates, but instead focus on the rates of formation and growth of etch pits. In this study, the in situ absolute retreat rates of gypsum (010) cleavage surfaces at etch pits, at cleavage steps, and at apparently defect-free portions of the surface are measured in flowing water by reflection digital holographic microscopy. Observations made on randomly sampled fields of view on seven different cleavage surfaces reveal a range of local dissolution rates, the local rate being determined by the topographical features at which material is removed. Four characteristic types of topographical activity are observed: 1) smooth regions, free of etch pits or other noticeable defects, where dissolution rates are relatively low; 2) shallow, wide etch pits bounded by faceted walls which grow gradually at rates somewhat greater than in smooth regions; 3) narrow, deep etch pits which form and grow throughout the observation period at rates that exceed those at the shallow etch pits; and 4) relatively few, submicrometer cleavage steps which move in a wave-like manner and yield local dissolution fluxes that are about five times greater than at etch pits. Molar dissolution rates at all topographical features except submicrometer steps can be aggregated into a continuous, mildly bimodal distribution with a mean of 3.0 µmolm -2 s -1 and a standard deviation of 0.7 µmolm -2 s -1 .

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

ERIC Educational Resources Information Center

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

1988-01-01

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

Determining Spacecraft Reaction Wheel Friction Parameters

NASA Technical Reports Server (NTRS)

Sarani, Siamak

2009-01-01

Software was developed to characterize the drag in each of the Cassini spacecraft's Reaction Wheel Assemblies (RWAs) to determine the RWA friction parameters. This tool measures the drag torque of RWAs for not only the high spin rates (greater than 250 RPM), but also the low spin rates (less than 250 RPM) where there is a lack of an elastohydrodynamic boundary layer in the bearings. RWA rate and drag torque profiles as functions of time are collected via telemetry once every 4 seconds and once every 8 seconds, respectively. Intermediate processing steps single-out the coast-down regions. A nonlinear model for the drag torque as a function of RWA spin rate is incorporated in order to characterize the low spin rate regime. The tool then uses a nonlinear parameter optimization algorithm based on the Nelder-Mead simplex method to determine the viscous coefficient, the Dahl friction, and the two parameters that account for the low spin-rate behavior.

Oxidation-driven surface dynamics on NiAl(100)

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

Qin, Hailang; Chen, Xidong; Li, Liang

Atomic steps, a defect common to all crystal surfaces, can play an important role in many physical and chemical processes. However, attempts to predict surface dynamics under nonequilibrium conditions are usually frustrated by poor knowledge of the atomic processes of surface motion arising from mass transport from/to surface steps. Using low-energy electron microscopy that spatially and temporally resolves oxide film growth during the oxidation of NiAl(100) we demonstrate that surface steps are impermeable to oxide film growth. The advancement of the oxide occurs exclusively on the same terrace and requires the coordinated migration of surface steps. The resulting piling upmore » of surface steps ahead of the oxide growth front progressively impedes the oxide growth. This process is reversed during oxide decomposition. The migration of the substrate steps is found to be a surface-step version of the well-known Hele-Shaw problem, governed by detachment (attachment) of Al atoms at step edges induced by the oxide growth (decomposition). As a result, by comparing with the oxidation of NiAl(110) that exhibits unimpeded oxide film growth over substrate steps, we suggest that whenever steps are the source of atoms used for oxide growth they limit the oxidation process; when atoms are supplied from the bulk, the oxidation rate is not limited by the motion of surface steps.« less

Oxidation-driven surface dynamics on NiAl(100)

DOE PAGES

Qin, Hailang; Chen, Xidong; Li, Liang; ...

2014-12-29

Atomic steps, a defect common to all crystal surfaces, can play an important role in many physical and chemical processes. However, attempts to predict surface dynamics under nonequilibrium conditions are usually frustrated by poor knowledge of the atomic processes of surface motion arising from mass transport from/to surface steps. Using low-energy electron microscopy that spatially and temporally resolves oxide film growth during the oxidation of NiAl(100) we demonstrate that surface steps are impermeable to oxide film growth. The advancement of the oxide occurs exclusively on the same terrace and requires the coordinated migration of surface steps. The resulting piling upmore » of surface steps ahead of the oxide growth front progressively impedes the oxide growth. This process is reversed during oxide decomposition. The migration of the substrate steps is found to be a surface-step version of the well-known Hele-Shaw problem, governed by detachment (attachment) of Al atoms at step edges induced by the oxide growth (decomposition). As a result, by comparing with the oxidation of NiAl(110) that exhibits unimpeded oxide film growth over substrate steps, we suggest that whenever steps are the source of atoms used for oxide growth they limit the oxidation process; when atoms are supplied from the bulk, the oxidation rate is not limited by the motion of surface steps.« less

Bifurcation analysis of a discrete-time ratio-dependent predator-prey model with Allee Effect

NASA Astrophysics Data System (ADS)

Cheng, Lifang; Cao, Hongjun

2016-09-01

A discrete-time predator-prey model with Allee effect is investigated in this paper. We consider the strong and the weak Allee effect (the population growth rate is negative and positive at low population density, respectively). From the stability analysis and the bifurcation diagrams, we get that the model with Allee effect (strong or weak) growth function and the model with logistic growth function have somewhat similar bifurcation structures. If the predator growth rate is smaller than its death rate, two species cannot coexist due to having no interior fixed points. When the predator growth rate is greater than its death rate and other parameters are fixed, the model can have two interior fixed points. One is always unstable, and the stability of the other is determined by the integral step size, which decides the species coexistence or not in some extent. If we increase the value of the integral step size, then the bifurcated period doubled orbits or invariant circle orbits may arise. So the numbers of the prey and the predator deviate from one stable state and then circulate along the period orbits or quasi-period orbits. When the integral step size is increased to a critical value, chaotic orbits may appear with many uncertain period-windows, which means that the numbers of prey and predator will be chaotic. In terms of bifurcation diagrams and phase portraits, we know that the complexity degree of the model with strong Allee effect decreases, which is related to the fact that the persistence of species can be determined by the initial species densities.

Large-scale uniform bilayer graphene prepared by vacuum graphitization of 6H-SiC(0001) substrates

NASA Astrophysics Data System (ADS)

Wang, Qingyan; Zhang, Wenhao; Wang, Lili; He, Ke; Ma, Xucun; Xue, Qikun

2013-03-01

We report on the preparation of large-scale uniform bilayer graphenes on nominally flat Si-polar 6H-SiC(0001) substrates by flash annealing in ultrahigh vacuum. The resulting graphenes have a single thickness of one bilayer and consist of regular terraces separated by the triple SiC bilayer steps on the 6H-SiC(0001) substrates. In situ scanning tunneling microscopy reveals that suppression of pit formation on terraces and uniformity of SiC decomposition at step edges are the key factors to the uniform thickness. By studying the surface morphologies prepared under different annealing rates, it is found that the annealing rate is directly related to SiC decomposition, diffusion of the released Si/C atoms and strain relaxation, which together determine the final step structure and density of defects.

On the tandem Morita-Baylis-Hillman/transesterification processes. Mechanistic insights for the role of protic solvents

NASA Astrophysics Data System (ADS)

Carpanez, Arthur G.; Coelho, Fernando; Amarante, Giovanni W.

2018-02-01

Despite the remarkable rate acceleration under protic solvents such as alcohols and water, the use of acrylates as activated alkenes places a problem due to the possibility of ester hydrolysis or transesterification. Therefore, the tandem transesterification/Morita-Baylis-Hillman (MBH) reactions were investigated by ESI(+)-MS/(MS) and 1H NMR techniques. For the first time, the MBH back-reaction was fully examined by ESI(+)-MS/(MS) using labelling reagents revealed the complex equilibrium involving the Michael-type addition step of DABCO to acrylate. C- and O-protonation were observed at this stage, showing the transesterification process occurs previous to the aldol step, which is the rate-determining step of the mechanism. At this stage, a short-lived tetrahedral intermediate might be involved and should be considered in these processes.

Large-scale uniform bilayer graphene prepared by vacuum graphitization of 6H-SiC(0001) substrates.

PubMed

Wang, Qingyan; Zhang, Wenhao; Wang, Lili; He, Ke; Ma, Xucun; Xue, Qikun

2013-03-06

We report on the preparation of large-scale uniform bilayer graphenes on nominally flat Si-polar 6H-SiC(0001) substrates by flash annealing in ultrahigh vacuum. The resulting graphenes have a single thickness of one bilayer and consist of regular terraces separated by the triple SiC bilayer steps on the 6H-SiC(0001) substrates. In situ scanning tunneling microscopy reveals that suppression of pit formation on terraces and uniformity of SiC decomposition at step edges are the key factors to the uniform thickness. By studying the surface morphologies prepared under different annealing rates, it is found that the annealing rate is directly related to SiC decomposition, diffusion of the released Si/C atoms and strain relaxation, which together determine the final step structure and density of defects.

Observation of inductive effects that cause a change in the rate-determining step for the conversion of rhenium azides to imido complexes.

PubMed

Travia, Nicholas E; Xu, Zhenggang; Keith, Jason M; Ison, Elon A; Fanwick, Phillip E; Hall, Michael B; Abu-Omar, Mahdi M

2011-10-17

The cationic oxorhenium(V) complex [Re(O)(hoz)(2)(CH(3)CN)][B(C(6)F(5))(4)] [1; Hhoz = 2-(2'-hydroxyphenyl)-2-oxazoline] reacts with aryl azides (N(3)Ar) to give cationic cis-rhenium(VII) oxoimido complexes of the general formula [Re(O)(NAr)(hoz)(2)][B(C(6)F(5))(4)] [2a-2f; Ar = 4-methoxyphenyl, 4-methylphenyl, phenyl, 3-methoxyphenyl, 4-chlorophenyl, and 4-(trifluoromethyl)phenyl]. The kinetics of formation of 2 in CH(3)CN are first-order in both azide (N(3)Ar) and oxorhenium(V) complex 1, with second-order rate constants ranging from 3.5 × 10(-2) to 1.7 × 10(-1) M(-1) s(-1). A strong inductive effect is observed for electron-withdrawing substituents, leading to a negative Hammett reaction constant ρ = -1.3. However, electron-donating substituents on phenyl azide deviate significantly from this trend. Enthalpic barriers (ΔH(‡)) determined by the Eyring-Polanyi equation are in the range 14-19 kcal mol(-1) for all aryl azides studied. However, electron-donating 4-methoxyphenyl azide exhibits a large negative entropy of activation, ΔS(‡) = -21 cal mol(-1) K(-1), which is in sharp contrast to the near zero ΔS(‡) observed for phenyl azide and 4-(trifluoromethyl)phenyl azide. The Hammett linear free-energy relationship and the activation parameters support a change in the mechanism between electron-withdrawing and electron-donating aryl azides. Density functional theory predicts that the aryl azides coordinate via N(α) and extrude N(2) directly. For the electron-withdrawing substituents, N(2) extrusion is rate-determining, while for the electron-donating substituents, the rate-determining step becomes the initial attack of the azide. The barriers for these two steps are inverted in their order with respect to the Hammett σ values; thus, the Hammett plot appears with a break in its slope.

Effects of Convective Solute and Impurity Transport in Protein Crystal Growth

NASA Technical Reports Server (NTRS)

Vekilov, Peter G.; Thomas, Bill R.; Rosenberger, Franz

1998-01-01

High-resolution optical interferometry was used to investigate the effects of forced solution convection on the crystal growth kinetics of the model protein lysozyme. Most experiments were conducted with 99.99% pure protein solutions. To study impurity effects, approx. 1% of lysozyme dimer (covalently bound) was added in some cases. We show that the unsteady kinetics, corresponding to bunching of growth steps, can be characterized by the Fourier components of time traces of the growth rate. Specific Fourier spectra are uniquely determined by the solution conditions (composition, temperature, and flow rate) and the growth layer source activity. We found that the average step velocity and growth rate increase by approx. I0% with increasing flow rate, as a result of the enhanced solute supply to the interface. More importantly, faster convective transport results in lower fluctuation amplitudes. This observation supports our rationale for system-dependent effects of transport on the structural perfection of protein crystals. We also found that solution flow rates greater than 500 microns/s result in stronger fluctuations while the average growth rate is decreased. This can lead to growth cessation at low supersaturations. With the intentionally contaminated solutions, these undesirable phenomena occurred at about half the flow rates required in pure solutions. Thus, we conclude that they are due to enhanced convective supply of impurities that are incorporated into the crystal during growth. Furthermore, we found that the impurity effects are reduced at higher crystal growth rates. Since the exposure time of terraces is inversely proportional to the growth rate, this observation suggests that the increased kinetics instability results from impurity adsorption on the interface. Finally, we provide evidence relating earlier observations of "slow protein crystal growth kinetics" to step bunch formation in response to nonsteady step generation.

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.

Numerical Simulation of Nanostructure Growth

NASA Technical Reports Server (NTRS)

Hwang, Helen H.; Bose, Deepak; Govindan, T. R.; Meyyappan, M.

2004-01-01

Nanoscale structures, such as nanowires and carbon nanotubes (CNTs), are often grown in gaseous or plasma environments. Successful growth of these structures is defined by achieving a specified crystallinity or chirality, size or diameter, alignment, etc., which in turn depend on gas mixture ratios. pressure, flow rate, substrate temperature, and other operating conditions. To date, there has not been a rigorous growth model that addresses the specific concerns of crystalline nanowire growth, while demonstrating the correct trends of the processing conditions on growth rates. Most crystal growth models are based on the Burton, Cabrera, and Frank (BCF) method, where adatoms are incorporated into a growing crystal at surface steps or spirals. When the supersaturation of the vapor is high, islands nucleate to form steps, and these steps subsequently spread (grow). The overall bulk growth rate is determined by solving for the evolving motion of the steps. Our approach is to use a phase field model to simulate the growth of finite sized nanowire crystals, linking the free energy equation with the diffusion equation of the adatoms. The phase field method solves for an order parameter that defines the evolving steps in a concentration field. This eliminates the need for explicit front tracking/location, or complicated shadowing routines, both of which can be computationally expensive, particularly in higher dimensions. We will present results demonstrating the effect of process conditions, such as substrate temperature, vapor supersaturation, etc. on the evolving morphologies and overall growth rates of the nanostructures.

Seismic data enhancement and regularization using finite offset Common Diffraction Surface (CDS) stack

NASA Astrophysics Data System (ADS)

Garabito, German; Cruz, João Carlos Ribeiro; Oliva, Pedro Andrés Chira; Söllner, Walter

2017-01-01

The Common Reflection Surface stack is a robust method for simulating zero-offset and common-offset sections with high accuracy from multi-coverage seismic data. For simulating common-offset sections, the Common-Reflection-Surface stack method uses a hyperbolic traveltime approximation that depends on five kinematic parameters for each selected sample point of the common-offset section to be simulated. The main challenge of this method is to find a computationally efficient data-driven optimization strategy for accurately determining the five kinematic stacking parameters on which each sample of the stacked common-offset section depends. Several authors have applied multi-step strategies to obtain the optimal parameters by combining different pre-stack data configurations. Recently, other authors used one-step data-driven strategies based on a global optimization for estimating simultaneously the five parameters from multi-midpoint and multi-offset gathers. In order to increase the computational efficiency of the global optimization process, we use in this paper a reduced form of the Common-Reflection-Surface traveltime approximation that depends on only four parameters, the so-called Common Diffraction Surface traveltime approximation. By analyzing the convergence of both objective functions and the data enhancement effect after applying the two traveltime approximations to the Marmousi synthetic dataset and a real land dataset, we conclude that the Common-Diffraction-Surface approximation is more efficient within certain aperture limits and preserves at the same time a high image accuracy. The preserved image quality is also observed in a direct comparison after applying both approximations for simulating common-offset sections on noisy pre-stack data.

Rate-dependent carbon and nitrogen kinetic isotope fractionation in hydrolysis of isoproturon.

PubMed

Penning, Holger; Cramer, Christopher J; Elsner, Martin

2008-11-01

Stable isotope fractionation permits quantifying contaminant degradation in the field when the transformation reaction is associated with a consistent isotope enrichment factor epsilon. When interpreted in conjunction with dual isotope plots, isotope fractionation is also particularly useful for elucidating reaction mechanisms. To assess the consistency of epsilon and dual isotope slopes in a two-step reaction, we investigated the abiotic hydrolysis of the herbicide isoproturon (3-(4-isopropylphenyl)-1,1-dimethylurea) using a fragmentation method that allows measuring isotope ratios in different parts of the molecule. Carbon and nitrogen position-specific isotope fractionation, as well as slopes in dual isotope plots, varied linearly with rate constants k(obs) depending on the presence of buffers that mediate the initial zwitterion formation. The correlation can be explained by two consecutive reaction steps (zwitterion formation followed by dimethylamine elimination) each of which has a different kinetic isotope effect and may be rate-limiting. Intrinsic isotope effects for both steps, extracted from our kinetic data using a novel theoretical treatment, agree well with values computed from density functional calculations. Our study therefore demonstrates that more variable isotope fractionation may be observed in simple chemical reactions than commonly thought, but that consistent epsilon or dual isotope slopes may nonetheless be encountered in certain molecular fragments.

Leading the Common Core State Standards: From Common Sense to Common Practice

ERIC Educational Resources Information Center

Dunkle, Cheryl A.

2012-01-01

Many educators agree that we already know how to foster student success, so what is keeping common sense from becoming common practice? The author provides step-by-step guidance for overcoming the barriers to adopting the Common Core State Standards (CCSS) and achieving equity and excellence for all students. As an experienced teacher and…

An Official American Thoracic Society Workshop Report

PubMed Central

Wilson, Kevin C.; Gould, Michael K.; Krishnan, Jerry A.; Boyd, Cynthia M.; Brozek, Jan L.; Cooke, Colin R.; Douglas, Ivor S.; Goodman, Richard A.; Joo, Min J.; Lareau, Suzanne; Mularski, Richard A.; Patel, Minal R.; Rosenfeld, Richard M.; Shanawani, Hasan; Slatore, Christopher; Sockrider, Marianna; Sufian, Beth; Thomson, Carey C.; Wiener, Renda Soylemez

2018-01-01

Coexistence of multiple chronic conditions (i.e., multimorbidity) is the most common chronic health problem in adults. However, clinical practice guidelines have primarily focused on patients with a single disease, resulting in uncertainty about the care of patients with multimorbidity. The American Thoracic Society convened a workshop with the goal of establishing a strategy to address multimorbidity within clinical practice guidelines. In this Workshop Report, we describe a framework that addresses multimorbidity in each of the key steps of guideline development: topic selection, panel composition, identifying clinical questions, searching for and synthesizing evidence, rating the quality of that evidence, summarizing benefits and harms, formulating recommendations, and rating the strength of the recommendations. For the consideration of multimorbidity in guidelines to be successful and sustainable, the process must be both feasible and pragmatic. It is likely that this will be achieved best by the step-wise addition and refinement of the various components of the framework. PMID:26963362

Investigation of Particle Sampling Bias in the Shear Flow Field Downstream of a Backward Facing Step

NASA Technical Reports Server (NTRS)

Meyers, James F.; Kjelgaard, Scott O.; Hepner, Timothy E.

1990-01-01

The flow field about a backward facing step was investigated to determine the characteristics of particle sampling bias in the various flow phenomena. The investigation used the calculation of the velocity:data rate correlation coefficient as a measure of statistical dependence and thus the degree of velocity bias. While the investigation found negligible dependence within the free stream region, increased dependence was found within the boundary and shear layers. Full classic correction techniques over-compensated the data since the dependence was weak, even in the boundary layer and shear regions. The paper emphasizes the necessity to determine the degree of particle sampling bias for each measurement ensemble and not use generalized assumptions to correct the data. Further, it recommends the calculation of the velocity:data rate correlation coefficient become a standard statistical calculation in the analysis of all laser velocimeter data.

Using Regression Analysis To Determine If Faculty Salaries Are Overly Compressed. AIR 1997 Annual Forum Paper.

ERIC Educational Resources Information Center

Toutkoushian, Robert K.

This paper proposes a five-step process by which to analyze whether the salary ratio between junior and senior college faculty exhibits salary compression, a term used to describe an unusually small differential between faculty with different levels of experience. The procedure utilizes commonly used statistical techniques (multiple regression…

Method and apparatus for optimizing determination of the originating depth of borehole cuttings

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

Mc Auley, J.A.; Eppler, S.G.

1987-11-24

This patent describes a method for determining the arrival at the surface of an identifiable material from a predetermined drilling depth independent of pump stroke rate and intermittent operations during the utilization of at least a drill bit, a positive displacement mud pump and drilling mud during the drilling of a well. The method comprises the steps of: adding identifiable material to the drilling mud as the drilling mud is being pumped downwardly into the well; initiate count of the pump strokes of the positive displacement mud pump as the previous step occurs; observe arrival of the identifiable material atmore » the surface of the earth as the drilling mud exits from the well; observe the accumulated count of the pump strokes of the positive displacement mud pump which occur between step one and step three; subtract, from the accumulated count of the previous step, the number of pump strokes of the positive displacement mud pump required to pump the identifiable material down to the drill bit to establish a number of lag strokes; and utilize the number obtained in the previous step to identify the arrival of drill cuttings from a predetermined depth.« less

Polarization curve measurements combined with potential probe sensing for determining current density distribution in vanadium redox-flow batteries

NASA Astrophysics Data System (ADS)

Becker, Maik; Bredemeyer, Niels; Tenhumberg, Nils; Turek, Thomas

2016-03-01

Potential probes are applied to vanadium redox-flow batteries for determination of effective felt resistance and current density distribution. During the measurement of polarization curves in 100 cm2 cells with different carbon felt compression rates, alternating potential steps at cell voltages between 0.6 V and 2.0 V are applied. Polarization curves are recorded at different flow rates and states of charge of the battery. Increasing compression rates lead to lower effective felt resistances and a more uniform resistance distribution. Low flow rates at high or low state of charge result in non-linear current density distribution with high gradients, while high flow rates give rise to a nearly linear behavior.

Index Fund Selections with GAs and Classifications Based on Turnover

NASA Astrophysics Data System (ADS)

Orito, Yukiko; Motoyama, Takaaki; Yamazaki, Genji

It is well known that index fund selections are important for the risk hedge of investment in a stock market. The`selection’means that for`stock index futures’, n companies of all ones in the market are selected. For index fund selections, Orito et al.(6) proposed a method consisting of the following two steps : Step 1 is to select N companies in the market with a heuristic rule based on the coefficient of determination between the return rate of each company in the market and the increasing rate of the stock price index. Step 2 is to construct a group of n companies by applying genetic algorithms to the set of N companies. We note that the rule of Step 1 is not unique. The accuracy of the results using their method depends on the length of time data (price data) in the experiments. The main purpose of this paper is to introduce a more`effective rule’for Step 1. The rule is based on turnover. The method consisting of Step 1 based on turnover and Step 2 is examined with numerical experiments for the 1st Section of Tokyo Stock Exchange. The results show that with our method, it is possible to construct the more effective index fund than the results of Orito et al.(6). The accuracy of the results using our method depends little on the length of time data (turnover data). The method especially works well when the increasing rate of the stock price index over a period can be viewed as a linear time series data.

47 CFR 54.605 - Determining the urban rate.

Code of Federal Regulations, 2010 CFR

2010-10-01

....605 Telecommunication FEDERAL COMMUNICATIONS COMMISSION (CONTINUED) COMMON CARRIER SERVICES (CONTINUED) UNIVERSAL SERVICE Universal Service Support for Health Care Providers § 54.605 Determining the urban rate. (a) If a rural health care provider requests an eligible service to be provided over a distance that...

Clomiphene citrate 'stair-step' protocol vs. traditional protocol in patients with polycystic ovary syndrome: a randomized controlled trial.

PubMed

Deveci, Canan Dura; Demir, Berfu; Sengul, Ozlem; Dilbaz, Berna; Goktolga, Umit

2015-01-01

To evaluate the efficacy of the stair-step protocol using clomiphene citrate (CC) and to assess the uterine and systemic side effects in patients with polycystic ovary syndrome (PCOS). A total of 60 PCOS patients who failed to respond to 50 mg/day for 5 days of CC treatment within the cycle were randomly allocated to the control (traditional protocol) and study (stair-step protocol) groups. In the stair-step protocol,patients were treated with CC 50 mg/day for 5 days and then in nonresponsive patients, the dosage was increased to 100 mg/day for 5 days in the same cycle. Patients who failed the 50 mg/day CC treatment in the previous cycle were stimulated with 100 mg/day CC and were accepted as the control group. Ovulation and pregnancy rates, duration of treatment and uterine and systemic side effects were evaluated. Ovulation and pregnancy rates were similar between the stair-step and the control group (43.3 vs. 33.3 %, respectively) (16.7 vs. 10 %, respectively). The duration of treatment was significantly shorter in stair-step compared to traditional protocol (20.5 ± 2.0 vs. 48.6 ± 2.4 days, respectively). There were no significant differences in the systemic side effects between the groups. Uterine side effects were evaluated with endometrial thickness and uterine artery Doppler ultrasound; no significant differences were observed in stair-step compared to traditional protocol. The stair-step protocol was determined to have a significantly shorter treatment period without any detrimental effect on the ovulation and pregnancy rates.

Effect of Processing Steps on the Mechanical Properties and Surface Appearance of 6063 Aluminium Extruded Products

PubMed Central

Asensio-Lozano, Juan; Suárez-Peña, Beatriz; Vander Voort, George F.

2014-01-01

6063 aluminum anodized extrusions may exhibit a common surface defect known as streaking, characterized by the formation of narrow bands with a surface gloss different from the surrounding material. The origin of this banding lies in the differential surface topography produced after etching during the anodizing stage, shown to be connected to certain microstructural characteristics. The present study has attempted to determine the origin of these defects and measure the mechanical properties in these zones, properties which were either barely acceptable or did not meet the specification’s requirements. Quantitative metallography and mechanical testing, both tensile and microhardness, were used for materials assessment at the different steps of the process of manufacturing 6063 anodized extrusions. The results of this research show that nonequilibrium solidification rates during billet casting could lead to the formation of coarse eutectic Mg2Si particles which have a deleterious effect on both mechanical properties and surface appearance in the anodized condition. However, differences in the size and density of the coarse Mg2Si particles have been found to exist in the streak profile compared to the surrounding zones. The study revealed the importance of these particles in explaining the origin of the marginal or sub-marginal properties and anodizing surface defects found. PMID:28788673

Effect of Processing Steps on the Mechanical Properties and Surface Appearance of 6063 Aluminium Extruded Products.

PubMed

Asensio-Lozano, Juan; Suárez-Peña, Beatriz; Vander Voort, George F

2014-05-30

6063 aluminum anodized extrusions may exhibit a common surface defect known as streaking, characterized by the formation of narrow bands with a surface gloss different from the surrounding material. The origin of this banding lies in the differential surface topography produced after etching during the anodizing stage, shown to be connected to certain microstructural characteristics. The present study has attempted to determine the origin of these defects and measure the mechanical properties in these zones, properties which were either barely acceptable or did not meet the specification's requirements. Quantitative metallography and mechanical testing, both tensile and microhardness, were used for materials assessment at the different steps of the process of manufacturing 6063 anodized extrusions. The results of this research show that nonequilibrium solidification rates during billet casting could lead to the formation of coarse eutectic Mg₂Si particles which have a deleterious effect on both mechanical properties and surface appearance in the anodized condition. However, differences in the size and density of the coarse Mg₂Si particles have been found to exist in the streak profile compared to the surrounding zones. The study revealed the importance of these particles in explaining the origin of the marginal or sub-marginal properties and anodizing surface defects found.

Computational modeling of soot nucleation

NASA Astrophysics Data System (ADS)

Chung, Seung-Hyun

Recent studies indicate that soot is the second most significant driver of climate change---behind CO2, but ahead of methane---and increased levels of soot particles in the air are linked to health hazards such as heart disease and lung cancer. Within the soot formation process, soot nucleation is the least understood step, and current experimental findings are still limited. This thesis presents computational modeling studies of the major pathways of the soot nucleation process. In this study, two regimes of soot nucleation---chemical growth and physical agglomeration---were evaluated and the results demonstrated that combustion conditions determine the relative importance of these two routes. Also, the dimerization process of polycyclic aromatic hydrocarbons, which has been regarded as one of the most important physical agglomeration processes in soot formation, was carefully examined with a new method for obtaining the nucleation rate using molecular dynamics simulation. The results indicate that the role of pyrene dimerization, which is the commonly accepted model, is expected to be highly dependent on various flame temperature conditions and may not be a key step in the soot nucleation process. An additional pathway, coronene dimerization in this case, needed to be included to improve the match with experimental data. The results of this thesis provide insight on the soot nucleation process and can be utilized to improve current soot formation models.

Oxidation of L-phenylalanine by diperiodatoargentate(III) in aqueous alkaline medium. A Mechanistic approach

NASA Astrophysics Data System (ADS)

Lamani, S. D.; Veeresh, T. M.; Nandibewoor, S. T.

2009-12-01

The kinetics of oxidation of L-phenylalanine (L-Phe) by diperiodatoargentate(III) (DPA) in alkaline medium at a constant ionic strength of 0.25 mol/dm-3 has been studied spectrophotometrically. The reaction between DPA and L-phenylalanine in alkaline medium exhibits 1: 1 stoichiometry (L-phenylalanine: DPA). The reaction shows first order in [DPA] and has less than unit order dependence each in both [L-Phe] and [Alkali] and retarding effect of [IO{4/-}] under the reaction conditions. The active species of DPA is understood to be as monoperiodatoargentate(III) (MPA). The reaction is shown to proceed via a MPA-L-Phe complex, which decomposes in a rate-determining step to give intermediates followed by a fast step to give the products. The products were identified by spot and spectroscopic studies. The reaction constants involved in the different steps of the mechanisms were calculated. The activation parameters with respect to slow step of the mechanism were computed and discussed. The thermodynamic quantities were also determined for the reaction.

Infliximab "Top-Down" Strategy is Superior to "Step-Up" in Maintaining Long-Term Remission in the Treatment of Pediatric Crohn Disease.

PubMed

Lee, Yoo Min; Kang, Ben; Lee, Yoon; Kim, Mi Jin; Choe, Yon Ho

2015-06-01

We aimed to compare the efficacy of remission maintenance between infliximab "top-down" and "step-up" strategies in moderate to severe pediatric Crohn disease during 3 years. We also aimed to determine prognostic factors that may influence the relapse-free rate in these patients. The present study was a retrospective review of a prospective cohort, based on an infliximab treatment protocol for pediatric Crohn disease used at Samsung Medical Center. A total of 31 patients (group A) were treated with early infliximab induction ("top-down" strategy) and 20 patients (group B) refractory to conventional therapy underwent infliximab treatment ("step-up" strategy). The efficacy of infliximab treatment was assessed by relapse-free rate and remission period rate for 3 years. A total of 11 prognostic factors that may influence the relapse-free rate were further analyzed. The relapse-free rates at 3 years were 35.5% (95% confidence interval [CI] 0.194-0.519) in group A and 15.0% (95% CI 0.037-0.335) in group B (P = 0.0094). Overall remission period rate for 3 years also showed a significant difference between the 2 groups (92.1%  ± 7.2% vs 78.3%  ± 16.6%; P = 0.005). Multivariable analysis revealed that the duration from the initial diagnosis to infliximab infusion was the only factor associated with relapse-free remission for 3 years (hazard ratio = 1.077; 95% CI 1.025-1.131). "Top-down" strategy had a longer remission period compared with the "step-up" strategy in pediatric Crohn disease during a study period of 3 years, based on relapse-free rate and remission period rate. Earlier introduction of infliximab is recommended in pediatric patients with moderate to severe Crohn disease.

Analysis of Convective Weather Impact on Pre-Departure Routing of Flights from Fort Worth Center to New York Center

NASA Technical Reports Server (NTRS)

Arneson, Heather; Bombelli, Alessandro; Segarra-Torne, Adria; Tse, Elmer

2017-01-01

In response to severe weather conditions, Traffic Managers specify flow constraints and reroutes to route air traffic around affected regions of airspace. Providing analysis and recommendations of available reroute options and associated airspace capacities would assist Traffic Managers in making more efficient decisions in response to convective weather. These recommendations can be developed by examining historical data to determine which previous reroute options were used in similar weather and traffic conditions. This paper describes the initial steps and methodology used towards this goal. The focus of this work is flights departing from Fort Worth Center destined for New York Center. Dominant routing structures used in the absence of convective weather are identified. A method to extract relevant features from the large volume of weather data available to quantify the impact of convective weather on this routing structure over a given time range is presented. Finally, a method of estimating flow rate capacity along commonly used routes during convective weather events is described. Results show that the flow rates drop exponentially as a function of the values of the proposed feature and that convective weather on the final third of the route was found to have a greater impact on the flow rate restriction than other portions of the route.

On-line approaches for the determination of residues and contaminants in complex samples.

PubMed

Fumes, Bruno Henrique; Andrade, Mariane Aissa; Franco, Maraíssa Silva; Lanças, Fernando Mauro

2017-01-01

The determination of residues and contaminants in complex matrices such as in the case of food, environmental, and biological samples requires a combination of several steps to succeed in the aimed goal. At least three independent steps are integrated to provide the best available situation to deal with such matrices: (1) a sample preparation technique is employed to isolate the target compounds from the rest of the matrix; (2) a chromatographic (second) step further "purifies" the isolated compounds from the co-extracted matrix interferences; (3) a spectroscopy-based device acts as chromatographic detector (ideally containing a tandem high-resolution mass analyzer) for the qualitative and quantitative analysis. These techniques can be operated in different modes including the off-line and the on-line modes. The present report focus the on-line coupling techniques aiming the determination of analytes present in complex matrices. The fundamentals of these approaches as well as the most common set ups are presented and discussed, as well as a review on the recent applications of these two approaches to the fields of bioanalytical, environmental, and food analysis are critically discussed. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Comparison of energy expenditure and heart rate responses between three commercial group fitness classes.

PubMed

Wickham, James B; Mullen, Nicholas J; Whyte, Douglas G; Cannon, Jack

2017-07-01

The objectives of this study were to compare the energy expenditure and heart rate responses between three commercial group fitness classes (group resistance exercise [PUMP]; indoor stationary cycling [RIDE]; and step aerobics [STEP]). One-Way Repeated Measures incorporating a Latin Square Design for class randomisation. Ten participants (5 males and 5 females) completed each group fitness class in random order with energy expenditure and heart rate determined using an Actiheart monitor. STEP and RIDE produced significantly (p<0.05) higher average heart rates (HR avg ) (85.8±5.1% and 86.4±4.3% of HR max , respectively) compared to PUMP (73.7±7% of HR max ). HR peak was also significantly (p<0.05) higher in STEP and RIDE (97.1±4.7% and 95.6±4.5% of HR max, respectively) when compared with the PUMP class (90±5.9% of HR max ). Total energy expenditure (TEE), both absolute and relative, were significantly (p<0.05) higher for STEP (2101.7±560.2kJ and 0.59±0.07kJkg -1 min -1 ) and RIDE (1880.4±420kJ and 0.58±0.03kJkg -1 min -1 ) when compared with the PUMP class (1385.1±504kJ and 0.36±0.07kJkg -1 min -1 ). These data suggest that overall exercise intensity and energy expenditure was highly comparable between RIDE and STEP, which suggests these group fitness classes are more effective for developing cardiovascular fitness and assisting with weight management compared with group resistance exercise classes when performed on a regular basis. Copyright © 2017 Sports Medicine Australia. Published by Elsevier Ltd. All rights reserved.

Kinetics of dissolution of UO2 in nitric acid solutions: A multiparametric study of the non-catalysed reaction

NASA Astrophysics Data System (ADS)

Cordara, T.; Szenknect, S.; Claparede, L.; Podor, R.; Mesbah, A.; Lavalette, C.; Dacheux, N.

2017-12-01

UO2 pellets were prepared by densification of oxides obtained from the conversion of the oxalate precursor. Then characterized in order to perform a multiparametric study of the dissolution in nitric acid medium. In this frame, for each sample, the densification rate, the grain size and the specific surface area of the prepared pellets were determined prior to the final dissolution experiments. By varying the concentration of the nitric acid solution and temperature, three different and successive steps were identified during the dissolution. Under the less aggressive conditions considered, a first transient step corresponding to the dissolution of the most reactive phases was observed at the solid/solution interface. Then, for all the tested conditions, a steady state step was established during which the normalised dissolution rate was found to be constant. It was followed by a third step characterized by a strong and continuous increase of the normalised dissolution rate. The duration of the steady state, also called "induction period", was found to vary drastically as a function of the HNO3 concentration and temperature. However, independently of the conditions, this steady state step stopped at almost similar dissolved material weight loss and dissolved uranium concentration. During the induction period, no important evolution of the topology of the solid/liquid interface was evidenced authorizing the use of the starting reactive specific surface area to evaluate the normalised dissolution rates thus the chemical durability of the sintered pellets. From the multiparametric study of UO2 dissolution proposed, oxidation of U(IV) to U(VI) by nitrate ions at the solid/liquid interface constitutes the limiting step in the overall dissolution mechanism associated to this induction period.

Biomechanical influences on balance recovery by stepping.

PubMed

Hsiao, E T; Robinovitch, S N

1999-10-01

Stepping represents a common means for balance recovery after a perturbation to upright posture. Yet little is known regarding the biomechanical factors which determine whether a step succeeds in preventing a fall. In the present study, we developed a simple pendulum-spring model of balance recovery by stepping, and used this to assess how step length and step contact time influence the effort (leg contact force) and feasibility of balance recovery by stepping. We then compared model predictions of step characteristics which minimize leg contact force to experimentally observed values over a range of perturbation strengths. At all perturbation levels, experimentally observed step execution times were higher than optimal, and step lengths were smaller than optimal. However, the predicted increase in leg contact force associated with these deviations was substantial only for large perturbations. Furthermore, increases in the strength of the perturbation caused subjects to take larger, quicker steps, which reduced their predicted leg contact force. We interpret these data to reflect young subjects' desire to minimize recovery effort, subject to neuromuscular constraints on step execution time and step length. Finally, our model predicts that successful balance recovery by stepping is governed by a coupling between step length, step execution time, and leg strength, so that the feasibility of balance recovery decreases unless declines in one capacity are offset by enhancements in the others. This suggests that one's risk for falls may be affected more by small but diffuse neuromuscular impairments than by larger impairment in a single motor capacity.

Quality Control of Structural MRI Images Applied Using FreeSurfer—A Hands-On Workflow to Rate Motion Artifacts

PubMed Central

Backhausen, Lea L.; Herting, Megan M.; Buse, Judith; Roessner, Veit; Smolka, Michael N.; Vetter, Nora C.

2016-01-01

In structural magnetic resonance imaging motion artifacts are common, especially when not scanning healthy young adults. It has been shown that motion affects the analysis with automated image-processing techniques (e.g., FreeSurfer). This can bias results. Several developmental and adult studies have found reduced volume and thickness of gray matter due to motion artifacts. Thus, quality control is necessary in order to ensure an acceptable level of quality and to define exclusion criteria of images (i.e., determine participants with most severe artifacts). However, information about the quality control workflow and image exclusion procedure is largely lacking in the current literature and the existing rating systems differ. Here, we propose a stringent workflow of quality control steps during and after acquisition of T1-weighted images, which enables researchers dealing with populations that are typically affected by motion artifacts to enhance data quality and maximize sample sizes. As an underlying aim we established a thorough quality control rating system for T1-weighted images and applied it to the analysis of developmental clinical data using the automated processing pipeline FreeSurfer. This hands-on workflow and quality control rating system will aid researchers in minimizing motion artifacts in the final data set, and therefore enhance the quality of structural magnetic resonance imaging studies. PMID:27999528

Cooperative catalytic methoxycarbonylation of alkenes: uncovering the role of palladium complexes with hemilabile ligands† †Electronic supplementary information (ESI) available. See DOI: 10.1039/c7sc02964k

PubMed Central

Dong, Kaiwu; Sang, Rui; Wei, Zhihong; Liu, Jie; Dühren, Ricarda; Spannenberg, Anke; Jiao, Haijun; Neumann, Helfried; Jackstell, Ralf; Franke, Robert

2018-01-01

Mechanistic studies of the catalyst [Pd2(dba)3/1,1′-bis(tert-butyl(pyridin-2-yl)phosphanyl)ferrocene, L2] for olefin alkoxycarbonylation reactions are described. X-ray crystallography reveals the coordination of the pyridyl nitrogen atom in L2 to the palladium center of the catalytic intermediates. DFT calculations on the elementary steps of the industrially relevant carbonylation of ethylene (the Lucite α-process) indicate that the protonated pyridyl moiety is formed immediately, which facilitates the formation of the active palladium hydride complex. The insertion of ethylene and CO into this intermediate leads to the corresponding palladium acyl species, which is kinetically reversible. Notably, this key species is stabilized by the hemilabile coordination of the pyridyl nitrogen atom in L2. The rate-determining alcoholysis of the acyl palladium complex is substantially facilitated by metal–ligand cooperation. Specifically, the deprotonation of the alcohol by the built-in base of the ligand allows a facile intramolecular nucleophilic attack on the acyl palladium species concertedly. Kinetic measurements support this mechanistic proposal and show that the rate of the carbonylation step is zero-order dependent on ethylene and CO. Comparing CH3OD and CH3OH as nucleophiles suggests the involvement of (de)protonation in the rate-determining step. PMID:29732128

Nonlinear Analyte Concentration Gradients for One-Step Kinetic Analysis Employing Optical Microring Resonators

PubMed Central

Marty, Michael T.; Kuhnline Sloan, Courtney D.; Bailey, Ryan C.; Sligar, Stephen G.

2012-01-01

Conventional methods to probe the binding kinetics of macromolecules at biosensor surfaces employ a stepwise titration of analyte concentrations and measure the association and dissociation to the immobilized ligand at each concentration level. It has previously been shown that kinetic rates can be measured in a single step by monitoring binding as the analyte concentration increases over time in a linear gradient. We report here the application of nonlinear analyte concentration gradients for determining kinetic rates and equilibrium binding affinities in a single experiment. A versatile nonlinear gradient maker is presented, which is easily applied to microfluidic systems. Simulations validate that accurate kinetic rates can be extracted for a wide range of association and dissociation rates, gradient slopes and curvatures, and with models for mass transport. The nonlinear analyte gradient method is demonstrated with a silicon photonic microring resonator platform to measure prostate specific antigen-antibody binding kinetics. PMID:22686186

Nonlinear analyte concentration gradients for one-step kinetic analysis employing optical microring resonators.

PubMed

Marty, Michael T; Sloan, Courtney D Kuhnline; Bailey, Ryan C; Sligar, Stephen G

2012-07-03

Conventional methods to probe the binding kinetics of macromolecules at biosensor surfaces employ a stepwise titration of analyte concentrations and measure the association and dissociation to the immobilized ligand at each concentration level. It has previously been shown that kinetic rates can be measured in a single step by monitoring binding as the analyte concentration increases over time in a linear gradient. We report here the application of nonlinear analyte concentration gradients for determining kinetic rates and equilibrium binding affinities in a single experiment. A versatile nonlinear gradient maker is presented, which is easily applied to microfluidic systems. Simulations validate that accurate kinetic rates can be extracted for a wide range of association and dissociation rates, gradient slopes, and curvatures, and with models for mass transport. The nonlinear analyte gradient method is demonstrated with a silicon photonic microring resonator platform to measure prostate specific antigen-antibody binding kinetics.

Determination of pyrophosphate and sulfate using polyhexamethylene guanidine hydrochloride-stabilized silver nanoparticles.

PubMed

Terenteva, E A; Apyari, V V; Dmitrienko, S G; Garshev, A V; Volkov, P A; Zolotov, Yu A

2018-04-01

Positively charged polyhexamethylene guanidine hydrochloride-stabilized silver nanoparticles (PHMG-AgNPs) were prepared and applied as a colorimetric probe for single-step determination of pyrophosphate and sulfate. The approach is based on the nanoparticles aggregation leading to change in their absorption spectra and color of the solution. Due to both electrostatic and steric stabilization these nanoparticles show decreased sensitivity relatively to many common anions, which allows for simple and rapid direct single-step determination of pyrophosphate and sulfate. Effects of different factors (time of interaction, pH, concentrations of anions and the nanoparticles) on aggregation of PHMG-AgNPs and analytical performance of the procedure were investigated. The method allows for the determination of pyrophosphate and sulfate in the range of 0.16-2μgmL -1 and 20-80μgmL -1 with RSD of 2-5%, respectively. The analysis can be performed using either spectrophotometry or naked-eye detection. Practical application of the method was shown by the example of pyrophosphate determination in baking powder sample. Copyright © 2017 Elsevier B.V. All rights reserved.

Lewis Acid-Induced Change from Four- to Two-Electron Reduction of Dioxygen Catalyzed by Copper Complexes Using Scandium Triflate

PubMed Central

Kakuda, Saya; Rolle, Clarence; Ohkubo, Kei; Siegler, Maxime A.; Karlin, Kenneth D.; Fukuzumi, Shunichi

2015-01-01

Mononuclear copper complexes, [(tmpa)CuII(CH3CN)](ClO4)2 (1, tmpa = tris(2-pyridylmethyl)amine) and [(BzQ)CuII(H2O)2](ClO4)2 (2, BzQ = bis(2-quinolinylmethyl)benzylamine)], act as efficient catalysts for the selective two-electron reduction of O2 by ferrocene derivatives in the presence of scandium triflate (Sc(OTf)3), in acetone, whereas 1 catalyzes the four-electron reduction of O2 by the same reductant in the presence of Brønsted acids such as triflic acid. Following formation of the peroxo-bridged dicopper(II) complex [(tmpa)CuII(O2)CuII(tmpa)]2+, the two-electron reduced product of O2 with Sc3+ is observed to be scandium peroxide ([Sc3+(O22−)]+). In the presence of three equiv of hexamethylphosphoric triamide (HMPA), [Sc3+(O22−)]+ was oxidized by [Fe(bpy)3]3+ (bpy = 2,2′-bipyridine) to the known superoxide species [(HMPA)3Sc3+(O2•−)]2+ as detected by EPR spectroscopy. A kinetic study revealed that the rate-determining step of the catalytic cycle for the two-electron reduction of O2 with 1 is electron transfer from Fc* to 1 to give a cuprous complex which is highly reactive toward O2, whereas the rate-determining step with 2 is changed to the reaction of the cuprous complex with O2 following electron transfer from ferrocene derivatives to 2. The explanation for the change in catalytic O2-reaction stoichiometry from four-electron with Brønsted acids to two-electron reduction in the presence of Sc3+ and also for the change in the rate-determining step is clarified based on a kinetics interrogation of the overall catalytic cycle as well as each step of the catalytic cycle with study of the observed effects of Sc3+ on copper-oxygen intermediates. PMID:25659416

Atomic-Scale Design of Iron Fischer-Tropsch Catalysts: A Combined Computational Chemistry, Experimental, and Microkinetic Modeling Approach

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

Manos Mavrikakis; James A. Dumesic; Rahul P. Nabar

2006-09-29

Work continued on the development of a microkinetic model of Fischer-Tropsch synthesis (FTS) on supported and unsupported Fe catalysts. The following aspects of the FT mechanism on unsupported iron catalysts were investigated on during this third year: (1) the collection of rate data in a Berty CSTR reactor based on sequential design of experiments; (2) CO adsorption and CO-TPD for obtaining the heat of adsorption of CO on polycrystalline iron; and (3) isothermal hydrogenation (IH) after Fischer Tropsch reaction to identify and quantify surface carbonaceous species. Rates of C{sub 2+} formation on unsupported iron catalysts at 220 C and 20more » atm correlated well to a Langmuir-Hinshelwood type expression, derived assuming carbon hydrogenation to CH and OH recombination to water to be rate-determining steps. From desorption of molecularly adsorbed CO at different temperatures the heat of adsorption of CO on polycrystalline iron was determined to be 100 kJ/mol. Amounts and types of carbonaceous species formed after FT reaction for 5-10 minutes at 150, 175, 200 and 285 C vary significantly with temperature. Mr. Brian Critchfield completed his M.S. thesis work on a statistically designed study of the kinetics of FTS on 20% Fe/alumina. Preparation of a paper describing this work is in progress. Results of these studies were reported at the Annual Meeting of the Western States Catalysis and at the San Francisco AIChE meeting. In the coming period, studies will focus on quantitative determination of the rates of kinetically-relevant elementary steps on unsupported Fe catalysts with/without K and Pt promoters by SSITKA method. This study will help us to (1) understand effects of promoter and support on elementary kinetic parameters and (2) build a microkinetics model for FTS on iron. Calculations using periodic, self-consistent Density Functional Theory (DFT) methods were performed on models of defected Fe surfaces, most significantly the stepped Fe(211) surface. Binding Energies (BE's), preferred adsorption sites and geometries of all the FTS relevant stable species and intermediates were evaluated. Each elementary step of our reaction model was fully characterized with respect to its thermochemistry and comparisons between the stepped Fe(211) facet and the most-stable Fe(110) facet were established. In most cases the BE's on Fe(211) reflected the trends observed earlier on Fe(110), yet there were significant variations imposed on the underlying trends. Vibrational frequencies were evaluated for the preferred adsorption configurations of each species with the aim of evaluating the entropy-changes and preexponential factors for each elementary step. Kinetic studies were performed for the early steps of FTS (up to CH{sub 4} formation) and CO dissociation. This involved evaluation of the Minimum Energy Pathway (MEP) and activation energy barrier for the steps involved. We concluded that Fe(211) would allow for far more facile CO dissociation in comparison to other Fe catalysts studied so far, but the other FTS steps studied remained mostly unchanged.« less

Specificity and kinetics of haloalkane dehalogenase.

PubMed

Schanstra, J P; Kingma, J; Janssen, D B

1996-06-21

Haloalkane dehalogenase converts halogenated alkanes to their corresponding alcohols. The active site is buried inside the protein and lined with hydrophobic residues. The reaction proceeds via a covalent substrate-enzyme complex. This paper describes a steady-state and pre-steady-state kinetic analysis of the conversion of a number of substrates of the dehalogenase. The kinetic mechanism for the "natural" substrate 1,2-dichloroethane and for the brominated analog and nematocide 1,2-dibromoethane are given. In general, brominated substrates had a lower Km, but a similar kcat than the chlorinated analogs. The rate of C-Br bond cleavage was higher than the rate of C-Cl bond cleavage, which is in agreement with the leaving group abilities of these halogens. The lower Km for brominated compounds therefore originates both from the higher rate of C-Br bond cleavage and from a lower Ks for bromo-compounds. However, the rate-determining step in the conversion (kcat) of 1, 2-dibromoethane and 1,2-dichloroethane was found to be release of the charged halide ion out of the active site cavity, explaining the different Km but similar kcat values for these compounds. The study provides a basis for the analysis of rate-determining steps in the hydrolysis of various environmentally important substrates.

Experimental study on the stability and failure of individual step-pool

NASA Astrophysics Data System (ADS)

Zhang, Chendi; Xu, Mengzhen; Hassan, Marwan A.; Chartrand, Shawn M.; Wang, Zhaoyin

2018-06-01

Step-pools are one of the most common bedforms in mountain streams, the stability and failure of which play a significant role for riverbed stability and fluvial processes. Given this importance, flume experiments were performed with a manually constructed step-pool model. The experiments were carried out with a constant flow rate to study features of step-pool stability as well as failure mechanisms. The results demonstrate that motion of the keystone grain (KS) caused 90% of the total failure events. The pool reached its maximum depth and either exhibited relative stability for a period before step failure, which was called the stable phase, or the pool collapsed before its full development. The critical scour depth for the pool increased linearly with discharge until the trend was interrupted by step failure. Variability of the stable phase duration ranged by one order of magnitude, whereas variability of pool scour depth was constrained within 50%. Step adjustment was detected in almost all of the runs with step-pool failure and was one or two orders smaller than the diameter of the step stones. Two discharge regimes for step-pool failure were revealed: one regime captures threshold conditions and frames possible step-pool failure, whereas the second regime captures step-pool failure conditions and is the discharge of an exceptional event. In the transitional stage between the two discharge regimes, pool and step adjustment magnitude displayed relatively large variabilities, which resulted in feedbacks that extended the duration of step-pool stability. Step adjustment, which was a type of structural deformation, increased significantly before step failure. As a result, we consider step deformation as the direct explanation to step-pool failure rather than pool scour, which displayed relative stability during step deformations in our experiments.

A modular modulation method for achieving increases in metabolite production.

PubMed

Acerenza, Luis; Monzon, Pablo; Ortega, Fernando

2015-01-01

Increasing the production of overproducing strains represents a great challenge. Here, we develop a modular modulation method to determine the key steps for genetic manipulation to increase metabolite production. The method consists of three steps: (i) modularization of the metabolic network into two modules connected by linking metabolites, (ii) change in the activity of the modules using auxiliary rates producing or consuming the linking metabolites in appropriate proportions and (iii) determination of the key modules and steps to increase production. The mathematical formulation of the method in matrix form shows that it may be applied to metabolic networks of any structure and size, with reactions showing any kind of rate laws. The results are valid for any type of conservation relationships in the metabolite concentrations or interactions between modules. The activity of the module may, in principle, be changed by any large factor. The method may be applied recursively or combined with other methods devised to perform fine searches in smaller regions. In practice, it is implemented by integrating to the producer strain heterologous reactions or synthetic pathways producing or consuming the linking metabolites. The new procedure may contribute to develop metabolic engineering into a more systematic practice. © 2015 American Institute of Chemical Engineers.

Relationship of Catalysis and Active Site Loop Dynamics in the (βα)8-Barrel Enzyme Indole-3-glycerol Phosphate Synthase.

PubMed

Schlee, Sandra; Klein, Thomas; Schumacher, Magdalena; Nazet, Julian; Merkl, Rainer; Steinhoff, Heinz-Jürgen; Sterner, Reinhard

2018-03-08

It is important to understand how the catalytic activity of enzymes is related to their conformational flexibility. We have studied this activity-flexibility correlation using the example of indole-3-glycerol phosphate synthase from Sulfolobus solfataricus (ssIGPS), which catalyzes the fifth step in the biosynthesis of tryptophan. ssIGPS is a thermostable representative of enzymes with the frequently encountered and catalytically versatile (βα) 8 -barrel fold. Four variants of ssIGPS with increased catalytic turnover numbers were analyzed by transient kinetics at 25 °C, and wild-type ssIGPS was likewise analyzed both at 25 °C and at 60 °C. Global fitting with a minimal three-step model provided the individual rate constants for substrate binding, chemical transformation, and product release. The results showed that in both cases, namely, the application of activating mutations and temperature increase, the net increase in the catalytic turnover number is afforded by acceleration of the product release rate relative to the chemical transformation steps. Measurements of the solvent viscosity effect at 25 °C versus 60 °C confirmed this change in the rate-determining step with temperature, which is in accordance with a kink in the Arrhenius diagram of ssIGPS at ∼40 °C. When rotational diffusion rates of electron paramagnetic spin-labels attached to active site loop β1α1 are plotted in the form of an Arrhenius diagram, kinks are observed at the same temperature. These findings, together with molecular dynamics simulations, demonstrate that a different degree of loop mobility correlates with different rate-limiting steps in the catalytic mechanism of ssIGPS.

Step length after discrete perturbation predicts accidental falls and fall-related injury in elderly people with a range of peripheral neuropathy.

PubMed

Allet, Lara; Kim, Hogene; Ashton-Miller, James; De Mott, Trina; Richardson, James K

2014-01-01

Distal symmetric polyneuropathy increases fall risk due to inability to cope with perturbations. We aimed to 1) identify the frontal plane lower limb sensorimotor functions which are necessary for robustness to a discrete, underfoot perturbation during gait; and 2) determine whether changes in the post-perturbed step parameters could distinguish between fallers and non fallers. Forty-two subjects (16 healthy old and 26 with diabetic PN) participated. Frontal plane lower limb sensorimotor functions were determined using established laboratory-based techniques. The subjects' most extreme alterations in step width or step length in response to a perturbation were measured. In addition, falls and fall-related injuries were prospectively recorded. Ankle proprioceptive threshold (APrT; p=.025) and hip abduction rate of torque generation (RTG; p=.041) independently predicted extreme step length after medial perturbation, with precise APrT and greater hip RTG allowing maintenance of step length. Injured subjects demonstrated greater extreme step length changes after medial perturbation than non-injured subjects (percent change = 18.5 ± 9.2 vs. 11.3 ± 4.57; p = .01). The ability to rapidly generate frontal plane hip strength and/or precisely perceive motion at the ankle is needed to maintain a normal step length after perturbation, a parameter which distinguishes between subjects sustaining a fall-related injury and those who did not. © 2014.

Step length after discrete perturbation predicts accidental falls and fall-related injury in elderly people with a range of peripheral neuropathy

PubMed Central

Allet, L; Kim, H; Ashton-Miller, JA; De Mott, T; Richardson, JK

2013-01-01

Aims Distal symmetric polyneuropathy increases fall risk due to inability to cope with perturbations. We aimed to 1) identify the frontal plane lower limb sensorimotor functions which are necessary for robustness to a discrete, underfoot perturbation during gait; and 2) determine whether changes in the post-perturbed step parameters could distinguish between fallers and non fallers. Methods Forty-two subjects (16 healthy old and 26 with diabetic PN) participated. Frontal plane lower limb sensorimotor functions were determined using established laboratory-based techniques. The subjects' most extreme alterations in step width or step length in response to a perturbation were measured. In addition, falls and fall-related injuries were prospectively recorded. Results Ankle proprioceptive threshold (APrT; p=.025) and hip abduction rate of torque generation (RTG; p=.041) independently predicted extreme step length after medial perturbation, with precise APrT and greater hip RTG allowing maintenance of step length. Fallers demonstrated greater extreme step length changes after medial perturbation than non fallers (percent change = 16.41±8.42 vs 11.0±4.95; p=.06) Conclusions The ability to rapidly generate frontal plane hip strength and/or precisely perceive motion at the ankle is needed to maintain a normal step length after perturbation, a parameter, which distinguishes between fallers and non fallers. PMID:24183899

Study of inhaler technique in asthma patients: differences between pediatric and adult patients

PubMed Central

Manríquez, Pablo; Acuña, Ana María; Muñoz, Luis; Reyes, Alvaro

2015-01-01

Objective: Inhaler technique comprises a set of procedures for drug delivery to the respiratory system. The oral inhalation of medications is the first-line treatment for lung diseases. Using the proper inhaler technique ensures sufficient drug deposition in the distal airways, optimizing therapeutic effects and reducing side effects. The purposes of this study were to assess inhaler technique in pediatric and adult patients with asthma; to determine the most common errors in each group of patients; and to compare the results between the two groups. Methods: This was a descriptive cross-sectional study. Using a ten-step protocol, we assessed inhaler technique in 135 pediatric asthma patients and 128 adult asthma patients. Results: The most common error among the pediatric patients was failing to execute a 10-s breath-hold after inhalation, whereas the most common error among the adult patients was failing to exhale fully before using the inhaler. Conclusions: Pediatric asthma patients appear to perform most of the inhaler technique steps correctly. However, the same does not seem to be true for adult patients. PMID:26578130

A quantum dynamical study of the He++2He-->He2++He reaction

NASA Astrophysics Data System (ADS)

Xie, Junkai; Poirier, Bill; Gellene, Gregory I.

2003-11-01

The temperature dependent rate of the He++2He→He2++He three-body association reaction is studied using two complementary quantum dynamical models. Model I presumes a two-step, reverse Lindemann mechanism, where the intermediate energized complex, He2+*, is interpreted as the rotational resonance states of He2+. The energy and width of these resonances are determined via "exact" quantum calculation using highly accurate potential-energy curves. Model II uses an alternate quantum rate expression as the thermal average of the cumulative recombination probability, N(E). This microcanonical quantity is computed approximately, over the He2+ space only, with the third-body interaction modeled using a special type of absorbing potential. Because Model II implicitly incorporates both the two-step reverse Lindemann mechanism, and a one-step, reverse collision induced dissociation mechanism, the relative importance of the two formation mechanisms can be estimated by a comparison of the Model I and Model II results. For T<300 K, the reaction is found to be dominated by the two-step mechanism, and a formation rate in good agreement with the available experimental results is obtained with essentially no adjustable parameters in the theory. Interestingly, a nonmonotonic He2+ formation rate is observed, with a maximum identified near 25 K. This maximum is associated with just two reaction intermediate resonance states, the lowest energy states that can contribute significantly to the formation kinetics.

40 CFR 75.72 - Determination of NOX mass emissions for common stack and multiple stack configurations.

Code of Federal Regulations, 2012 CFR

2012-07-01

... the affected units as the difference between NOX mass emissions measured in the common stack and NOX... emissions using the maximum potential NOX emission rate, the maximum potential flow rate, and either the maximum potential CO2 concentration or the minimum potential O2 concentration (as applicable). The maximum...

Using degrees of rate control to improve selective n-butane oxidation over model MOF-encapsulated catalysts: sterically-constrained Ag 3 Pd(111)

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

Dix, Sean T.; Scott, Joseph K.; Getman, Rachel B.

2016-01-01

Metal nanoparticles encapsulated within metal organic frameworks (MOFs) offer steric restrictions near the catalytic metal that can improve selectivity, much like in enzymes. A microkinetic model is developed for the regio-selective oxidation ofn-butane to 1-butanol with O 2over a model for MOF-encapsulated bimetallic nanoparticles. The model consists of a Ag 3Pd(111) surface decorated with a 2-atom-thick ring of (immobile) helium atoms which creates an artificial pore of similar size to that in common MOFs, which sterically constrains the adsorbed reaction intermediates. The kinetic parameters are based on energies calculated using density functional theory (DFT). The microkinetic model was analysed atmore » 423 K to determine the dominant pathways and which species (adsorbed intermediates and transition states in the reaction mechanism) have energies that most sensitively affect the reaction rates to the different products, using degree-of-rate-control (DRC) analysis. This analysis revealed that activation of the C–H bond is assisted by adsorbed oxygen atoms, O*. Unfortunately, O* also abstracts H from adsorbed 1-butanol and butoxy as well, leading to butanal as the only significant product. This suggested to (1) add water to produce more OH*, thus inhibiting these undesired steps which produce OH*, and (2) eliminate most of the O 2pressure to reduce the O* coverage, thus also inhibiting these steps. Combined with increasing butane pressure, this dramatically improved the 1-butanol selectivity (from 0 to 95%) and the rate (to 2 molecules per site per s). Moreover, 40% less O 2was consumed per oxygen atom in the products. Under these conditions, a terminal H in butane is directly eliminated to the Pd site, and the resulting adsorbed butyl combines with OH* to give the desired 1-butanol. These results demonstrate that DRC analysis provides a powerful approach for optimizing catalytic process conditions, and that highly selectivity oxidation can sometimes be achieved by using a mixture of O 2and H 2O as the oxidant. This was further demonstrated by DRC analysis of a second microkinetic model based on a related but hypothetical catalyst, where the activation energies for two of the steps were modified.« less

Efficiency and Safety of One-Step Procedure Combined Laparoscopic Cholecystectomy and Eretrograde Cholangiopancreatography for Treatment of Cholecysto-Choledocholithiasis: A Randomized Controlled Trial.

PubMed

Liu, Zhiyi; Zhang, Luyao; Liu, Yanling; Gu, Yang; Sun, Tieliang

2017-11-01

We aimed to evaluate the efficiency and safety of one-step procedure combined endoscopic retrograde cholangiopancreatography (ERCP) and laparoscopic cholecystectomy (LC) for treatment of patients with cholecysto-choledocholithiasis. A prospective randomized study was performed on 63 consecutive cholecysto-choledocholithiasis patients during 2008 and 2011. The efficiency and safety of one-step procedure was assessed by comparing the two-step LC with ERCP + endoscopic sphincterotomy (EST). Outcomes including intraoperative features, postoperative features (length of stay and postoperative complications) were evaluated. One- or two-step procedure of LC with ERCP + EST was successfully performed in all patients, and common bile duct stones were completely removed. Statistical analyses showed that length of stay and pulmonary infection rate were significantly lower in the test group compared with that in the control group (P < 0.05), whereas no statistical difference in other outcomes was found between the two groups (all P > 0.05). The one-step procedure of LC with ERCP + EST is superior to the two-step procedure for treatment of patients with cholecysto-choledocholithiasis regarding to the reduced hospital stay and inhibited occurrence of pulmonary infections. Compared with two-step procedure, one-step procedure of LC with ERCP + EST may be a superior option for cholecysto-choledocholithiasis patients treatment regarding to hospital stay and pulmonary infections.

Multisensor data fusion across time and space

NASA Astrophysics Data System (ADS)

Villeneuve, Pierre V.; Beaven, Scott G.; Reed, Robert A.

2014-06-01

Field measurement campaigns typically deploy numerous sensors having different sampling characteristics for spatial, temporal, and spectral domains. Data analysis and exploitation is made more difficult and time consuming as the sample data grids between sensors do not align. This report summarizes our recent effort to demonstrate feasibility of a processing chain capable of "fusing" image data from multiple independent and asynchronous sensors into a form amenable to analysis and exploitation using commercially-available tools. Two important technical issues were addressed in this work: 1) Image spatial registration onto a common pixel grid, 2) Image temporal interpolation onto a common time base. The first step leverages existing image matching and registration algorithms. The second step relies upon a new and innovative use of optical flow algorithms to perform accurate temporal upsampling of slower frame rate imagery. Optical flow field vectors were first derived from high-frame rate, high-resolution imagery, and then finally used as a basis for temporal upsampling of the slower frame rate sensor's imagery. Optical flow field values are computed using a multi-scale image pyramid, thus allowing for more extreme object motion. This involves preprocessing imagery to varying resolution scales and initializing new vector flow estimates using that from the previous coarser-resolution image. Overall performance of this processing chain is demonstrated using sample data involving complex too motion observed by multiple sensors mounted to the same base. Multiple sensors were included, including a high-speed visible camera, up to a coarser resolution LWIR camera.

Combining hygrothermal and corrosion models to predict corrosion of metal fasteners embedded in wood

Treesearch

Samuel L. Zelinka; Dominique Derome; Samuel V. Glass

2011-01-01

A combined heat, moisture, and corrosion model is presented and used to simulate the corrosion of metal fasteners embedded in solid wood exposed to the exterior environment. First, the moisture content and temperature at the wood/fastener interface is determined at each time step. Then, the amount of corrosion is determined spatially using an empirical corrosion rate...

Height Growth of American Sycamore in Southeastern Louisiana

Treesearch

Charles B. Briscoe; Mitchell D. Ferrill

1958-01-01

The determination of site quality is one of the early steps preceding intensive forest management; it is most commonly assessed by a total height-age relationship know as site index, with quality being expressed by the height at a chosen index age. Because an intensive review of the literature has revealed no site index curves nor yield tables for American sycamore (...

Common Sense Housing Investment Act of 2013

THOMAS, 113th Congress

Rep. Ellison, Keith [D-MN-5

2013-03-15

House - 03/15/2013 Referred to the Committee on Ways and Means, and in addition to the Committee on Financial Services, for a period to be subsequently determined by the Speaker, in each case for consideration of such provisions as fall within the jurisdiction of the committee... (All Actions) Tracker: This bill has the status IntroducedHere are the steps for Status of Legislation:

A Fresh Look at the Crystal Violet Lab with Handheld Camera Colorimetry

ERIC Educational Resources Information Center

Knutson, Theodore R.; Knutson, Cassandra M.; Mozzetti, Abbie R.; Campos, Antonio R.; Haynes, Christy L.; Penn, R. Lee

2015-01-01

Chemical kinetic experiments to determine rate laws are common in high school and college chemistry courses. For reactions involving a color change, rate laws can be determined experimentally using spectrophotometric or colorimetric equipment though this equipment can be cost prohibitive. Previous work demonstrated that inexpensive handheld camera…

Unifying Temporal and Structural Credit Assignment Problems

NASA Technical Reports Server (NTRS)

Agogino, Adrian K.; Tumer, Kagan

2004-01-01

Single-agent reinforcement learners in time-extended domains and multi-agent systems share a common dilemma known as the credit assignment problem. Multi-agent systems have the structural credit assignment problem of determining the contributions of a particular agent to a common task. Instead, time-extended single-agent systems have the temporal credit assignment problem of determining the contribution of a particular action to the quality of the full sequence of actions. Traditionally these two problems are considered different and are handled in separate ways. In this article we show how these two forms of the credit assignment problem are equivalent. In this unified frame-work, a single-agent Markov decision process can be broken down into a single-time-step multi-agent process. Furthermore we show that Monte-Carlo estimation or Q-learning (depending on whether the values of resulting actions in the episode are known at the time of learning) are equivalent to different agent utility functions in a multi-agent system. This equivalence shows how an often neglected issue in multi-agent systems is equivalent to a well-known deficiency in multi-time-step learning and lays the basis for solving time-extended multi-agent problems, where both credit assignment problems are present.

Stepped chute training wall height requirements

USDA-ARS?s Scientific Manuscript database

Stepped chutes are commonly used for overtopping protection for embankment dams. Aerated flow is commonly associated with stepped chutes if the chute has sufficient length. The aeration and turbulence of the flow can create a significant amount of splash over the training wall if not appropriately...

Electrochemistry and the mechanisms of nucleation and growth of neodymium during electroreduction from LiCl-KCl eutectic salts on Mo substrate

NASA Astrophysics Data System (ADS)

Tang, Hao; Pesic, Batric

2015-03-01

The electrochemical behavior of NdCl3 was studied on a Mo electrode in molten LiCl-KCl eutectic salts. The electroreduction of Nd(III)/Nd(0) involved two reaction steps, as confirmed by three different electrochemical techniques. In the first reaction step, Nd(III) is converted into soluble Nd(II), which undergoes further reduction into metallic Nd(0) in the second reaction step. The standard reaction rate constants for each reaction step were determined by Nicholson method. The rate constant values were used in Matsuda-Ayabe's criteria for testing the electrochemical reversibility. Accordingly, both reaction steps were quasi-reversible redox reactions. The nucleation mechanisms of neodymium metal deposited on a Mo substrate were predicted by using Scharifker-Hill model, and tested for the first time by scanning electron microscopy (SEM) studies of the electrode surface. The SEM studies confirmed that for the low initial concentration of NdCl3, neodymium nucleates and grows progressively, while for higher NdCl3 concentrations, the related mechanism is instantaneous. Both are governed by the aggregative growth mechanisms based on surface mobility of formed nanoclusters.

Slow slip and self-similar asymptotics of rate-strengthening faults

NASA Astrophysics Data System (ADS)

Viesca, R. C.; Dublanchet, P.

2016-12-01

We examine how slow slip progresses on rate-strengthening faults. We consider that the source of rate-strengthening may be a linear or non-linear (power-law) viscous fault rheology, a logarithmic rate-dependence, or a Dieterich-Ruina dependence on slip rate and its history. We show the existence of self-similar asymptotic solutions for slip rate of the form V = t^alpha f(x/t^beta). The exponent beta is determined by the nature of the elastic interaction (for slip between elastic half-spaces in contact, beta = 1; and for layer sliding above a substrate, beta = 1/2). The similarity exponent alpha is determined by the type of initial or boundary conditions. Such conditions may be, for example, an imposed (i) boundary slip rate or (ii) a sudden change in stress on the fault. We consider in-plane or anti-plane slip for examples (i) and (ii) and present the asymptotic solutions thereof, which may be found numerically or in closed form. The self-similar behavior of scenario (i) is, for a step increase in stress, that of an initially elevated slip rate decaying in time while spreading in space; and of scenario (ii) is that an elevated slip rate propagating along the fault. Under scenario (i) we show that the disparate fault rheologies share a common closed-form similarity solution for the decay of slip rate following the initial stress change. For comparison, we compute numerical solutions to the evolution equation for slip rate (and state, when applicable) and find precise agreement with the above analysis. We illustrate how the above solutions provide robust, low-parameter models to test whether there is a frictional basis for spatio-temporal observations indicating the accumulation of post-seismic slip or the occurrence of slow slip event. Such observations include those derived from (a) geodetic observations [e.g., Hsu et al., Science 2006], or migration of (b) low-frequency earthquakes and tremor [e.g., Obara and Hirose, Tectonophys. 2006], and of (c) micro-seismicity [e.g., Bourouis and Bernard, Geophys. J. Int., 2007].

A model for trace metal sorption processes at the calcite surface: Adsorption of Cd2+ and subsequent solid solution formation

USGS Publications Warehouse

Davis, J.A.; Fuller, C.C.; Cook, A.D.

1987-01-01

The rate of Cd2+ sorption by calcite was determined as a function of pH and Mg2+ in aqueous solutions saturated with respect to calcite but undersaturated with respect to CdCO3. The sorption is characterized by two reaction steps, with the first reaching completion within 24 hours. The second step proceeded at a slow and nearly constant rate for at least 7 days. The rate of calcite recrystallization was also studied, using a Ca2+ isotopic exchange technique. Both the recrystallization rate of calcite and the rate of slow Cd2+ sorption decrease with increasing pH or with increasing Mg2+. The recrystallization rate could be predicted from the number of moles of Ca present in the hydrated surface layer. A model is presented which is consistent with the rates of Cd2+ sorption and Ca2+ isotopic exchange. In the model, the first step in Cd2+ sorption involves a fast adsorption reaction that is followed by diffusion of Cd2+ into a surface layer of hydrated CaCO3 that overlies crystalline calcite. Desorption of Cd2+ from the hydrated layer is slow. The second step is solid solution formation in new crystalline material, which grows from the disordered mixture of Cd and Ca carbonate in the hydrated surface layer. Calculated distribution coefficients for solid solutions formed at the surface are slightly greater than the ratio of equilibrium constants for dissolution of calcite and CdCO3, which is the value that would be expected for an ideal solid solution in equilibrium with the aqueous solution. ?? 1987.

Handling of Diskus dry powder inhaler in Chinese chronic obstructive pulmonary disease patients.

PubMed

Li, Huaidong; Chen, Yuanyuan; Zhang, Zhaorui; Dong, Xiaoxuan; Zhang, Guogang; Zhang, Hui

2014-06-01

The incorrect handling of Diskus inhalers in Chinese patients with chronic obstructive pulmonary disease (COPD) is not well documented. The present study was conducted to evaluate in detail the handling errors related to the Diskus device, and to elucidate the importance of educating COPD patients on the proper use of the device. A total of 384 COPD patients from a pulmonary clinic in China over a period of 5 years were included in the study. The compliance of COPD patients to the 13 discrete steps of Diskus usage were scored and analyzed by three measures: (1) On day 0, patients were given only a package insert on Diskus, and the handling error rate was assessed. Then the patients were given instruction on the 13-step Diskus procedure until they could demonstrate the proper technique. (2) On days 1, 2, and 3, the observation group was continuously educated on a 13-step procedure, and the percentage of patients who scored 100% for each step was recorded. The control group had no such training. (3) On days 10, 20, and 30, the percentage of all subjects correctly performing the Diskus 13-step inhalation procedure was assessed. Incorrect handling techniques on Diskus usage were widely distributed among Chinese COPD patients. Step 8 ("Inhale forcefully from the beginning, slowly, deeply, and uniformly during the inspiratory phase until the lungs are full") was the most commonly mishandled step (93.8%). The total score and individual step scores of the patients from the observation group were significantly improved during 3-day continuous education. There was also a significantly higher percentage of correctly performed steps in the observation group than in the control group upon assessment on day 10 (96.24% vs. 85.63%, respectively; p<0.01), day 20 (97.31% vs. 86.09%, respectively; p<0.01), and day 30 (98.19% vs. 87.39%, respectively; p<0.01). Handling errors of the Diskus 13-step inhalation procedure were commonly observed in Chinese COPD patients. Continuous educational interventions and regular supervision by health-care providers are therefore crucial for the optimum use of the Diskus inhaler.

The HERSCHEL/PACS early Data Products

NASA Astrophysics Data System (ADS)

Wieprecht, E.; Wetzstein, M.; Huygen, R.; Vandenbussche, B.; De Meester, W.

2006-07-01

ESA's Herschel Space Observatory to be launched in 2007, is the first space observatory covering the full far-infrared and submillimeter wavelength range (60 - 670 microns). The Photodetector Array Camera & Spectrometer (PACS) is one of the three science instruments. It contains two Ge:Ga photoconductor arrays and two bolometer arrays to perform imaging line spectroscopy and imaging photometry in the 60 - 210 micron wavelength band. The HERSCHEL ground segment (Herschel Common Science System - HCSS) is implemented using JAVA technology and written in a common effort by the HERSCHEL Science Center and the three instrument teams. The PACS Common Software System (PCSS) is based on the HCSS and used for the online and offline analysis of PACS data. For telemetry bandwidth reasons PACS science data are partially processed on board, compressed, cut into telemetry packets and transmitted to the ground. These steps are instrument mode dependent. We will present the software model which allows to reverse the discrete on board processing steps and evaluate the data. After decompression and reconstruction the detector data and instrument status information are organized in two main PACS Products. The design of these JAVA classes considers the individual sampling rates, data formats, memory and performance optimization aspects and comfortable user interfaces.

Direct water decomposition on transition metal surfaces: Structural dependence and catalytic screening

DOE PAGES

Tsai, Charlie; Lee, Kyoungjin; Yoo, Jong Suk; ...

2016-02-16

Density functional theory calculations are used to investigate thermal water decomposition over the close-packed (111), stepped (211), and open (100) facets of transition metal surfaces. A descriptor-based approach is used to determine that the (211) facet leads to the highest possible rates. As a result, a range of 96 binary alloys were screened for their potential activity and a rate control analysis was performed to assess how the overall rate could be improved.

Analysis of suicide deaths in a 15-year period in Eskisehir, western Anatolia, Turkey and the determination of risk factors.

PubMed

Karbeyaz, Kenan; Akkaya, Harun; Balci, Yasemin

2013-01-01

It is estimated that every year 1 million people die all around the world due to suicide. The average rate of suicide in the world is reported as 16/100,000. In this study, we aimed to evaluate and discuss the suicide cases in our city Eskisehir that is located in western Anatolia. This is a retrospective study covering the period 1997-2011. All deaths in Eskisehir caused due to the consumption of forensic medicines in a 15-year period between 1997 and 2011 were evaluated retrospectively. A total of 553 cases were determined to be suicidal following both forensic and criminal investigations, and were included in the study. Furthermore, death examination and autopsy reports were investigated, and judicial investigation records were also taken into account. In this period, the average rate of suicide in our city was determined as 5.1/100,000 of which 71.4% of the cases were male. It was determined that the suicides most commonly occurred between the ages of 19 and 29 (32.4%, n=179). The most commonly encountered suicide method was hanging (60.9%, n=337). It was ascertained that the suicide rate in our city was lower than the average rate in the world, but it was higher than the average rate in Turkey. Unemployment was determined as the most common risk factor in our study. A follow-up should be provided for people with a history of attempting to commit suicide or with a tendency to committing suicide due to a psychological disorder.

Role of step stiffness and kinks in the relaxation of vicinal (001) with zigzag [110] steps

NASA Astrophysics Data System (ADS)

Mahjoub, B.; Hamouda, Ajmi BH.; Einstein, TL.

2017-08-01

We present a kinetic Monte Carlo study of the relaxation dynamics and steady state configurations of 〈110〉 steps on a vicinal (001) simple cubic surface. This system is interesting because 〈110〉 (fully kinked) steps have different elementary excitation energetics and favor step diffusion more than 〈100〉 (nominally straight) steps. In this study we show how this leads to different relaxation dynamics as well as to different steady state configurations, including that 2-bond breaking processes are rate determining for 〈110〉 steps in contrast to 3-bond breaking processes for 〈100〉-steps found in previous work [Surface Sci. 602, 3569 (2008)]. The analysis of the terrace-width distribution (TWD) shows a significant role of kink-generation-annihilation processes during the relaxation of steps: the kinetic of relaxation, toward the steady state, is much faster in the case of 〈110〉-zigzag steps, with a higher standard deviation of the TWD, in agreement with a decrease of step stiffness due to orientation. We conclude that smaller step stiffness leads inexorably to faster step dynamics towards the steady state. The step-edge anisotropy slows the relaxation of steps and increases the strength of step-step effective interactions.

The Kinetic Mechanism of Phenylalanine Hydroxylase: Intrinsic Binding and Rate Constants from Single Turnover Experiments†

PubMed Central

Roberts, Kenneth M.; Pavon, Jorge Alex; Fitzpatrick, Paul F.

2013-01-01

Phenylalanine hydroxylase (PheH) catalyzes the key step in the catabolism of dietary phenylalanine, its hydroxylation to tyrosine using tetrahydrobiopterin (BH4) and O2. A complete kinetic mechanism for PheH was determined by global analysis of single turnover data in the reaction of PheHΔ117, a truncated form of the enzyme lacking the N-terminal regulatory domain. Formation of the productive PheHΔ117-BH4-phenylalanine complex begins with the rapid binding of BH4 (Kd = 65 µM). Subsequent addition of phenylalanine to the binary complex to form the productive ternary complex (Kd = 130 µM) is approximately ten-fold slower. Both substrates can also bind to the free enzyme to form inhibitory binary complexes. O2 rapidly binds to the productive ternary complex; this is followed by formation of an unidentified intermediate, detectable as a decrease in absorbance at 340 nm, with a rate constant of 140 s−1. Formation of the 4a-hydroxypterin and Fe(IV)O intermediates is ten-fold slower and is followed by the rapid hydroxylation of the amino acid. Product release is the rate-determining step and largely determines kcat. Similar reactions using 6-methyltetrahydropterin indicate a preference for the physiological pterin during hydroxylation. PMID:23327364

Transition metal catalyzed manipulation of non-polar carbon–hydrogen bonds for synthetic purpose

PubMed Central

MURAI, Shinji

2011-01-01

The direct addition of ortho C–H bonds in various aromatic compounds such as ketones, esters, imines, imidates, nitriles, and aldehydes to olefins and acetylenes can be achieved with the aid of transition metal catalysts. The ruthenium catalyzed reaction is usually highly efficient and useful as a general synthetic method. The coordination to the metal center by a heteroatom in a directing group such as carbonyl and imino groups in aromatic compounds is the key step in this process. Mechanistically, the reductive elimination to form a C–C bond is the rate-determining step, while the C–H bond cleavage step is not. PMID:21558759

Mechanism and microstructures in Ga2O3 pseudomartensitic solid phase transition.

PubMed

Zhu, Sheng-Cai; Guan, Shu-Hui; Liu, Zhi-Pan

2016-07-21

Solid-to-solid phase transition, although widely exploited in making new materials, challenges persistently our current theory for predicting its complex kinetics and rich microstructures in transition. The Ga2O3α-β phase transformation represents such a common but complex reaction with marked change in cation coordination and crystal density, which was known to yield either amorphous or crystalline products under different synthetic conditions. Here we, via recently developed stochastic surface walking (SSW) method, resolve for the first time the atomistic mechanism of Ga2O3α-β phase transformation, the pathway of which turns out to be the first reaction pathway ever determined for a new type of diffusionless solid phase transition, namely, pseudomartensitic phase transition. We demonstrate that the sensitivity of product crystallinity is caused by its multi-step, multi-type reaction pathway, which bypasses seven intermediate phases and involves all types of elementary solid phase transition steps, i.e. the shearing of O layers (martensitic type), the local diffusion of Ga atoms (reconstructive type) and the significant lattice dilation (dilation type). While the migration of Ga atoms across the close-packed O layers is the rate-determining step and yields "amorphous-like" high energy intermediates, the shearing of O layers contributes to the formation of coherent biphase junctions and the presence of a crystallographic orientation relation, (001)α//(201[combining macron])β + [120]α//[13[combining macron]2]β. Our experiment using high-resolution transmission electron microscopy further confirms the theoretical predictions on the atomic structure of biphase junction and the formation of (201[combining macron])β twin, and also discovers the late occurrence of lattice expansion in the nascent β phase that grows out from the parent α phase. By distinguishing pseudomartensitic transition from other types of mechanisms, we propose general rules to predict the product crystallinity of solid phase transition. The new knowledge on the kinetics of pseudomartensitic transition complements the theory of diffusionless solid phase transition.

Thermochemical hydrogen production via a cycle using barium and sulfur - Reaction between barium sulfide and water

NASA Technical Reports Server (NTRS)

Ota, K.; Conger, W. L.

1977-01-01

The reaction between barium sulfide and water, a reaction found in several sulfur based thermochemical cycles, was investigated kinetically at 653-866 C. Gaseous products were hydrogen and hydrogen sulfide. The rate determining step for hydrogen formation was a surface reaction between barium sulfide and water. An expression was derived for the rate of hydrogen formation.

Aerodynamic performance of a low-speed wind tunnel.

PubMed

Frechen, F-B; Frey, M; Wett, M; Löser, C

2004-01-01

The determination of the odour mass flow emitted from a source is a very important step and forms the basis for all subsequent considerations and calculations. Wastewater treatment plants, as well as waste treatment facilities, consist of different kinds of odour sources. Unfortunately, most of the sources are passive sources, where no outward air flow-rate can be measured, but where odorants are obviously emitted. Thus, a type of sampling is required that allows to measure the emitted odour flow-rate (OFR). To achieve this, different methods are in use worldwide. Besides indirect methods, such as micrometeorological atmospheric dispersion models, which have not been used in Germany (in other countries due to different problems, direct methods are also used). Direct measurements include hood methods, commonly divided into static flux chambers, dynamic flux chambers and wind tunnels. The wind tunnel that we have been operating in principle since 1983 is different from all subsequent presented wind tunnels, in that we operate it at a considerably lower wind speed than the others. To describe the behaviour of this wind tunnel, measurement of the flow pattern in this low-speed tunnel are under way, and some initial results are presented here.

Effect of a limited-enforcement intelligent tutoring system in dermatopathology on student errors, goals and solution paths.

PubMed

Payne, Velma L; Medvedeva, Olga; Legowski, Elizabeth; Castine, Melissa; Tseytlin, Eugene; Jukic, Drazen; Crowley, Rebecca S

2009-11-01

Determine effects of a limited-enforcement intelligent tutoring system in dermatopathology on student errors, goals and solution paths. Determine if limited enforcement in a medical tutoring system inhibits students from learning the optimal and most efficient solution path. Describe the type of deviations from the optimal solution path that occur during tutoring, and how these deviations change over time. Determine if the size of the problem-space (domain scope), has an effect on learning gains when using a tutor with limited enforcement. Analyzed data mined from 44 pathology residents using SlideTutor-a Medical Intelligent Tutoring System in Dermatopathology that teaches histopathologic diagnosis and reporting skills based on commonly used diagnostic algorithms. Two subdomains were included in the study representing sub-algorithms of different sizes and complexities. Effects of the tutoring system on student errors, goal states and solution paths were determined. Students gradually increase the frequency of steps that match the tutoring system's expectation of expert performance. Frequency of errors gradually declines in all categories of error significance. Student performance frequently differs from the tutor-defined optimal path. However, as students continue to be tutored, they approach the optimal solution path. Performance in both subdomains was similar for both errors and goal differences. However, the rate at which students progress toward the optimal solution path differs between the two domains. Tutoring in superficial perivascular dermatitis, the larger and more complex domain was associated with a slower rate of approximation towards the optimal solution path. Students benefit from a limited-enforcement tutoring system that leverages diagnostic algorithms but does not prevent alternative strategies. Even with limited enforcement, students converge toward the optimal solution path.

Determinants of modern family planning use among women of reproductive age in the Nkwanta district of Ghana: a case–control study

PubMed Central

2014-01-01

Background Average contraceptive prevalence rate in the Nkwanta district of Ghana was estimated to be 6.2% relative to the national average at the time, of 19%. While several efforts had been made to improve family planning in the country, the district still had very low use of modern family planning methods. This study sought to determine the factors that influenced modern family planning use in general and specifically, the factors that determined the consistently low use of modern family planning methods in the district. Methods A case–control study was conducted in the Nkwanta district of Ghana to determine socio-economic, socio-cultural and service delivery factors influencing family planning usage. One hundred and thirty cases and 260 controls made up of women aged 15–49 years were interviewed using structured questionnaires. A logistic regression was fitted. Results Awareness and knowledge of modern family planning methods were high among cases and controls (over 90%). Lack of formal education among women, socio-cultural beliefs and spousal communication were found to influence modern family planning use. Furthermore, favourable opening hours of the facilities and distance to health facilities influenced the use of modern contraceptives. Conclusion While modern family planning seemed to be common knowledge among these women, actual use of such contraceptives was limited. There is need to improve use of modern family planning methods in the district. In addition to providing health facilities and consolidating close-to-client service initiatives in the district, policies directed towards improving modern family planning method use need to consider the influence of formal education. Promoting basic education, especially among females, will be a crucial step as the district is faced with high levels of school dropout and illiteracy rates. PMID:25117887

Determinants of modern family planning use among women of reproductive age in the Nkwanta district of Ghana: a case-control study.

PubMed

Eliason, Sebastian; Awoonor-Williams, John K; Eliason, Cecilia; Novignon, Jacob; Nonvignon, Justice; Aikins, Moses

2014-08-13

Average contraceptive prevalence rate in the Nkwanta district of Ghana was estimated to be 6.2% relative to the national average at the time, of 19%. While several efforts had been made to improve family planning in the country, the district still had very low use of modern family planning methods. This study sought to determine the factors that influenced modern family planning use in general and specifically, the factors that determined the consistently low use of modern family planning methods in the district. A case-control study was conducted in the Nkwanta district of Ghana to determine socio-economic, socio-cultural and service delivery factors influencing family planning usage. One hundred and thirty cases and 260 controls made up of women aged 15-49 years were interviewed using structured questionnaires. A logistic regression was fitted. Awareness and knowledge of modern family planning methods were high among cases and controls (over 90%). Lack of formal education among women, socio-cultural beliefs and spousal communication were found to influence modern family planning use. Furthermore, favourable opening hours of the facilities and distance to health facilities influenced the use of modern contraceptives. While modern family planning seemed to be common knowledge among these women, actual use of such contraceptives was limited. There is need to improve use of modern family planning methods in the district. In addition to providing health facilities and consolidating close-to-client service initiatives in the district, policies directed towards improving modern family planning method use need to consider the influence of formal education. Promoting basic education, especially among females, will be a crucial step as the district is faced with high levels of school dropout and illiteracy rates.

Development of a Novel Approach for Fatigue Life Prediction of Structural Materials

DTIC Science & Technology

2008-12-01

applied when the crack length was 8.45 mm and 14.96 mm, respectively, on these two specimens. A third specimen was subjected to a constant amplitude...The crack growth rate at the middle point (the third point) was determined from the derivative of the parabola. The stress intensity factor for...minimum load was identical in the two loading steps (Fig. 32(b)). The third specimen experienced two-step loading with identical /?-ratio in the two

Rates and time scales of clay-mineral formation by weathering in saprolitic regoliths of the southern Appalachians from geochemical mass balance

Treesearch

Jason R. Price; Michael A. Velbel; Lina C. Patino

2005-01-01

Rates of clay formation in three watersheds located at the Coweeta Hydrologic Laboratory, western North Carolina, have been determined from solute flux-based mass balance methods. A system of mass balance equations with enough equations and unknowns to allow calculation of secondary mineral formation rates as well as the more commonly determined primary-...

Gas-Phase Formation Rates of Nitric Acid and Its Isomers Under Urban Conditions

NASA Technical Reports Server (NTRS)

Okumura, M.; Mollner, A. K.; Fry, J. L.; Feng, L.

2005-01-01

Ozone formation in urban smog is controlled by a complex set of reactions which includes radical production from photochemical processes, catalytic cycles which convert NO to NO2, and termination steps that tie up reactive intermediates in long-lived reservoirs. The reaction OH + NO2 + M -4 HONO2 + M (la) is a key termination step because it transforms two short-lived reactive intermediates, OH and NO2, into relatively long-lived nitric acid. Under certain conditions (low VOC/NOx), ozone production in polluted urban airsheds can be highly sensitive to this reaction, but the rate parameters are not well constrained. This report summarizes the results of new laboratory studies of the OH + NO2 + M reaction including direct determination of the overall rate constant and branching ratio for the two reaction channels under atmospherically relevant conditions.

Neighbourhood characteristics, social capital and self-rated health - A population-based survey in Sweden

PubMed Central

2010-01-01

Background In previous public health surveys large differences in health have been shown between citizens living in different neighbourhoods in the Örebro municipality, which has about 125000 inhabitants. The aim of this study was to investigate the determinants of health with an emphasis on the importance of neighbourhood characteristics such as the influence of neighbourhood social cohesion and social capital. The point of departure in this study was a conceptual model inspired by the work of Carpiano, where different factors related to the neighbourhood have been used to find associations to individual self-rated health. Methods We used data from the survey 'Life & Health 2004' sent to inhabitants aged 18-84 years in Örebro municipality, Sweden. The respondents (n = 2346) answered a postal questionnaire about living conditions, housing conditions, health risk factors and individual health. The outcome variable was self-rated health. In the analysis we applied logistic regression modelling in various model steps following a conceptual model. Results The results show that poor self-rated health was associated with social capital, such as lack of personal support and no experience of being made proud even after controlling for strong factors related to health, such as age, disability pension, ethnicity and economic stress. Also the neighbourhood factors, housing area and residential stability were associated with self-rated health. Poor self-rated health was more common among people living in areas with predominately large blocks of flats or areas outside the city centre. Moreover, people who had lived in the same area 1-5 years reported poor health more frequently than those who had lived there longer. Conclusions The importance of the neighbourhood and social capital for individual health is confirmed in this study. The neighbourhoods could be emphasized as settings for health promotion. They can be constructed to promote social interaction which in turn supports the development of social networks, social support and social capital - all important determinants of health. PMID:20964808

Neighbourhood characteristics, social capital and self-rated health--a population-based survey in Sweden.

PubMed

Lindén-Boström, Margareta; Persson, Carina; Eriksson, Charli

2010-10-21

In previous public health surveys large differences in health have been shown between citizens living in different neighbourhoods in the Örebro municipality, which has about 125000 inhabitants. The aim of this study was to investigate the determinants of health with an emphasis on the importance of neighbourhood characteristics such as the influence of neighbourhood social cohesion and social capital. The point of departure in this study was a conceptual model inspired by the work of Carpiano, where different factors related to the neighbourhood have been used to find associations to individual self-rated health. We used data from the survey 'Life & Health 2004' sent to inhabitants aged 18-84 years in Örebro municipality, Sweden. The respondents (n = 2346) answered a postal questionnaire about living conditions, housing conditions, health risk factors and individual health. The outcome variable was self-rated health. In the analysis we applied logistic regression modelling in various model steps following a conceptual model. The results show that poor self-rated health was associated with social capital, such as lack of personal support and no experience of being made proud even after controlling for strong factors related to health, such as age, disability pension, ethnicity and economic stress. Also the neighbourhood factors, housing area and residential stability were associated with self-rated health. Poor self-rated health was more common among people living in areas with predominately large blocks of flats or areas outside the city centre. Moreover, people who had lived in the same area 1-5 years reported poor health more frequently than those who had lived there longer. The importance of the neighbourhood and social capital for individual health is confirmed in this study. The neighbourhoods could be emphasized as settings for health promotion. They can be constructed to promote social interaction which in turn supports the development of social networks, social support and social capital--all important determinants of health.

The use of think-aloud protocols to identify a decision-making process of community pharmacists aimed at improving CMS Star Ratings scores.

PubMed

George, David L; Smith, Michael J; Draugalis, JoLaine R; Tolma, Eleni L; Keast, Shellie L; Wilson, Justin B

2018-03-01

The Center for Medicare and Medicaid Services (CMS) created the Star Rating system based on multiple measures that indicate the overall quality of health plans. Community pharmacists can impact certain Star Ratings measure scores through medication adherence and patient safety interventions. To explore methods, needs, and workflow issues of community pharmacists to improve CMS Star Ratings measures. Think-aloud protocols (TAPs) were conducted with active community retail pharmacists in Oklahoma. Each TAP was audio recorded and transcribed to documents for analysis. Analysts agreed on common themes, illuminated differences in findings, and saturation of the data gathered. Methods, needs, and workflow themes of community pharmacists associated with improving Star Ratings measures were compiled and organized to exhibit a decision-making process. Five TAPs were performed among three independent pharmacy owners, one multi-store owner, and one chain-store administrator. A thematically common 4-step process to monitor and improve CMS Star Ratings scores among participants was identified. To improve Star Ratings measures, pharmacists: 1) used technology to access scores, 2) analyzed data to strategically set goals, 3) assessed individual patient information for comprehensive assessment, and 4) decided on interventions to best impact Star Ratings scores. Participants also shared common needs, workflow issues, and benefits associated with methods used in improving Star Ratings. TAPs were useful in exploring processes of pharmacists who improve CMS Star Ratings scores. Pharmacists demonstrated and verbalized their methods, workflow issues, needs, and benefits related to performing the task. The themes and decision-making process identified to improving CMS Star Ratings scores will assist in the development of training and education programs for pharmacists in the community setting. Published by Elsevier Inc.

Optimization of Surface Roughness and Wall Thickness in Dieless Incremental Forming Of Aluminum Sheet Using Taguchi

NASA Astrophysics Data System (ADS)

Hamedon, Zamzuri; Kuang, Shea Cheng; Jaafar, Hasnulhadi; Azhari, Azmir

2018-03-01

Incremental sheet forming is a versatile sheet metal forming process where a sheet metal is formed into its final shape by a series of localized deformation without a specialised die. However, it still has many shortcomings that need to be overcome such as geometric accuracy, surface roughness, formability, forming speed, and so on. This project focus on minimising the surface roughness of aluminium sheet and improving its thickness uniformity in incremental sheet forming via optimisation of wall angle, feed rate, and step size. Besides, the effect of wall angle, feed rate, and step size to the surface roughness and thickness uniformity of aluminium sheet was investigated in this project. From the results, it was observed that surface roughness and thickness uniformity were inversely varied due to the formation of surface waviness. Increase in feed rate and decrease in step size will produce a lower surface roughness, while uniform thickness reduction was obtained by reducing the wall angle and step size. By using Taguchi analysis, the optimum parameters for minimum surface roughness and uniform thickness reduction of aluminium sheet were determined. The finding of this project helps to reduce the time in optimising the surface roughness and thickness uniformity in incremental sheet forming.

Analyzing the Rate at Which Languages Lose the Influence of a Common Ancestor

ERIC Educational Resources Information Center

Rafferty, Anna N.; Griffiths, Thomas L.; Klein, Dan

2014-01-01

Analyzing the rate at which languages change can clarify whether similarities across languages are solely the result of cognitive biases or might be partially due to descent from a common ancestor. To demonstrate this approach, we use a simple model of language evolution to mathematically determine how long it should take for the distribution over…

Towards an optimal therapy strategy for myogenous TMD, physiotherapy compared with occlusal splint therapy in an RCT with therapy-and-patient-specific treatment durations.

PubMed

van Grootel, Robert J; Buchner, Rob; Wismeijer, Daniël; van der Glas, Hilbert W

2017-02-10

Temporomandibular Disorders (TMD) may be characterized by pain and restricted jaw movements. In the absence of somatic factors in the temporomandibular joint, mainly myogenous, psychobiological, and psychosocial factors may be involved in the aetiology of myogenous TMD. An occlusal appliance (splint) is commonly used as a basic therapy of the dental practice. Alternatively, a type of physiotherapy which includes, apart from massage of sore muscles, aspects of cognitive-behavioural therapy might be a basic therapy for myogenous TMD. Treatment outcome of physiotherapy (Ph-Tx) was evaluated in comparison to that of splint therapy (Sp-Tx), using the index Treatment Duration Control (TDC) that enabled a randomized controlled trial with, comparable to clinical care, therapy-and-patient-specific treatment durations. Seventy-two patients were randomly assigned to either Ph-Tx or Sp-Tx, with an intended treatment duration between 10 and 21 or 12 and 30 weeks respectively. Using TDC, the clinician controlled treatment duration and the number of visits needed. A blinded assessor recorded anamnestic and clinical data to determine TDC-values following treatment and a 1-year follow-up, yielding success rate (SR) and effectiveness (mean TDC) as treatment outcomes. Cohen's d, was determined for pain intensity. Overall SR for stepped-care was assessed in a theoretical model, i.e. a second of the two studied therapies was applied if the first treatment was unsuccessful, and the effect of therapy sequence and difference in success rates was examined. SR and effectiveness were similar for Ph-Tx and Sp-Tx (long-term SR: 51-60%; TDC: -0.512- -0.575). Cohen's d was 0.86 (Ph-Tx) and 1.39 (Sp-Tx). Treatment duration was shorter for Ph-Tx (on average 10.4 weeks less; p < 0.001). Sp-Tx needed 7.1 less visits (p < 0.001). Physiotherapy may be preferred as initial therapy over occlusal splint therapy in stepped-care of myogenous TMD. With a similar SR and effectiveness, physiotherapy has a shorter duration. Thus patients whose initial physiotherapy is unsuccessful can continue earlier with subsequent treatment. The stepped-care model reinforces the conclusion on therapy preference as the overall SR hardly depends on therapy sequence. isrctn.com/ISRCTN17469828 . Retrospectively registered: 11/11/2016.

The Reaction Kinetics of 3-Hydroxybenzoate 6-Hydroxylase from Rhodococcus jostii RHA1 Provide an Understanding of the para-Hydroxylation Enzyme Catalytic Cycle*

PubMed Central

Sucharitakul, Jeerus; Tongsook, Chanakan; Pakotiprapha, Danaya; van Berkel, Willem J. H.; Chaiyen, Pimchai

2013-01-01

3-Hydroxybenzoate 6-hydroxylase (3HB6H) from Rhodococcus jostii RHA1 is an NADH-specific flavoprotein monooxygenase that catalyzes the para-hydroxylation of 3-hydroxybenzoate (3HB) to form 2,5-dihydroxybenzoate (2,5-DHB). Based on results from stopped-flow spectrophotometry, the reduced enzyme-3HB complex reacts with oxygen to form a C4a-peroxy flavin with a rate constant of 1.13 ± 0.01 × 106 m−1 s−1 (pH 8.0, 4 °C). This intermediate is subsequently protonated to form a C4a-hydroperoxyflavin with a rate constant of 96 ± 3 s−1. This step shows a solvent kinetic isotope effect of 1.7. Based on rapid-quench measurements, the hydroxylation occurs with a rate constant of 36 ± 2 s−1. 3HB6H does not exhibit substrate inhibition on the flavin oxidation step, a common characteristic found in most ortho-hydroxylation enzymes. The apparent kcat at saturating concentrations of 3HB, NADH, and oxygen is 6.49 ± 0.02 s−1. Pre-steady state and steady-state kinetic data were used to construct the catalytic cycle of the reaction. The data indicate that the steps of product release (11.7 s−1) and hydroxylation (36 ± 2 s−1) partially control the overall turnover. PMID:24129570

Discovering functional interdependence relationship in PPI networks for protein complex identification.

PubMed

Lam, Winnie W M; Chan, Keith C C

2012-04-01

Protein molecules interact with each other in protein complexes to perform many vital functions, and different computational techniques have been developed to identify protein complexes in protein-protein interaction (PPI) networks. These techniques are developed to search for subgraphs of high connectivity in PPI networks under the assumption that the proteins in a protein complex are highly interconnected. While these techniques have been shown to be quite effective, it is also possible that the matching rate between the protein complexes they discover and those that are previously determined experimentally be relatively low and the "false-alarm" rate can be relatively high. This is especially the case when the assumption of proteins in protein complexes being more highly interconnected be relatively invalid. To increase the matching rate and reduce the false-alarm rate, we have developed a technique that can work effectively without having to make this assumption. The name of the technique called protein complex identification by discovering functional interdependence (PCIFI) searches for protein complexes in PPI networks by taking into consideration both the functional interdependence relationship between protein molecules and the network topology of the network. The PCIFI works in several steps. The first step is to construct a multiple-function protein network graph by labeling each vertex with one or more of the molecular functions it performs. The second step is to filter out protein interactions between protein pairs that are not functionally interdependent of each other in the statistical sense. The third step is to make use of an information-theoretic measure to determine the strength of the functional interdependence between all remaining interacting protein pairs. Finally, the last step is to try to form protein complexes based on the measure of the strength of functional interdependence and the connectivity between proteins. For performance evaluation, PCIFI was used to identify protein complexes in real PPI network data and the protein complexes it found were matched against those that were previously known in MIPS. The results show that PCIFI can be an effective technique for the identification of protein complexes. The protein complexes it found can match more known protein complexes with a smaller false-alarm rate and can provide useful insights into the understanding of the functional interdependence relationships between proteins in protein complexes.

Fundamental Reaction Pathway and Free Energy Profile for Butyrylcholinesterase-Catalyzed Hydrolysis of Heroin

PubMed Central

Qiao, Yan; Han, Keli; Zhan, Chang-Guo

2013-01-01

The pharmacological function of heroin requires an activation process which transforms heroin into 6-monoacetylmorphine (6-MAM) which is the most active form. The primary enzyme responsible for this activation process in human plasma is butyrylcholinesterase (BChE). The detailed reaction pathway of the activation process via BChE-catalyzed hydrolysis has been explored computationally, for the first time, in the present study by performing molecular dynamics simulation and first-principles quantum mechanical/molecular mechanical free energy calculations. It has been demonstrated that the whole reaction process includes acylation and deacylation stages. The acylation consists of two reaction steps, i.e. the nucleophilic attack on the carbonyl carbon of 3-acetyl group of heroin by the hydroxyl oxygen of Ser198 side chain and the dissociation of 6-MAM. The deacylation also consists of two reaction steps, i.e. the nucleophilic attack on the carbonyl carbon of the acyl-enzyme intermediate by a water molecule and the dissociation of the acetic acid from Ser198. The calculated free energy profile reveals that the second transition state (TS2) should be rate-determining. The structural analysis reveals that the oxyanion hole of BChE plays an important role in the stabilization of the rate-determining transition state TS2. The free energy barrier (15.9±0.2 or 16.1±0.2 kcal/mol) calculated for the rate-determining step is in good agreement with the experimentally-derived activation free energy (~16.2 kcal/mol), suggesting that the mechanistic insights obtained from the present computational study are reliable. The obtained structural and mechanistic insights could be valuable for use in future rational design of a novel therapeutic treatment of heroin abuse. PMID:23992153

Geomorphic and hydraulic Analyses of In-stream Step-pool Structures (I)

NASA Astrophysics Data System (ADS)

Kuo, W. C.; Hu, Y. L.; Wang, H. W.

2016-12-01

Longitudinal stair-like structures, such as alternating steps and pools, are found commonly in steep mountain streams. In a way to mimic the natural characteristics, many implementations of constructing artificial step structures have long been found in field practice to stabilize streambeds and enhance aquatic systems. To better understand how constructed step-pool systems form and function, this paper discusses the hydraulic and geomorphic factors based on flume experiments, and further compare to our field observations in Chijiawan Creek in Taiwan. We constructed a 2.9-m-long, 0.15-wide, and 0.3-m-high acrylic walled recirculating channel and conducted experiments to understand the formation, hydraulic features, and channel stability of step-pools of scenarios considering different channel slopes, discharges, feeding sediments. The results indicated that the keystones played a crucial role in stabilizing step-pool structures. The grain sizes of keystones from the experiments ranged approximately from one-third to one-tenth of channel width, while those from the field observations were about one-ninth to two-ninths. While the experimental discharge increased from 0.0012 cms to 0.006 cms, the flow transformed from nappe flow to skimming flow and the difference of average velocity between steps and pools reduced 30%. Besides, experiments showed that the step-pool structures failed immediately after keystones destroyed at a sediment transportation rate about 1.5 times of sediment feeding rate. It highlights the step-pools and channel stability is highly related to keystones. We further found the step-pools were buried at the experimental cases with coarse sediment fed upstream, similar to our field observations in Chijiawan Creek, with an approximately 1 3m deposition after Typhoon Soudelor, a 5-year event. The results obtained in this study would serve as a basis for ongoing discussions on how constructed step-pool structures would function and fail. More efforts of field investigations, flume experiments, and field experiments in helping developing specific recommendations and providing scientific insights for not only in Taiwan but around the world are still in need.

Development of a standardized training course for laparoscopic procedures using Delphi methodology.

PubMed

Bethlehem, Martijn S; Kramp, Kelvin H; van Det, Marc J; ten Cate Hoedemaker, Henk O; Veeger, Nicolaas J G M; Pierie, Jean Pierre E N

2014-01-01

Content, evaluation, and certification of laparoscopic skills and procedure training lack uniformity among different hospitals in The Netherlands. Within the process of developing a new regional laparoscopic training curriculum, a uniform and transferrable curriculum was constructed for a series of laparoscopic procedures. The aim of this study was to determine regional expert consensus regarding the key steps for laparoscopic appendectomy and cholecystectomy using Delphi methodology. Lists of suggested key steps for laparoscopic appendectomy and cholecystectomy were created using surgical textbooks, available guidelines, and local practice. A total of 22 experts, working for teaching hospitals throughout the region, were asked to rate the suggested key steps for both procedures on a Likert scale from 1-5. Consensus was reached with Crohnbach's α ≥ 0.90. Of the 22 experts, 21 completed and returned the survey (95%). Data analysis already showed consensus after the first round of Delphi on the key steps for laparoscopic appendectomy (Crohnbach's α = 0.92) and laparoscopic cholecystectomy (Crohnbach's α = 0.90). After the second round, 15 proposed key steps for laparoscopic appendectomy and 30 proposed key steps for laparoscopic cholecystectomy were rated as important (≥4 by at least 80% of the expert panel). These key steps were used for the further development of the training curriculum. By using the Delphi methodology, regional consensus was reached on the key steps for laparoscopic appendectomy and cholecystectomy. These key steps are going to be used for standardized training and evaluation purposes in a new regional laparoscopic curriculum. Copyright © 2014 Association of Program Directors in Surgery. Published by Elsevier Inc. All rights reserved.

Long range personalized cancer treatment strategies incorporating evolutionary dynamics.

PubMed

Yeang, Chen-Hsiang; Beckman, Robert A

2016-10-22

Current cancer precision medicine strategies match therapies to static consensus molecular properties of an individual's cancer, thus determining the next therapeutic maneuver. These strategies typically maintain a constant treatment while the cancer is not worsening. However, cancers feature complicated sub-clonal structure and dynamic evolution. We have recently shown, in a comprehensive simulation of two non-cross resistant therapies across a broad parameter space representing realistic tumors, that substantial improvement in cure rates and median survival can be obtained utilizing dynamic precision medicine strategies. These dynamic strategies explicitly consider intratumoral heterogeneity and evolutionary dynamics, including predicted future drug resistance states, and reevaluate optimal therapy every 45 days. However, the optimization is performed in single 45 day steps ("single-step optimization"). Herein we evaluate analogous strategies that think multiple therapeutic maneuvers ahead, considering potential outcomes at 5 steps ahead ("multi-step optimization") or 40 steps ahead ("adaptive long term optimization (ALTO)") when recommending the optimal therapy in each 45 day block, in simulations involving both 2 and 3 non-cross resistant therapies. We also evaluate an ALTO approach for situations where simultaneous combination therapy is not feasible ("Adaptive long term optimization: serial monotherapy only (ALTO-SMO)"). Simulations utilize populations of 764,000 and 1,700,000 virtual patients for 2 and 3 drug cases, respectively. Each virtual patient represents a unique clinical presentation including sizes of major and minor tumor subclones, growth rates, evolution rates, and drug sensitivities. While multi-step optimization and ALTO provide no significant average survival benefit, cure rates are significantly increased by ALTO. Furthermore, in the subset of individual virtual patients demonstrating clinically significant difference in outcome between approaches, by far the majority show an advantage of multi-step or ALTO over single-step optimization. ALTO-SMO delivers cure rates superior or equal to those of single- or multi-step optimization, in 2 and 3 drug cases respectively. In selected virtual patients incurable by dynamic precision medicine using single-step optimization, analogous strategies that "think ahead" can deliver long-term survival and cure without any disadvantage for non-responders. When therapies require dose reduction in combination (due to toxicity), optimal strategies feature complex patterns involving rapidly interleaved pulses of combinations and high dose monotherapy. This article was reviewed by Wendy Cornell, Marek Kimmel, and Andrzej Swierniak. Wendy Cornell and Andrzej Swierniak are external reviewers (not members of the Biology Direct editorial board). Andrzej Swierniak was nominated by Marek Kimmel.

Heating of a fully saturated darcian half-space: Pressure generation, fluid expulsion, and phase change

USGS Publications Warehouse

Delaney, P.

1984-01-01

Analytical solutions are developed for the pressurization, expansion, and flow of one- and two-phase liquids during heating of fully saturated and hydraulically open Darcian half-spaces subjected to a step rise in temperature at its surface. For silicate materials, advective transfer is commonly unimportant in the liquid region; this is not always the case in the vapor region. Volume change is commonly more important than heat of vaporization in determining the position of the liquid-vapor interface, assuring that the temperatures cannot be determined independently of pressures. Pressure increases reach a maximum near the leading edge of the thermal front and penetrate well into the isothermal region of the body. Mass flux is insensitive to the hydraulic properties of the half-space. ?? 1984.

One Step Back? Reassessing an Ideal Security State for Northeast Asia 2025

DTIC Science & Technology

2011-03-01

kept policy interest rates below 2% for three years , from December 2001 to November 2004, which made low-interest loans available to households and...three consecutive years of CA imbalances exceeding 2% of her GDP, the exchange rate will move to correct the imbalance. This market discipline works... exchange rates . Movement in the yuan is more or less determined by the policy goals of the People’s Republic of China (PRC), not by market forces. Tight

["More Market" does not induce health--the relationship between social risks and the assurance of solidarity].

PubMed

Hengsbach, F

2008-06-01

The prevailing fashion of German macroeconomics has meanwhile extended the common apprehension against the special characteristic of labour towards the good "health". Against the background of this currently prevailing trend, a school of thought which claims a qualitative difference between food, industrial goods or shares and good "health" is provocative. This is true even if society is getting used to a rhetoric of health markets and of the factors determining the supply and demand of health goods. In a first step it will be made transparent how, currently, commercial imperatives are dominating the health-care system. In a second step political interventions will be named that have reinforced commercial imperatives. The chances of solidarity-based alternatives for the health-care system are presented and discussed in a third step.

Noise analysis of genome-scale protein synthesis using a discrete computational model of translation

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

Racle, Julien; Hatzimanikatis, Vassily, E-mail: vassily.hatzimanikatis@epfl.ch; Swiss Institute of Bioinformatics

2015-07-28

Noise in genetic networks has been the subject of extensive experimental and computational studies. However, very few of these studies have considered noise properties using mechanistic models that account for the discrete movement of ribosomes and RNA polymerases along their corresponding templates (messenger RNA (mRNA) and DNA). The large size of these systems, which scales with the number of genes, mRNA copies, codons per mRNA, and ribosomes, is responsible for some of the challenges. Additionally, one should be able to describe the dynamics of ribosome exchange between the free ribosome pool and those bound to mRNAs, as well as howmore » mRNA species compete for ribosomes. We developed an efficient algorithm for stochastic simulations that addresses these issues and used it to study the contribution and trade-offs of noise to translation properties (rates, time delays, and rate-limiting steps). The algorithm scales linearly with the number of mRNA copies, which allowed us to study the importance of genome-scale competition between mRNAs for the same ribosomes. We determined that noise is minimized under conditions maximizing the specific synthesis rate. Moreover, sensitivity analysis of the stochastic system revealed the importance of the elongation rate in the resultant noise, whereas the translation initiation rate constant was more closely related to the average protein synthesis rate. We observed significant differences between our results and the noise properties of the most commonly used translation models. Overall, our studies demonstrate that the use of full mechanistic models is essential for the study of noise in translation and transcription.« less

A rapid, straightforward, and print house compatible mass fabrication method for integrating 3D paper-based microfluidics.

PubMed

Xiao, Liangpin; Liu, Xianming; Zhong, Runtao; Zhang, Kaiqing; Zhang, Xiaodi; Zhou, Xiaomian; Lin, Bingcheng; Du, Yuguang

2013-11-01

Three-dimensional (3D) paper-based microfluidics, which is featured with high performance and speedy determination, promise to carry out multistep sample pretreatment and orderly chemical reaction, which have been used for medical diagnosis, cell culture, environment determination, and so on with broad market prospect. However, there are some drawbacks in the existing fabrication methods for 3D paper-based microfluidics, such as, cumbersome and time-consuming device assembly; expensive and difficult process for manufacture; contamination caused by organic reagents from their fabrication process. Here, we present a simple printing-bookbinding method for mass fabricating 3D paper-based microfluidics. This approach involves two main steps: (i) wax-printing, (ii) bookbinding. We tested the delivery capability, diffusion rate, homogeneity and demonstrated the applicability of the device to chemical analysis by nitrite colorimetric assays. The described method is rapid (<30 s), cheap, easy to manipulate, and compatible with the flat stitching method that is common in a print house, making itself an ideal scheme for large-scale production of 3D paper-based microfluidics. © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Creep Strain and Strain Rate Response of 2219 Al Alloy at High Stress Levels

NASA Technical Reports Server (NTRS)

Taminger, Karen M. B.; Wagner, John A.; Lisagor, W. Barry

1998-01-01

As a result of high localized plastic deformation experienced during proof testing in an International Space Station connecting module, a study was undertaken to determine the deformation response of a 2219-T851 roll forging. After prestraining 2219-T851 Al specimens to simulate strains observed during the proof testing, creep tests were conducted in the temperature range from ambient temperature to 107 C (225 F) at stress levels approaching the ultimate tensile strength of 2219-T851 Al. Strain-time histories and strain rate responses were examined. The strain rate response was extremely high initially, but decayed rapidly, spanning as much as five orders of magnitude during primary creep. Select specimens were subjected to incremental step loading and exhibited initial creep rates of similar magnitude for each load step. Although the creep rates decreased quickly at all loads, the creep rates dropped faster and reached lower strain rate levels for lower applied loads. The initial creep rate and creep rate decay associated with primary creep were similar for specimens with and without prestrain; however, prestraining (strain hardening) the specimens, as in the aforementioned proof test, resulted in significantly longer creep life.

Optimizing the number of steps in learning tasks for complex skills.

PubMed

Nadolski, Rob J; Kirschner, Paul A; van Merriënboer, Jeroen J G

2005-06-01

Carrying out whole tasks is often too difficult for novice learners attempting to acquire complex skills. The common solution is to split up the tasks into a number of smaller steps. The number of steps must be optimized for efficient and effective learning. The aim of the study is to investigate the relation between the number of steps provided to learners and the quality of their learning of complex skills. It is hypothesized that students receiving an optimized number of steps will learn better than those receiving either the whole task in only one step or those receiving a large number of steps. Participants were 35 sophomore law students studying at Dutch universities, mean age=22.8 years (SD=3.5), 63% were female. Participants were randomly assigned to 1 of 3 computer-delivered versions of a multimedia programme on how to prepare and carry out a law plea. The versions differed only in the number of learning steps provided. Videotaped plea-performance results were determined, various related learning measures were acquired and all computer actions were logged and analyzed. Participants exposed to an intermediate (i.e. optimized) number of steps outperformed all others on the compulsory learning task. No differences in performance on a transfer task were found. A high number of steps proved to be less efficient for carrying out the learning task. An intermediate number of steps is the most effective, proving that the number of steps can be optimized for improving learning.

General Template for the FMEA Applications in Primary Food Processing.

PubMed

Özilgen, Sibel; Özilgen, Mustafa

Data on the hazards involved in the primary steps of processing cereals, fruit and vegetables, milk and milk products, meat and meat products, and fats and oils are compiled with a wide-ranging literature survey. After determining the common factors from these data, a general FMEA template is offered, and its use is explained with a case study on pasteurized milk production.

Specific and non-specific symptoms of colorectal cancer and contact to general practice.

PubMed

Rasmussen, Sanne; Larsen, Pia V; Søndergaard, Jens; Elnegaard, Sandra; Svendsen, Rikke P; Jarbøl, Dorte E

2015-08-01

To improve survival rates for colorectal cancer, referral guidelines have been implemented. First step in the diagnostic process is for the individual to recognize the symptoms and contact his/her general practitioner (GP) for evaluation. To determine (i) the prevalence of specific and non-specific symptom experiences indicative of colorectal cancer, (ii) the proportion of subsequent contacts to GPs, (iii) to explore the possible differences in symptom experience and contact to GPs between age and sex. A nationwide study of 100000 adults, aged 20 years and older, were randomly selected in the general population and invited to participate in an internet-based survey. Items regarding experience of specific and non-specific alarm symptoms of colorectal cancer within the preceding 4 weeks and contact to GP were included. A total of 49706 subjects completed the questionnaire. Abdominal pain was the most common specific alarm symptom (19.7%) and tiredness was the most common non-specific symptom (49.8%). The experiences of symptoms were more common among women and more common in the youngest age groups for both sexes. The symptom leading to the highest proportion of GP contacts was rectal bleeding (33.8%). When experiencing any combination of two specific alarm symptoms, the proportion who contacted a GP was less than 50%. The combination of a non-specific and a specific alarm symptom gave rise to the highest proportion of GP contacts. Although specific and non-specific alarm symptoms of colorectal cancer are common in the general population, the proportion of GP contacts is low. © The Author 2015. Published by Oxford University Press. All rights reserved. For permissions, please e-mail: journals.permissions@oup.com.

Biologic considerations regarding the one and two step procedures in the management of patients with invasive carcinoma of the breast.

PubMed

Fisher, E R; Sass, R; Fisher, B

1985-09-01

Investigation of the biologic significance of delay between biopsy and mastectomy was performed upon women with invasive carcinoma of the breast in protocol four of the NSABP. Since the period of delay was two weeks or less in approximately 75 per cent, no comment concerning the possible effects of longer periods can be made. Life table analyses failed to reveal any difference in ten year survival rates between patients undergoing radical mastectomy management by the one and two step procedures. Similarly, no difference in adjusted ten year survival rate was observed between women managed by the two step procedure who did or did not have residual tumor identified in the mastectomy specimen after the first step or biopsy. Importantly, the clinical or pathologic stages, sizes of tumor or histologic grades were similar in women managed by the one and two step procedures minimizing selection bias. The material used also allowed for study of the possible causative role of biopsy of the breast on the development of sinus histiocytosis in regional axillary lymph nodes. No difference in degree or types of this nodal reaction could be discerned in the lymph nodes of the mastectomy specimens obtained from patients who had undergone the one and two step procedures. This finding indicates that nodal sinus histiocytosis is indeed related to the neoplastic process, albeit in an undefined manner, rather than the trauma of biopsy per se as has been suggested. These results do not invalidate the use of the one step procedure in the management of patients with carcinoma of the breast. Indeed, it is highly likely that it will be commonly used now that breast-conserving operations appear to represent a viable alternative modality for the primary surgical treatment of carcinoma of the breast. Yet, it is apparent that the one step procedure will be performed for technical and practical rather than biologic reasons.

Music and movement share a dynamic structure that supports universal expressions of emotion

PubMed Central

Sievers, Beau; Polansky, Larry; Casey, Michael; Wheatley, Thalia

2013-01-01

Music moves us. Its kinetic power is the foundation of human behaviors as diverse as dance, romance, lullabies, and the military march. Despite its significance, the music-movement relationship is poorly understood. We present an empirical method for testing whether music and movement share a common structure that affords equivalent and universal emotional expressions. Our method uses a computer program that can generate matching examples of music and movement from a single set of features: rate, jitter (regularity of rate), direction, step size, and dissonance/visual spikiness. We applied our method in two experiments, one in the United States and another in an isolated tribal village in Cambodia. These experiments revealed three things: (i) each emotion was represented by a unique combination of features, (ii) each combination expressed the same emotion in both music and movement, and (iii) this common structure between music and movement was evident within and across cultures. PMID:23248314

The “Health Coaching” programme: a new patient-centred and visually supported approach for health behaviour change in primary care

PubMed Central

2013-01-01

Background Health related behaviour is an important determinant of chronic disease, with a high impact on public health. Motivating and assisting people to change their unfavourable health behaviour is thus a major challenge for health professionals. The objective of the study was to develop a structured programme of counselling in primary care practice, and to test its feasibility and acceptance among general practitioners (GPs) and their patients. Methods Our new concept integrates change of roles, shared responsibility, patient-centredness, and modern communication techniques—such as motivational interviewing. A new colour-coded visual communication tool is used for the purpose of leading through the 4-step counselling process. As doctors’ communication skills are crucial, communication training is a mandatory part of the programme. We tested the feasibility and acceptance of the “Health Coaching” programme with 20 GPs and 1045 patients, using questionnaires and semistructured interviewing techniques. The main outcomes were participation rates; the duration of counselling; patients’ self-rated behavioural change in their areas of choice; and ratings of motivational, conceptual, acceptance, and feasibility issues. Results In total, 37% (n=350) of the patients enrolled in step 1 completed the entire 4-Step counselling process, with each step taking 8–22 minutes. 50% of ratings (n=303) improved by one or two categories in the three-colour circle, and the proportion of favourable health behaviour ratings increased from 9% to 39%. The ratings for motivation, concept, acceptance, and feasibility of the “Health Coaching” programme were consistently high. Conclusions Our innovative, patient-centred counselling programme for health behaviour change was well accepted and feasible among patients and physicians in a primary care setting. Randomised controlled studies will have to establish cost-effectiveness and promote dissemination. PMID:23865509

The "Health Coaching" programme: a new patient-centred and visually supported approach for health behaviour change in primary care.

PubMed

Neuner-Jehle, Stefan; Schmid, Margareta; Grüninger, Ueli

2013-07-17

Health related behaviour is an important determinant of chronic disease, with a high impact on public health. Motivating and assisting people to change their unfavourable health behaviour is thus a major challenge for health professionals. The objective of the study was to develop a structured programme of counselling in primary care practice, and to test its feasibility and acceptance among general practitioners (GPs) and their patients. Our new concept integrates change of roles, shared responsibility, patient-centredness, and modern communication techniques-such as motivational interviewing. A new colour-coded visual communication tool is used for the purpose of leading through the 4-step counselling process. As doctors' communication skills are crucial, communication training is a mandatory part of the programme. We tested the feasibility and acceptance of the "Health Coaching" programme with 20 GPs and 1045 patients, using questionnaires and semistructured interviewing techniques. The main outcomes were participation rates; the duration of counselling; patients' self-rated behavioural change in their areas of choice; and ratings of motivational, conceptual, acceptance, and feasibility issues. In total, 37% (n=350) of the patients enrolled in step 1 completed the entire 4-Step counselling process, with each step taking 8-22 minutes. 50% of ratings (n=303) improved by one or two categories in the three-colour circle, and the proportion of favourable health behaviour ratings increased from 9% to 39%. The ratings for motivation, concept, acceptance, and feasibility of the "Health Coaching" programme were consistently high. Our innovative, patient-centred counselling programme for health behaviour change was well accepted and feasible among patients and physicians in a primary care setting. Randomised controlled studies will have to establish cost-effectiveness and promote dissemination.

Examining attrition rates at one specialty addiction treatment provider in the United States: a case study using a retrospective chart review.

PubMed

Loveland, David; Driscoll, Hilary

2014-09-25

Engaging individuals who have a substance use disorder (SUD) in treatment continues to be a challenge for the specialty addiction treatment field. Research has consistently revealed high rates of missed appointments at each step of the enrollment process: 1. between calling for services and assessment, 2. between assessment and enrollment, and 3. between enrollment and completion of treatment. Extensive research has examined each step of the process; however, there is limited research examining the overall attrition rate across all steps. A single case study of a specialty addiction treatment agency was used to examine the attrition rates across the first three steps of the enrollment process. Attrition rates were tracked between August 1, 2011 and July 31, 2012. The cohort included 1822 unique individuals who made an initial request for addiction treatment services. Monthly retrospective reviews of medical records, phone logs, and billing data were used to calculate attrition rates. Attrition rates reported in the literature were collected and compared to the rates found at the target agency. Median time between request for treatment and assessment was 6 days (mean 7.5) and between assessment and treatment enrollment was 8 days (mean 12.5). An overall attrition rate of 80% was observed, including 45% between call and assessment, 32% between assessment and treatment enrollment (another 17% could not be determined), and 37% left or were removed from treatment before 30 days. Women were less likely to complete 30 days of treatment compared to men. No other demographics were related to attrition rates. One out of every five people who requested treatment completed a minimum of 30 days of a treatment. The attrition rate was high, yet similar to rates noted in the literature. Limitations of the single case study are noted. Attrition rates in the U.S. are high with approximately 75% to 80% of treatment seekers disengaging at one of the multiple stages of the enrollment and treatment process. Significant changes in the system are needed to improve engagement rates.

Kinetic mechanism of human DNA ligase I reveals magnesium-dependent changes in the rate-limiting step that compromise ligation efficiency.

PubMed

Taylor, Mark R; Conrad, John A; Wahl, Daniel; O'Brien, Patrick J

2011-07-01

DNA ligase I (LIG1) catalyzes the ligation of single-strand breaks to complete DNA replication and repair. The energy of ATP is used to form a new phosphodiester bond in DNA via a reaction mechanism that involves three distinct chemical steps: enzyme adenylylation, adenylyl transfer to DNA, and nick sealing. We used steady state and pre-steady state kinetics to characterize the minimal mechanism for DNA ligation catalyzed by human LIG1. The ATP dependence of the reaction indicates that LIG1 requires multiple Mg(2+) ions for catalysis and that an essential Mg(2+) ion binds more tightly to ATP than to the enzyme. Further dissection of the magnesium ion dependence of individual reaction steps revealed that the affinity for Mg(2+) changes along the reaction coordinate. At saturating concentrations of ATP and Mg(2+) ions, the three chemical steps occur at similar rates, and the efficiency of ligation is high. However, under conditions of limiting Mg(2+), the nick-sealing step becomes rate-limiting, and the adenylylated DNA intermediate is prematurely released into solution. Subsequent adenylylation of enzyme prevents rebinding to the adenylylated DNA intermediate comprising an Achilles' heel of LIG1. These ligase-generated 5'-adenylylated nicks constitute persistent breaks that are a threat to genomic stability if they are not repaired. The kinetic and thermodynamic framework that we have determined for LIG1 provides a starting point for understanding the mechanism and specificity of mammalian DNA ligases.

Reinterpretation of curved Hammett plots in reaction of nucleophiles with aryl benzoates: change in rate-determining step or mechanism versus ground-state stabilization.

PubMed

Um, Ik-Hwan; Han, Hyun-Joo; Ahn, Jung-Ae; Kang, Swan; Buncel, Erwin

2002-11-29

A kinetic study is reported for the reaction of the anionic nucleophiles OH-, CN-, and N 3 - with aryl benzoates containing substituents on the benzoyl as well as the aryloxy moiety, in 80 mol % H2O - 20 mol % dimethyl sulfoxide at 25.0 degrees C. Hammett log k vs sigma plots for these systems are consistently nonlinear. However, a possible traditional explanation in terms of a mechanism involving a tetrahedral intermediate with curvature resulting from a change in rate-determining step is considered but rejected. The proposed explanation involves ground-state stabilization through resonance interaction between the benzoyl substituent and the electrophilic carbonyl center in the two-stage mechanism. Accordingly, the data are nicely accommodated on the basis of the Yukawa-Tsuno equation, which gives linear plots for all three nuceophiles. Literature reports of the mechanism of acyl transfer processes are reconsidered in this light.

Use of intradermal dilutional testing and skin prick testing: clinical relevance and cost efficiency.

PubMed

Seshul, Merritt; Pillsbury, Harold; Eby, Thomas

2006-09-01

The objective was to determine the agreement of the positive results from a multiple skin prick test (SPT) device with the ability to determine a definable endpoint through intradermal dilutional testing (IDT) to compare semiquantitatively the degree of positivity of SPT results with quantitative results from IDT and to analyze the cost of immunotherapy based on SPT compared with IDT guided by SPT. Retrospective review of clinical data (random accrual). One hundred thirty-four patients underwent allergy screening using a multiple SPT device. Antigens testing positive by skin prick device were tested using IDT on a separate day. Antigens testing negative by SPT were not evaluated by IDT. Regional allergy testing practice patterns were determined, and a cost analysis using Medicare rates was performed There was good agreement between an antigen testing positive by SPT and the determination of a definable endpoint (93.33%, n = 1,334 antigens). The degree of positivity from the SPT correlated poorly with the final endpoint concentration (r = 0.40, P < .0001). Blended testing techniques were similar in cost when compared with several commonly used allergy testing protocols. Antigens which show reactivity to a multiple SPT device usually have a treatable endpoint that is independent of the degree of positivity of the SPT result. IDT is an important step in the determination of the strongest starting dose of immunotherapy that may be safely administered. Initiating immunotherapy in this manner may potentially create significant health care savings by shortening the time required for a patient to reach their individual maximally tolerated dose. The use of a relatively large screening panel is cost effective and does not increase the average number of antigens treated by immunotherapy. Blended allergy testing techniques that include IDT in their protocol are comparable in cost with commonly used allergy testing protocols.

Theoretical study on the reaction mechanism of hydrogenation of furfural to furfuryl alcohol on Lewis acidic BEA zeolites: effects of defect structure and tetravalent metals substitution.

PubMed

Injongkol, Yuwanda; Maihom, Thana; Treesukul, Piti; Sirijaraensre, Jakkapan; Boekfa, Bundet; Limtrakul, Jumras

2017-09-13

Furfural acquired from agricultural sources is receiving extensive attention in the petrochemical industry as it offers an alternative route to generate more valuable hydrocarbon compounds. Herein, we investigate the furfural hydrogenation to furfuryl alcohol catalyzed by Lewis acidic BEA zeolites at the molecular level by means of the M06-L density functional theory. The mechanistic pictures in the catalytic procedure are revealed. The possible reaction pathways are considered to proceed via either concerted or stepwise mechanisms. With the contribution of zeolite oxygen bridging for the H-H splitting, the rate determining step activation barrier for the stepwise mechanism is 14.7 kcal mol -1 lower than that for the concerted mechanism. The stepwise reaction therefore seems to be favored compared to the concerted one. The catalytic effect of the defect zeolite framework on the stepwise mechanism is also investigated. The activation energy for the stepwise rate-determining step over this site is significantly lower than the corresponding step over the perfect one by 14.1 kcal mol -1 . Finally, the catalytic activity of tetravalent metal centers (Sn, Ge, Zr and Hf) substituted in BEA is also preliminarily compared and it is found to follow the order of Hf > Zr > Sn > Ge based on activation energies and the reaction rate. The difference in the activation energy can be traced back to the difference in the charge transfer from the catalytic site to the adsorbed molecules.

Effects of Alloyed Metal on the Catalysis Activity of Pt for Ethanol Partial Oxidation: Adsorption and Dehydrogenation on Pt3M (M=Pt, Ru, Sn, Re, Rh, and Pd)

PubMed Central

Xu, Zhen-Feng; Wang, Yixuan

2011-01-01

The adsorption and dehydrogenation reactions of ethanol over bimetallic clusters, Pt3M (M = Pt, Ru, Sn, Re, Rh, and Pd), have been extensively investigated with density functional theory. Both the α-hydrogen and hydroxyl adsorptions on Pt as well as on the alloyed transition metal M sites of PtM were considered as initial reaction steps. The adsorptions of ethanol on Pt and M sites of some PtM via the α-hydrogen were well established. Although the α-hydrogen adsorption on Pt site is weaker than the hydroxyl, the potential energy profiles show that the dehydrogenation via the α-hydrogen path has much lower energy barrier than that via the hydroxyl path. Generally for the α-hydrogen path the adsorption is a rate-determining-step because of rather low dehydrogenation barrier for the α-hydrogen adsorption complex (thermodynamic control), while the hydroxyl path is determined by its dehydrogenation step (kinetic control). The effects of alloyed metal on the catalysis activity of Pt for ethanol partial oxidation, including adsorption energy, energy barrier, electronic structure, and eventually rate constant were discussed. Among all of the alloyed metals only Sn enhances the rate constant of the dehydrogenation via the α-hydrogen path on the Pt site of Pt3Sn as compared with Pt alone, which interprets why the PtSn is the most active to the oxidation of ethanol. PMID:22102920

A hazard rate analysis of fertility using duration data from Malaysia.

PubMed

Chang, C

1988-01-01

Data from the Malaysia Fertility and Family Planning Survey (MFLS) of 1974 were used to investigate the effects of biological and socioeconomic variables on fertility based on the hazard rate model. Another study objective was to investigate the robustness of the findings of Trussell et al. (1985) by comparing the findings of this study with theirs. The hazard rate of conception for the jth fecundable spell of the ith woman, hij, is determined by duration dependence, tij, measured by the waiting time to conception; unmeasured heterogeneity (HETi; the time-invariant variables, Yi (race, cohort, education, age at marriage); and time-varying variables, Xij (age, parity, opportunity cost, income, child mortality, child sex composition). In this study, all the time-varying variables were constant over a spell. An asymptotic X2 test for the equality of constant hazard rates across birth orders, allowing time-invariant variables and heterogeneity, showed the importance of time-varying variables and duration dependence. Under the assumption of fixed effects heterogeneity and the Weibull distribution for the duration of waiting time to conception, the empirical results revealed a negative parity effect, a negative impact from male children, and a positive effect from child mortality on the hazard rate of conception. The estimates of step functions for the hazard rate of conception showed parity-dependent fertility control, evidence of heterogeneity, and the possibility of nonmonotonic duration dependence. In a hazard rate model with piecewise-linear-segment duration dependence, the socioeconomic variables such as cohort, child mortality, income, and race had significant effects, after controlling for the length of the preceding birth. The duration dependence was consistant with the common finding, i.e., first increasing and then decreasing at a slow rate. The effects of education and opportunity cost on fertility were insignificant.

Experimental and computational fluid dynamic studies of mixing for complex oral health products

NASA Astrophysics Data System (ADS)

Garcia, Marti Cortada; Mazzei, Luca; Angeli, Panagiota

2015-11-01

Mixing high viscous non-Newtonian fluids is common in the consumer health industry. Sometimes this process is empirical and involves many pilot plants trials which are product specific. The first step to study the mixing process is to build on knowledge on the rheology of the fluids involved. In this research a systematic approach is used to validate the rheology of two liquids: glycerol and a gel formed by polyethylene glycol and carbopol. Initially, the constitutive equation is determined which relates the viscosity of the fluids with temperature, shear rate, and concentration. The key variable for the validation is the power required for mixing, which can be obtained both from CFD and experimentally using a stirred tank and impeller of well-defined geometries at different impeller speeds. A good agreement between the two values indicates a successful validation of the rheology and allows the CFD model to be used for the study of mixing in the complex vessel geometries and increased sizes encountered during scale up.

Modeling residence-time distribution in horizontal screw hydrolysis reactors

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

Sievers, David A.; Stickel, Jonathan J.

The dilute-acid thermochemical hydrolysis step used in the production of liquid fuels from lignocellulosic biomass requires precise residence-time control to achieve high monomeric sugar yields. Difficulty has been encountered reproducing residence times and yields when small batch reaction conditions are scaled up to larger pilot-scale horizontal auger-tube type continuous reactors. A commonly used naive model estimated residence times of 6.2-16.7 min, but measured mean times were actually 1.4-2.2 the estimates. Here, this study investigated how reactor residence-time distribution (RTD) is affected by reactor characteristics and operational conditions, and developed a method to accurately predict the RTD based on key parameters.more » Screw speed, reactor physical dimensions, throughput rate, and process material density were identified as major factors affecting both the mean and standard deviation of RTDs. The general shape of RTDs was consistent with a constant value determined for skewness. The Peclet number quantified reactor plug-flow performance, which ranged between 20 and 357.« less

Modeling residence-time distribution in horizontal screw hydrolysis reactors

DOE PAGES

Sievers, David A.; Stickel, Jonathan J.

2017-10-12

The dilute-acid thermochemical hydrolysis step used in the production of liquid fuels from lignocellulosic biomass requires precise residence-time control to achieve high monomeric sugar yields. Difficulty has been encountered reproducing residence times and yields when small batch reaction conditions are scaled up to larger pilot-scale horizontal auger-tube type continuous reactors. A commonly used naive model estimated residence times of 6.2-16.7 min, but measured mean times were actually 1.4-2.2 the estimates. Here, this study investigated how reactor residence-time distribution (RTD) is affected by reactor characteristics and operational conditions, and developed a method to accurately predict the RTD based on key parameters.more » Screw speed, reactor physical dimensions, throughput rate, and process material density were identified as major factors affecting both the mean and standard deviation of RTDs. The general shape of RTDs was consistent with a constant value determined for skewness. The Peclet number quantified reactor plug-flow performance, which ranged between 20 and 357.« less

Determination of the diffusion coefficient and phase-transfer rate parameter in LaNi{sub 5} and MmNi{sub 3.6}Co{sub 0.8}Mn{sub 0.4}Al{sub 0.3} using microelectrodes

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

Lundqvist, A.; Lindbergh, G.

1998-11-01

A potential-step method for determining the diffusion coefficient and phase-transfer parameter in metal hydrides by using microelectrodes was investigated. It was shown that a large potential step is not enough to ensure a completely diffusion-limited mass transfer if a surface-phase transfer reaction takes place at a finite rate. It was shown, using a kinetic expression for the surface phase-transfer reaction, that the slope of the logarithm of the current vs. time curve will be constant both in the case of the mass-transfer limited by diffusion or by diffusion and a surface-phase transfer. The diffusion coefficient and phase-transfer rate parameter weremore » accurately determined for MmNi{sub 3.6}Co{sub 0.8}Mn{sub 0.4}Al{sub 0.3} using a fit to the whole transient. The diffusion coefficient was found to be (1.3 {+-} 0.3) {times} 10{sup {minus}13} m{sup 2}/s. The fit was good and showed that a pure diffusion model was not enough to explain the observed transient. The diffusion coefficient and phase-transfer rate parameter were also estimated for pure LaNi{sub 5}. A fit of the whole curve showed that neither a pure diffusion model nor a model including phase transfer could explain the whole transient.« less

Numerical investigation and performance characteristic mapping of an Archimedean screw hydroturbine

NASA Astrophysics Data System (ADS)

Schleicher, W. Chris

Computational Fluid Dynamics (CFD) is a crucial tool in the design and analysis of hydraulic machinery, especially in the design of a micro hydro turbine. The micro hydro turbine in question is for a low head (less than 60 meters), low volumetric flow rate (0.005 m3/s to 0.5 m 3/s) application with rotation rates varying from 200 RPM to 1500 RPM. The design of the runner geometry is discussed, specifically a non-uniform Archimedean Spiral with an outer diameter of 6 inches and length of 19.5 inches. The transient simulation method, making use of a frame of reference change and a rotating mesh between time-steps, is explained as well as the corresponding boundary conditions. Both simulation methods are compared and are determined to produce similar results. The rotating frame of reference method was determined to be the most suitable method for the mapping of performance characteristic such as required head, torque, power, and efficiency. Results of simulations for a non-uniform Archimedean Spiral are then presented. First, a spectral and temporal convergence study is conducted to make sure that the results are independent of time-step and mesh selection. Performance characteristics of a non-uniform pitched blade turbine are determined for a wide range of volumetric flow rates and rotation rates. The maximum efficiency of the turbine is calculated around 72% for the design of the turbine blade considered in the present study.

Structure reactivity and thermodynamic analysis on the oxidation of ampicillin drug by copper(III) complex in aqueous alkaline medium (stopped-flow technique)

NASA Astrophysics Data System (ADS)

Shetti, Nagaraj P.; Hegde, Rajesh N.; Nandibewoor, Sharanappa T.

2009-07-01

Oxidation of penicillin derivative, ampicillin (AMP) by diperiodatocuprate(III) (DPC) in alkaline medium at a constant ionic strength of 0.01-mol dm -3 was studied spectrophotometrically. The reaction between DPC and ampicillin in alkaline medium exhibits 1:4 stoichiometry (ampicillin:DPC). Intervention of free radicals was observed in the reaction. Based on the observed orders and experimental evidences, a mechanism involving the protonated form of DPC as the reactive oxidant species has been proposed. The oxidation reaction in alkaline medium has been shown to proceed via a DPC-AMP complex, which decomposes slowly in a rate determining step to yield phenyl glycine (PG) and free radical species of 6-aminopenicillanic acid (6-APA), followed by other fast steps to give the products. The two major products were characterized by IR, NMR, LC-MS and Spot test. The reaction constants involved in the different steps of the mechanism were calculated. The activation parameters with respect to slow step of the mechanism were computed and discussed and thermodynamic quantities were also determined.

Extravascular transport in normal and tumor tissues.

PubMed

Jain, R K; Gerlowski, L E

1986-01-01

The transport characteristics of the normal and tumor tissue extravascular space provide the basis for the determination of the optimal dosage and schedule regimes of various pharmacological agents in detection and treatment of cancer. In order for the drug to reach the cellular space where most therapeutic action takes place, several transport steps must first occur: (1) tissue perfusion; (2) permeation across the capillary wall; (3) transport through interstitial space; and (4) transport across the cell membrane. Any of these steps including intracellular events such as metabolism can be the rate-limiting step to uptake of the drug, and these rate-limiting steps may be different in normal and tumor tissues. This review examines these transport limitations, first from an experimental point of view and then from a modeling point of view. Various types of experimental tumor models which have been used in animals to represent human tumors are discussed. Then, mathematical models of extravascular transport are discussed from the prespective of two approaches: compartmental and distributed. Compartmental models lump one or more sections of a tissue or body into a "compartment" to describe the time course of disposition of a substance. These models contain "effective" parameters which represent the entire compartment. Distributed models consider the structural and morphological aspects of the tissue to determine the transport properties of that tissue. These distributed models describe both the temporal and spatial distribution of a substance in tissues. Each of these modeling techniques is described in detail with applications for cancer detection and treatment in mind.

Impact of enhanced sensory input on treadmill step frequency: infants born with myelomeningocele.

PubMed

Pantall, Annette; Teulier, Caroline; Smith, Beth A; Moerchen, Victoria; Ulrich, Beverly D

2011-01-01

To determine the effect of enhanced sensory input on the step frequency of infants with myelomeningocele (MMC) when supported on a motorized treadmill. Twenty-seven infants aged 2 to 10 months with MMC lesions at, or caudal to, L1 participated. We supported infants upright on the treadmill for 2 sets of 6 trials, each 30 seconds long. Enhanced sensory inputs within each set were presented in random order and included baseline, visual flow, unloading, weights, Velcro, and friction. Overall friction and visual flow significantly increased step rate, particularly for the older subjects. Friction and Velcro increased stance-phase duration. Enhanced sensory input had minimal effect on leg activity when infants were not stepping. : Increased friction via Dycem and enhancing visual flow via a checkerboard pattern on the treadmill belt appear to be more effective than the traditional smooth black belt surface for eliciting stepping patterns in infants with MMC.

Impact of Enhanced Sensory Input on Treadmill Step Frequency: Infants Born With Myelomeningocele

PubMed Central

Pantall, Annette; Teulier, Caroline; Smith, Beth A; Moerchen, Victoria; Ulrich, Beverly D.

2012-01-01

Purpose To determine the effect of enhanced sensory input on the step frequency of infants with myelomeningocele (MMC) when supported on a motorized treadmill. Methods Twenty seven infants aged 2 to 10 months with MMC lesions at or caudal to L1 participated. We supported infants upright on the treadmill for 2 sets of 6 trials, each 30s long. Enhanced sensory inputs within each set were presented in random order and included: baseline, visual flow, unloading, weights, Velcro and friction. Results Overall friction and visual flow significantly increased step rate, particularly for the older group. Friction and Velcro increased stance phase duration. Enhanced sensory input had minimal effect on leg activity when infants were not stepping. Conclusions Increased friction via Dycem and enhancing visual flow via a checkerboard pattern on the treadmill belt appear more effective than the traditional smooth black belt surface for eliciting stepping patterns in infants with MMC. PMID:21266940

United States Medical Licensing Examination and American Board of Pediatrics Certification Examination Results: Does the Residency Program Contribute to Trainee Achievement.

PubMed

Welch, Thomas R; Olson, Brad G; Nelsen, Elizabeth; Beck Dallaghan, Gary L; Kennedy, Gloria A; Botash, Ann

2017-09-01

To determine whether training site or prior examinee performance on the US Medical Licensing Examination (USMLE) step 1 and step 2 might predict pass rates on the American Board of Pediatrics (ABP) certifying examination. Data from graduates of pediatric residency programs completing the ABP certifying examination between 2009 and 2013 were obtained. For each, results of the initial ABP certifying examination were obtained, as well as results on National Board of Medical Examiners (NBME) step 1 and step 2 examinations. Hierarchical linear modeling was used to nest first-time ABP results within training programs to isolate program contribution to ABP results while controlling for USMLE step 1 and step 2 scores. Stepwise linear regression was then used to determine which of these examinations was a better predictor of ABP results. A total of 1110 graduates of 15 programs had complete testing results and were subject to analysis. Mean ABP scores for these programs ranged from 186.13 to 214.32. The hierarchical linear model suggested that the interaction of step 1 and 2 scores predicted ABP performance (F[1,1007.70] = 6.44, P = .011). By conducting a multilevel model by training program, both USMLE step examinations predicted first-time ABP results (b = .002, t = 2.54, P = .011). Linear regression analyses indicated that step 2 results were a better predictor of ABP performance than step 1 or a combination of the two USMLE scores. Performance on the USMLE examinations, especially step 2, predicts performance on the ABP certifying examination. The contribution of training site to ABP performance was statistically significant, though contributed modestly to the effect compared with prior USMLE scores. Copyright © 2017 Elsevier Inc. All rights reserved.

A linearly frequency-swept high-speed-rate multi-wavelength laser for optical coherence tomography

NASA Astrophysics Data System (ADS)

Wang, Qiyu; Wang, Zhaoying; Yuan, Quan; Ma, Rui; Du, Tao; Yang, Tianxin

2017-02-01

We proposed and demonstrated a linearly frequency-swept multi-wavelength laser source for optical coherence tomography (OCT) eliminating the need of wavenumber space resampling in the postprocessing progress. The source consists of a multi-wavelength fiber laser source (MFS) and an optical sweeping loop. In this novel laser source, an equally spaced multi-wavelength laser is swept simultaneously by a certain step each time in the frequency domain in the optical sweeping loop. The sweeping step is determined by radio frequency (RF) signal which can be precisely controlled. Thus the sweeping behavior strictly maintains a linear relationship between time and frequency. We experimentally achieved linear time-frequency sweeping at a sweeping rate of 400 kHz with our laser source.

An introduction to data reduction: space-group determination, scaling and intensity statistics.

PubMed

Evans, Philip R

2011-04-01

This paper presents an overview of how to run the CCP4 programs for data reduction (SCALA, POINTLESS and CTRUNCATE) through the CCP4 graphical interface ccp4i and points out some issues that need to be considered, together with a few examples. It covers determination of the point-group symmetry of the diffraction data (the Laue group), which is required for the subsequent scaling step, examination of systematic absences, which in many cases will allow inference of the space group, putting multiple data sets on a common indexing system when there are alternatives, the scaling step itself, which produces a large set of data-quality indicators, estimation of |F| from intensity and finally examination of intensity statistics to detect crystal pathologies such as twinning. An appendix outlines the scoring schemes used by the program POINTLESS to assign probabilities to possible Laue and space groups.

Construction of moment-matching multinomial lattices using Vandermonde matrices and Gröbner bases

NASA Astrophysics Data System (ADS)

Lundengârd, Karl; Ogutu, Carolyne; Silvestrov, Sergei; Ni, Ying; Weke, Patrick

2017-01-01

In order to describe and analyze the quantitative behavior of stochastic processes, such as the process followed by a financial asset, various discretization methods are used. One such set of methods are lattice models where a time interval is divided into equal time steps and the rate of change for the process is restricted to a particular set of values in each time step. The well-known binomial- and trinomial models are the most commonly used in applications, although several kinds of higher order models have also been examined. Here we will examine various ways of designing higher order lattice schemes with different node placements in order to guarantee moment-matching with the process.

DON'T BE TRICKED BY YOUR INTEGRATED RATE PLOT!

EPA Science Inventory

Reaction order can be determined from kinetic data in a variety of ways. Two methods commonly employed are comparison of initial rates (while varying reactant concentration) and plotting integrated rate expressions. Both of these are introduced in general and physical chemistry t...

An Official American Thoracic Society Workshop Report. A Framework for Addressing Multimorbidity in Clinical Practice Guidelines for Pulmonary Disease, Critical Illness, and Sleep Disorders.

PubMed

Wilson, Kevin C; Gould, Michael K; Krishnan, Jerry A; Boyd, Cynthia M; Brozek, Jan L; Cooke, Colin R; Douglas, Ivor S; Goodman, Richard A; Joo, Min J; Lareau, Suzanne; Mularski, Richard A; Patel, Minal R; Rosenfeld, Richard M; Shanawani, Hasan; Slatore, Christopher; Sockrider, Marianna; Sufian, Beth; Thomson, Carey C; Wiener, Renda Soylemez

2016-03-01

Coexistence of multiple chronic conditions (i.e., multimorbidity) is the most common chronic health problem in adults. However, clinical practice guidelines have primarily focused on patients with a single disease, resulting in uncertainty about the care of patients with multimorbidity. The American Thoracic Society convened a workshop with the goal of establishing a strategy to address multimorbidity within clinical practice guidelines. In this Workshop Report, we describe a framework that addresses multimorbidity in each of the key steps of guideline development: topic selection, panel composition, identifying clinical questions, searching for and synthesizing evidence, rating the quality of that evidence, summarizing benefits and harms, formulating recommendations, and rating the strength of the recommendations. For the consideration of multimorbidity in guidelines to be successful and sustainable, the process must be both feasible and pragmatic. It is likely that this will be achieved best by the step-wise addition and refinement of the various components of the framework.

Rapid determination of vial heat transfer parameters using tunable diode laser absorption spectroscopy (TDLAS) in response to step-changes in pressure set-point during freeze-drying.

PubMed

Kuu, Wei Y; Nail, Steven L; Sacha, Gregory

2009-03-01

The purpose of this study was to perform a rapid determination of vial heat transfer parameters, that is, the contact parameter K(cs) and the separation distance l(v), using the sublimation rate profiles measured by tunable diode laser absorption spectroscopy (TDLAS). In this study, each size of vial was filled with pure water followed by a freeze-drying cycle using a LyoStar II dryer (FTS Systems) with step-changes of the chamber pressure set-point at to 25, 50, 100, 200, 300, and 400 mTorr. K(cs) was independently determined by nonlinear parameter estimation using the sublimation rates measured at the pressure set-point of 25 mTorr. After obtaining K(cs), the l(v) value for each vial size was determined by nonlinear parameter estimation using the pooled sublimation rate profiles obtained at 25 to 400 mTorr. The vial heat transfer coefficient K(v), as a function of the chamber pressure, was readily calculated, using the obtained K(cs) and l(v) values. It is interesting to note the significant difference in K(v) of two similar types of 10 mL Schott tubing vials, primary due to the geometry of the vial-bottom, as demonstrated by the images of the contact areas of the vial-bottom. (c) 2008 Wiley-Liss, Inc. and the American Pharmacists Association

NiCu single atom alloys catalyze the C—H bond activation in the selective non- oxidative ethanol dehydrogenation reaction

DOE PAGES

Shan, Junjun; Liu, Jilei; Li, Mengwei; ...

2017-12-29

Here, NiCu single atom alloy (SAA) nanoparticles supported on silica are reported to catalyze the non-oxidative dehydrogenation of ethanol, selectively to acetaldehyde and hydrogen products by facilitating the C—H bond cleavage. The activity and selectivity of the NiCu SAA catalysts were compared to monometallic copper and to PtCu and PdCu single atom alloys, in a flow reactor at moderate temperatures. In-situ DRIFTS showed that the silica support facilitates the O—H bond cleavage of ethanol to form ethoxy intermediates over all the supported alloy catalysts. However, these remain unreactive up to 250°C for the Cu/SiO 2 monometallic nanoparticles, while in themore » NiCu SAA, acetaldehyde is formed at much lower temperatures, below 150°C. In situ DRIFTS was also used to identify the C—H activation step as the rate determining step of this reaction on all the copper catalysts we examined. The presence of atomically dispersed Ni in Cu significantly lowers the C—H bond activation barrier, whereas Pt and Pd atoms were found less effective. This work provides direct evidence that the C—H bond cleavage is the rate determining step in ethanol dehydrogenation over this type catalyst.« less

NiCu single atom alloys catalyze the C—H bond activation in the selective non- oxidative ethanol dehydrogenation reaction

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

Shan, Junjun; Liu, Jilei; Li, Mengwei

Here, NiCu single atom alloy (SAA) nanoparticles supported on silica are reported to catalyze the non-oxidative dehydrogenation of ethanol, selectively to acetaldehyde and hydrogen products by facilitating the C—H bond cleavage. The activity and selectivity of the NiCu SAA catalysts were compared to monometallic copper and to PtCu and PdCu single atom alloys, in a flow reactor at moderate temperatures. In-situ DRIFTS showed that the silica support facilitates the O—H bond cleavage of ethanol to form ethoxy intermediates over all the supported alloy catalysts. However, these remain unreactive up to 250°C for the Cu/SiO 2 monometallic nanoparticles, while in themore » NiCu SAA, acetaldehyde is formed at much lower temperatures, below 150°C. In situ DRIFTS was also used to identify the C—H activation step as the rate determining step of this reaction on all the copper catalysts we examined. The presence of atomically dispersed Ni in Cu significantly lowers the C—H bond activation barrier, whereas Pt and Pd atoms were found less effective. This work provides direct evidence that the C—H bond cleavage is the rate determining step in ethanol dehydrogenation over this type catalyst.« less

Conformational Changes Represent the Rate-Limiting Step in the Transport Cycle of Maize SUCROSE TRANSPORTER1[C][W

PubMed Central

Derrer, Carmen; Wittek, Anke; Bamberg, Ernst; Carpaneto, Armando; Dreyer, Ingo; Geiger, Dietmar

2013-01-01

Proton-driven Suc transporters allow phloem cells of higher plants to accumulate Suc to more than 1 M, which is up to ∼1000-fold higher than in the surrounding extracellular space. The carrier protein can accomplish this task only because proton and Suc transport are tightly coupled. This study provides insights into this coupling by resolving the first step in the transport cycle of the Suc transporter SUT1 from maize (Zea mays). Voltage clamp fluorometry measurements combining electrophysiological techniques with fluorescence-based methods enable the visualization of conformational changes of SUT1 expressed in Xenopus laevis oocytes. Using the Suc derivate sucralose, binding of which hinders conformational changes of SUT1, the association of protons to the carrier could be dissected from transport-associated movements of the protein. These combined approaches enabled us to resolve the binding of protons to the carrier and its interrelationship with the alternating movement of the protein. The data indicate that the rate-limiting step of the reaction cycle is determined by the accessibility of the proton binding site. This, in turn, is determined by the conformational change of the SUT1 protein, alternately exposing the binding pockets to the inward and to the outward face of the membrane. PMID:23964025

Fatigue Life Methodology for Bonded Composite Skin/Stringer Configurations

NASA Technical Reports Server (NTRS)

Krueger, Ronald; Paris, Isabelle L.; OBrien, T. Kevin; Minguet, Pierre J.

2001-01-01

A methodology is presented for determining the fatigue life of composite structures based on fatigue characterization data and geometric nonlinear finite element (FE) analyses. To demonstrate the approach, predicted results were compared to fatigue tests performed on specimens which represented a tapered composite flange bonded onto a composite skin. In a first step, tension tests were performed to evaluate the debonding mechanisms between the flange and the skin. In a second step, a 2D FE model was developed to analyze the tests. To predict matrix cracking onset, the relationship between the tension load and the maximum principal stresses transverse to the fiber direction was determined through FE analysis. Transverse tension fatigue life data were used to -enerate an onset fatigue life P-N curve for matrix cracking. The resulting prediction was in good agreement with data from the fatigue tests. In a third step, a fracture mechanics approach based on FE analysis was used to determine the relationship between the tension load and the critical energy release rate. Mixed mode energy release rate fatigue life data were used to create a fatigue life onset G-N curve for delamination. The resulting prediction was in good agreement with data from the fatigue tests. Further, the prediction curve for cumulative life to failure was generated from the previous onset fatigue life curves. The results showed that the methodology offers a significant potential to Predict cumulative fatigue life of composite structures.

An error criterion for determining sampling rates in closed-loop control systems

NASA Technical Reports Server (NTRS)

Brecher, S. M.

1972-01-01

The determination of an error criterion which will give a sampling rate for adequate performance of linear, time-invariant closed-loop, discrete-data control systems was studied. The proper modelling of the closed-loop control system for characterization of the error behavior, and the determination of an absolute error definition for performance of the two commonly used holding devices are discussed. The definition of an adequate relative error criterion as a function of the sampling rate and the parameters characterizing the system is established along with the determination of sampling rates. The validity of the expressions for the sampling interval was confirmed by computer simulations. Their application solves the problem of making a first choice in the selection of sampling rates.

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

Glascoe, E A; Zaug, J M; Burnham, A K

The effect of pressure on the thermal decomposition rate of the energetic material HMX was studied. HMX was precompressed in a diamond anvil cell (DAC) and heated at various rates. The parent species population was monitored as a function of time and temperature using Fourier transform infrared (FTIR) spectroscopy. Decomposition rates were determined by fitting the fraction reacted to the extended-Prout-Tompkins nucleation-growth model and the Friedman isoconversional method. The results of these experiments and analysis indicate that pressure accelerates the decomposition at low to moderate pressures (i.e. between ambient pressure and 1 GPa) and decelerates the decomposition at higher pressures.more » The decomposition acceleration is attributed to pressure enhanced autocatalysis whereas the deceleration at high pressures is attributed pressure inhibiting bond homolysis step(s), which would result in an increase in volume. These results indicate that both {beta} and {delta} phase HMX are sensitive to pressure in the thermally induced decomposition kinetics.« less

Towards numerical prediction of cavitation erosion.

PubMed

Fivel, Marc; Franc, Jean-Pierre; Chandra Roy, Samir

2015-10-06

This paper is intended to provide a potential basis for a numerical prediction of cavitation erosion damage. The proposed method can be divided into two steps. The first step consists in determining the loading conditions due to cavitation bubble collapses. It is shown that individual pits observed on highly polished metallic samples exposed to cavitation for a relatively small time can be considered as the signature of bubble collapse. By combining pitting tests with an inverse finite-element modelling (FEM) of the material response to a representative impact load, loading conditions can be derived for each individual bubble collapse in terms of stress amplitude (in gigapascals) and radial extent (in micrometres). This step requires characterizing as accurately as possible the properties of the material exposed to cavitation. This characterization should include the effect of strain rate, which is known to be high in cavitation erosion (typically of the order of several thousands s(-1)). Nanoindentation techniques as well as compressive tests at high strain rate using, for example, a split Hopkinson pressure bar test system may be used. The second step consists in developing an FEM approach to simulate the material response to the repetitive impact loads determined in step 1. This includes a detailed analysis of the hardening process (isotropic versus kinematic) in order to properly account for fatigue as well as the development of a suitable model of material damage and failure to account for mass loss. Although the whole method is not yet fully operational, promising results are presented that show that such a numerical method might be, in the long term, an alternative to correlative techniques used so far for cavitation erosion prediction.

Towards numerical prediction of cavitation erosion

PubMed Central

Fivel, Marc; Franc, Jean-Pierre; Chandra Roy, Samir

2015-01-01

This paper is intended to provide a potential basis for a numerical prediction of cavitation erosion damage. The proposed method can be divided into two steps. The first step consists in determining the loading conditions due to cavitation bubble collapses. It is shown that individual pits observed on highly polished metallic samples exposed to cavitation for a relatively small time can be considered as the signature of bubble collapse. By combining pitting tests with an inverse finite-element modelling (FEM) of the material response to a representative impact load, loading conditions can be derived for each individual bubble collapse in terms of stress amplitude (in gigapascals) and radial extent (in micrometres). This step requires characterizing as accurately as possible the properties of the material exposed to cavitation. This characterization should include the effect of strain rate, which is known to be high in cavitation erosion (typically of the order of several thousands s−1). Nanoindentation techniques as well as compressive tests at high strain rate using, for example, a split Hopkinson pressure bar test system may be used. The second step consists in developing an FEM approach to simulate the material response to the repetitive impact loads determined in step 1. This includes a detailed analysis of the hardening process (isotropic versus kinematic) in order to properly account for fatigue as well as the development of a suitable model of material damage and failure to account for mass loss. Although the whole method is not yet fully operational, promising results are presented that show that such a numerical method might be, in the long term, an alternative to correlative techniques used so far for cavitation erosion prediction. PMID:26442139

The natural weathering of staurolite: crystal-surface textures, relative stability, and the rate-determining step

Treesearch

Michael A. Velbel; Charles L. Basso; Michael J. Zieg

1996-01-01

Mineral surface-textures on naturally weathered crystals of staurolite [monoclinic, pseudo-orthorhombic; Fe4Al18Si8O46(OH)2] indicate that staurolite weathering is generally interface-limited. Etch pits on naturally weathered staurolites are disk-shaped,...

RNA-seq Data: Challenges in and Recommendations for Experimental Design and Analysis.

PubMed

Williams, Alexander G; Thomas, Sean; Wyman, Stacia K; Holloway, Alisha K

2014-10-01

RNA-seq is widely used to determine differential expression of genes or transcripts as well as identify novel transcripts, identify allele-specific expression, and precisely measure translation of transcripts. Thoughtful experimental design and choice of analysis tools are critical to ensure high-quality data and interpretable results. Important considerations for experimental design include number of replicates, whether to collect paired-end or single-end reads, sequence length, and sequencing depth. Common analysis steps in all RNA-seq experiments include quality control, read alignment, assigning reads to genes or transcripts, and estimating gene or transcript abundance. Our aims are two-fold: to make recommendations for common components of experimental design and assess tool capabilities for each of these steps. We also test tools designed to detect differential expression, since this is the most widespread application of RNA-seq. We hope that these analyses will help guide those who are new to RNA-seq and will generate discussion about remaining needs for tool improvement and development. Copyright © 2014 John Wiley & Sons, Inc.

A review of available analytical technologies for qualitative and quantitative determination of nitramines.

PubMed

Lindahl, Sofia; Gundersen, Cathrine Brecke; Lundanes, Elsa

2014-08-01

This review aims to summarize the available analytical methods in the open literature for the determination of some aliphatic and cyclic nitramines. Nitramines covered in this review are the ones that can be formed from the use of amines in post-combustion CO2 capture (PCC) plants and end up in the environment. Since the literature is quite scarce regarding the determination of nitramines in aqueous and soil samples, methods for determination of nitramines in other matrices have also been included. Since the nitramines are found in complex matrices and/or in very low concentration, an extraction step is often necessary before their determination. Liquid-liquid extraction (LLE) using dichloromethane and solid phase extraction (SPE) with an activated carbon based material have been the two most common extraction methods. Gas chromatography (GC) or reversed phase liquid chromatography (RPLC) has been used often combined with mass spectrometry (MS) in the final determination step. Presently there is no comprehensive method available that can be used for determination of all nitramines included in this review. The lowest concentration limit of quantification (cLOQ) is in the ng L(-1) range, however, most methods appear to have a cLOQ in the μg L(-1) range, if the cLOQ has been given.

Cardiorespiratory instability in monitored step-down unit patients: using cluster analysis to identify patterns of change

PubMed Central

Clermont, Gilles; Chen, Lujie; Dubrawski, Artur W.; Ren, Dianxu; Hoffman, Leslie A.; Pinsky, Michael R.; Hravnak, Marilyn

2018-01-01

Cardiorespiratory instability (CRI) in monitored step-down unit (SDU) patients has a variety of etiologies, and likely manifests in patterns of vital signs (VS) changes. We explored use of clustering techniques to identify patterns in the initial CRI epoch (CRI1; first exceedances of VS beyond stability thresholds after SDU admission) of unstable patients, and inter-cluster differences in admission characteristics and outcomes. Continuous noninvasive monitoring of heart rate (HR), respiratory rate (RR), and pulse oximetry (SpO2) were sampled at 1/20 Hz. We identified CRI1 in 165 patients, employed hierarchical and k-means clustering, tested several clustering solutions, used 10-fold cross validation to establish the best solution and assessed inter-cluster differences in admission characteristics and outcomes. Three clusters (C) were derived: C1) normal/high HR and RR, normal SpO2 (n = 30); C2) normal HR and RR, low SpO2 (n = 103); and C3) low/normal HR, low RR and normal SpO2 (n = 32). Clusters were significantly different based on age (p < 0.001; older patients in C2), number of comorbidities (p = 0.008; more C2 patients had ≥ 2) and hospital length of stay (p = 0.006; C1 patients stayed longer). There were no between-cluster differences in SDU length of stay, or mortality. Three different clusters of VS presentations for CRI1 were identified. Clusters varied on age, number of comorbidities and hospital length of stay. Future study is needed to determine if there are common physiologic underpinnings of VS clusters which might inform clinical decision-making when CRI first manifests. PMID:28229353

LFER Studies Evaluating Solvent Effects on an α-Chloro-and two β,β,β-Trichloro-Ethyl Chloroformate Esters

PubMed Central

D’Souza, Malcolm J.; Sandosky, Brandon; Fernandez-Bueno, Gabriel A.; McAneny, Matthew J.; Kevill, Dennis N.

2014-01-01

To provide insight and to identify the occurrence of mechanistic changes in relation to variance in solvent-type, the solvent effects on the rates of solvolysis of three substrates, 2,2,2-trichloro-1,1-dimethylethyl chloroformate, 2,2,2-trichloroethyl chloroformate, and 1-chloroethyl chloroformate, are analyzed using linear free energy relationships (LFERs) such as the extended Grunwald-Winstein equation, and a similarity-based LFER model approach that is based on the solvolysis of phenyl chloroformate. At 25.0 °C, in four common solvents, the α-chloroethyl chloroformate was found to react considerably faster than the two β,β,β-trichloro-substituted analogs. This immense rate enhancement can be directly related to the proximity of the electron-withdrawing α-chlorine atom to the carbonyl carbon reaction center. In the thirteen solvents studied, 1-chloroethyl chloroformate was found to strictly follow a carbonyl addition process, with the addition-step being rate-determining. For the two β,β,β-trichloro-substrates, in aqueous mixtures that are very rich in a fluoroalcohol component, there is compelling evidence for the occurrence of side-by-side addition-elimination and ionization mechanisms, with the ionization pathway being predominant. The presence of the two methyl groups on the α-carbon of 2,2,2-trichloro-1,1-dimethylethyl chloroformate has additive steric and stereoelectronic implications, causing its rate of reaction to be significantly slower than that of 2,2,2-trichloroethyl chloroformate. PMID:24812595

On-off closed-loop control of vagus nerve stimulation for the adaptation of heart rate.

PubMed

Ugalde, Hector Romero; Le Rolle, Virginie; Bel, Alain; Bonnet, Jean-Luc; Andreu, David; Mabo, Philippe; Carrault, Guy; Hernández, Alfredo I

2014-01-01

Vagus nerve stimulation (VNS) is a potential therapeutic approach in a number of clinical applications. Although VNS is commonly delivered in an open-loop approach, it is now recognized that closed-loop approaches may be necessary to optimize the therapy and minimize side effects of neuro-stimulation devices. In this paper, we describe a prototype system for real-time control of the instantaneous heart rate, working synchronously with the heart period. As a first step, an on-off control method has been integrated. The system is evaluated on one sheep with induced heart failure, showing the interest of the proposed approach.

Determination of in vivo regulation kinetics of small non-coding RNA in bacteria

NASA Astrophysics Data System (ADS)

Fei, Jingyi

Small RNAs (sRNAs) play important roles in regulating gene expression through a variety of mechanisms. As one of the most common strategies, sRNA induced target messenger RNA (mRNA) includes two major steps: target search by base-pairing interactions with the and downstream execution by modulating translation or the stability of the mRNA. Here we describe a new imaging and analysis platform based on super-resolution fluorescence microscopy, which enabled the first in vivo kinetic measurement of sRNA-mediated gene regulation. Specifically, this platform was used to investigate a sugar-phosphate stress-induced bacterial sRNA that induces the degradation of target mRNAs. The data reveal that the sRNA binds to a primary target mRNA in a reversible and dynamic fashion, and that formation of the sRNA-mRNA complexes is the rate-limiting step, dictating the overall efficiency of regulation in vivo; whereas the downstream co-degradation of sRNA-mRNA complex can kinetically compete with the fast complex disassembly. Examination of a secondary target of this sRNA indicated that differences in the target search kinetics contribute to setting the regulation priority among different target mRNAs. This super-resolution imaging and analysis approach provides a conceptual framework that can be generalized to other sRNA systems and other target search processes.

Algorithms for bioluminescence tomography incorporating anatomical information and reconstruction of tissue optical properties

PubMed Central

Naser, Mohamed A.; Patterson, Michael S.

2010-01-01

Reconstruction algorithms are presented for a two-step solution of the bioluminescence tomography (BLT) problem. In the first step, a priori anatomical information provided by x-ray computed tomography or by other methods is used to solve the continuous wave (cw) diffuse optical tomography (DOT) problem. A Taylor series expansion approximates the light fluence rate dependence on the optical properties of each region where first and second order direct derivatives of the light fluence rate with respect to scattering and absorption coefficients are obtained and used for the reconstruction. In the second step, the reconstructed optical properties at different wavelengths are used to calculate the Green’s function of the system. Then an iterative minimization solution based on the L1 norm shrinks the permissible regions where the sources are allowed by selecting points with higher probability to contribute to the source distribution. This provides an efficient BLT reconstruction algorithm with the ability to determine relative source magnitudes and positions in the presence of noise. PMID:21258486

Procedural key steps in laparoscopic colorectal surgery, consensus through Delphi methodology.

PubMed

Dijkstra, Frederieke A; Bosker, Robbert J I; Veeger, Nicolaas J G M; van Det, Marc J; Pierie, Jean Pierre E N

2015-09-01

While several procedural training curricula in laparoscopic colorectal surgery have been validated and published, none have focused on dividing surgical procedures into well-identified segments, which can be trained and assessed separately. This enables the surgeon and resident to focus on a specific segment, or combination of segments, of a procedure. Furthermore, it will provide a consistent and uniform method of training for residents rotating through different teaching hospitals. The goal of this study was to determine consensus on the key steps of laparoscopic right hemicolectomy and laparoscopic sigmoid colectomy among experts in our University Medical Center and affiliated hospitals. This will form the basis for the INVEST video-assisted side-by-side training curriculum. The Delphi method was used for determining consensus on key steps of both procedures. A list of 31 steps for laparoscopic right hemicolectomy and 37 steps for laparoscopic sigmoid colectomy was compiled from textbooks and national and international guidelines. In an online questionnaire, 22 experts in 12 hospitals within our teaching region were invited to rate all steps on a Likert scale on importance for the procedure. Consensus was reached in two rounds. Sixteen experts agreed to participate. Of these 16 experts, 14 (88%) completed the questionnaire for both procedures. Of the 14 who completed the first round, 13 (93%) completed the second round. Cronbach's alpha was 0.79 for the right hemicolectomy and 0.91 for the sigmoid colectomy, showing high internal consistency between the experts. For the right hemicolectomy, 25 key steps were established; for the sigmoid colectomy, 24 key steps were established. Expert consensus on the key steps for laparoscopic right hemicolectomy and laparoscopic sigmoid colectomy was reached. These key steps will form the basis for a video-assisted teaching curriculum.

Accurate identification of microseismic P- and S-phase arrivals using the multi-step AIC algorithm

NASA Astrophysics Data System (ADS)

Zhu, Mengbo; Wang, Liguan; Liu, Xiaoming; Zhao, Jiaxuan; Peng, Ping'an

2018-03-01

Identification of P- and S-phase arrivals is the primary work in microseismic monitoring. In this study, a new multi-step AIC algorithm is proposed. This algorithm consists of P- and S-phase arrival pickers (P-picker and S-picker). The P-picker contains three steps: in step 1, a preliminary P-phase arrival window is determined by the waveform peak. Then a preliminary P-pick is identified using the AIC algorithm. Finally, the P-phase arrival window is narrowed based on the above P-pick. Thus the P-phase arrival can be identified accurately by using the AIC algorithm again. The S-picker contains five steps: in step 1, a narrow S-phase arrival window is determined based on the P-pick and the AIC curve of amplitude biquadratic time-series. In step 2, the S-picker automatically judges whether the S-phase arrival is clear to identify. In step 3 and 4, the AIC extreme points are extracted, and the relationship between the local minimum and the S-phase arrival is researched. In step 5, the S-phase arrival is picked based on the maximum probability criterion. To evaluate of the proposed algorithm, a P- and S-picks classification criterion is also established based on a source location numerical simulation. The field data tests show a considerable improvement of the multi-step AIC algorithm in comparison with the manual picks and the original AIC algorithm. Furthermore, the technique is independent of the kind of SNR. Even in the poor-quality signal group which the SNRs are below 5, the effective picking rates (the corresponding location error is <15 m) of P- and S-phase arrivals are still up to 80.9% and 76.4% respectively.

Atomic-Scale Design of Iron Fischer-Tropsch Catalysts: A Combined Computational Chemistry, Experimental, and Microkinetic Modeling Approach

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

Manos Mavrikakis; James A. Dumesic; Amit A. Gokhale

2006-03-03

Efforts during this second year focused on four areas: (1) continued searching and summarizing of published Fischer-Tropsch synthesis (FTS) mechanistic and kinetic studies of FTS reactions on iron catalysts; (2) investigation of CO adsorption/desorption and temperature programmed hydrogenation (TPH) of carbonaceous species after FTS on unsupported iron and alumina-supported iron catalysts; (3) activity tests of alumina-supported iron catalysts in a fixed bed reactor; (4) sequential design of experiments, for the collection of rate data in a Berty CSTR reactor, and nonlinear-regression analysis to obtain kinetic parameters. Literature sources describing mechanistic and kinetic studies of Fischer-Tropsch synthesis on iron catalysts weremore » compiled in a review. Temperature-programmed desorption/reaction methods (the latter using mass-spectrometry detection and also thermogravimetric analyzer (TGA)) were utilized to study CO adsorption/-desorption on supported and unsupported iron catalysts. Molecular and dissociative adsorptions of CO occur on iron catalysts at 25-150 C. The amounts adsorbed and bond strengths of adsorption are influenced by supports and promoters. That CO adsorbs dissociatively on polycrystalline Fe at temperatures well below those of FT reaction indicates that CO dissociation is facile and unlikely to be the rate-limiting step during FTS. Carbonaceous species formed after FT reaction for only 5 minutes at 200 C were initially hydrogenated under mild, isothermal condition (200 C and 1 atm), followed by TPH to 800 C. During the mild, isothermal hydrogenation, only about 0.1-0.2 mL of atomic carbon is apparently removed, while during TPH to 800 C multilayer equivalents of atomic, polymeric, carbidic, and graphitic carbons are removed. Rates of CO conversion on alumina-supported iron catalysts at 220-260 C and 20 atm are correlated well by a Langmuir-Hinshelwood expression, derived assuming carbon hydrogenation to CH and OH recombination to water to be rate-determining steps. In the coming year, studies will focus on quantitative determination of the rates of kinetically-relevant elementary steps on Fe catalysts with/without K and Pt promoters and at various levels of Al{sub 2}O{sub 3} support, providing a database for understanding (1) effects of promoter and support on elementary kinetic parameters and (2) for validation of computational models that incorporate effects of surface structure and promoters. Kinetic parameters will be incorporated into a microkinetics model, enabling prediction of rate without invoking assumptions, e.g. of a rate-determining step or a most-abundant surface intermediate. Calculations using periodic, self-consistent Density Functional Theory (DFT) methods were performed on two model surfaces: (1) Fe(110) with 1/4 ML subsurface carbon, and (2) Fe(110) with 1/4 ML Pt adatoms. Reaction networks for FTS on these systems were characterized in full detail by evaluating the thermodynamics and kinetics of each elementary step. We discovered that subsurface C stabilizes all the reactive intermediates, in contrast to Pt, which destabilizes most of them. A comparative study of the reactivities of the modified-Fe surfaces against pure Fe is expected to yield a more comprehensive understanding of promotion mechanisms for FTS on Fe.« less

An on-line pre-concentration system for determination of cadmium in drinking water using FAAS.

PubMed

dos Santos, Walter N L; Costa, Jorge L O; Araujo, Rennan G O; de Jesus, Djane S; Costa, Antônio C S

2006-10-11

In the present paper, a minicolumn of polyurethane foam loaded with 4-(2-pyridylazo)-resorcinol (PAR) is proposed as pre-concentration system for cadmium determination in drinking water samples by flame atomic absorption spectrometry. The optimization step was performed using two-level full factorial design and Doehlert matrix, involving the variables: sampling flow rate, elution concentration, buffer concentration and pH. Using the established experimental conditions in the optimization step of: pH 8.2, sampling flow rate 8.5 mL min(-1), buffer concentration 0.05 mol L(-1) and elution concentration of 1.0 mol L(-1), this system allows the determination of cadmium with detection limit (LD) (3sigma/S) of 20.0 ng L(-1) and quantification limit (LQ) (10sigma/S) of 64 ng L(-1), precision expressed as relative standard deviation (R.S.D.) of 5.0 and 4.7% for cadmium concentration of 5.0 and 40.0 microg L(-1), respectively, and a pre-concentration factor of 158 for a sample volume of 20.0 mL. The accuracy was confirmed by cadmium determination in the standard reference material, NIST SRM 1643d trace elements in natural water. This procedure was applied for cadmium determination in drinking water samples collected from Salvador City, Bahia, Brazil. For five samples analyzed, the achieved concentrations varied from 0.31 to 0.86 microg L(-1).

Projection of Maximum Software Maintenance Manning Levels.

DTIC Science & Technology

1982-06-01

mainte- nance team development and for outyear support resource estimation, and to provide an analysis of applications of the model in areas other...by General Research Corporation of Santa Barbara, Ca., indicated that the Planning and Resource Management Information System (PARRIS) at the Air Force...determined that when the optimal input effort is applied, steps in the development would be achieved at a rate proportional to V(t). Thus the work-rate could

Urinary Tract Infection as a Preventable Cause of Pregnancy Complications: Opportunities, Challenges, and a Global Call to Action

PubMed Central

Gilbert, Nicole M.; O'Brien, Valerie P.; Hultgren, Scott; Macones, George; Lewis, Warren G.

2013-01-01

The urinary tract is a common site of infection in humans. During pregnancy, urinary tract infection (UTI) is associated with increased risks of maternal and neonatal morbidity and mortality, even when the infection is asymptomatic. By mapping available rates of UTI in pregnancy across different populations, we emphasize this as a problem of global significance. Many countries with high rates of preterm birth and neonatal mortality also have rates of UTI in pregnancy that exceed rates seen in more developed countries. A global analysis of the etiologies of UTI revealed familiar culprits as well as emerging threats. Screening and treatment of UTI have improved birth outcomes in several more developed countries and would likely improve maternal and neonatal health worldwide. However, challenges of implementation in resource-poor settings must be overcome. We review the nature of the barriers occurring at each step of the screening and treatment pipeline and highlight steps necessary to overcome these obstacles. It is our hope that the information compiled here will increase awareness of the global significance of UTI in maternal and neonatal health and embolden governments, nongovernmental organizations, and researchers to do their part to make urine screening and UTI treatment a reality for all pregnant women. PMID:24416696

Urinary tract infection as a preventable cause of pregnancy complications: opportunities, challenges, and a global call to action.

PubMed

Gilbert, Nicole M; O'Brien, Valerie P; Hultgren, Scott; Macones, George; Lewis, Warren G; Lewis, Amanda L

2013-09-01

The urinary tract is a common site of infection in humans. During pregnancy, urinary tract infection (UTI) is associated with increased risks of maternal and neonatal morbidity and mortality, even when the infection is asymptomatic. By mapping available rates of UTI in pregnancy across different populations, we emphasize this as a problem of global significance. Many countries with high rates of preterm birth and neonatal mortality also have rates of UTI in pregnancy that exceed rates seen in more developed countries. A global analysis of the etiologies of UTI revealed familiar culprits as well as emerging threats. Screening and treatment of UTI have improved birth outcomes in several more developed countries and would likely improve maternal and neonatal health worldwide. However, challenges of implementation in resource-poor settings must be overcome. We review the nature of the barriers occurring at each step of the screening and treatment pipeline and highlight steps necessary to overcome these obstacles. It is our hope that the information compiled here will increase awareness of the global significance of UTI in maternal and neonatal health and embolden governments, nongovernmental organizations, and researchers to do their part to make urine screening and UTI treatment a reality for all pregnant women.

43 CFR 3162.7-4 - Royalty rates on oil; sliding and step-scale leases (public land only).

Code of Federal Regulations, 2011 CFR

2011-10-01

... to Public Lands (Continued) BUREAU OF LAND MANAGEMENT, DEPARTMENT OF THE INTERIOR MINERALS MANAGEMENT... on a leasehold are commercially productive, including in that category all wells, whether produced or... production from the leasehold. The authorized officer will determine which commercially productive wells...

Knowing When to Retire: The First Step towards Financial Planning in Malaysia

ERIC Educational Resources Information Center

Kock, Tan Hoe; Yoong, Folk Jee

2011-01-01

This article draws upon expected retirement age cohorts as a main determinant to financial planning preparation in Malaysia. The return rate was 55% from 600 questionnaires distributed. Five hypotheses were analyzed using hierarchical and stepwise regression analysis. The results revealed that expected retirement age cohort variables made…

Survey by the European Board and College of Obstetrics and Gynaecology on screening for gestational diabetes in Europe.

PubMed

Benhalima, Katrien; Mathieu, Chantal; Van Assche, André; Damm, Peter; Devlieger, Roland; Mahmood, Tahir; Dunne, Fidelma

2016-06-01

More uniformity is necessary in screening and diagnosis for gestational diabetes (GDM) across Europe. The European Board and College of Obstetrics and Gynaecology (EBCOG) has recently recommended to use the 2013 World Health Organization (WHO) criteria for the diagnosis of GDM. We evaluated the uptake of these EBCOG recommendations in guidelines for GDM screening across Europe. Between September and November 2015, an online survey on the current national or regional recommendations for GDM screening was directed to the 33 European countries that are members of EBCOG. There was a response rate of 84.8% (28 countries). From Belgium, data were separately obtained from the Dutch-and the French-speaking parts and from the UK data were also obtained from Scotland, leading to data from 30 responders. The response rates were high in Central Europe (100%), Northern Europe (100%) and Southern Europe (85.7%) with lower response rates in Eastern Europe (71.4%). 82.1% of guidelines recommend screening for unknown diabetes at first prenatal visit and 67.9% recommend to screen for GDM before 24 weeks of pregnancy. All guidelines recommend to screen for GDM ≥24 weeks, based on risk factors in 64.3% and by universal screening in 35.7%. The most commonly used diagnostic criteria for GDM are the 2013 WHO criteria in 67.9%, the 1999 WHO criteria in 10.7%, the European Association for the Study of Diabetes criteria in 7.1% and the Carpenter & Coustan criteria in 7.1%. Of all societies advising the use of the 2013 WHO criteria, 52.6% recommends this based on risk factors, 10.5% recommends universal screening in a two-step strategy and 36.8% recommends a universal one-step approach with a 75g OGTT. Our survey shows that the majority of European societies now advise to use the 2013 WHO criteria for GDM. However, only 36.8% recommends a universal one-step approach with a 75g OGTT with the majority of societies recommending screening based on risk factors. The use of common diagnostic criteria for GDM by the majority of societies is an important first step towards achieving uniformity in GDM screening across Europe. Copyright © 2016 Elsevier Ireland Ltd. All rights reserved.

Comparison of phosphorus recovery from incineration and gasification sewage sludge ash.

PubMed

Parés Viader, Raimon; Jensen, Pernille Erland; Ottosen, Lisbeth M; Thomsen, Tobias P; Ahrenfeldt, Jesper; Hauggaard-Nielsen, Henrik

2017-03-01

Incineration of sewage sludge is a common practice in many western countries. Gasification is an attractive option because of its high energy efficiency and flexibility in the usage of the produced gas. However, they both unavoidably produce sewage sludge ashes, a material that is rich in phosphorus, but which is commonly landfilled or used in construction materials. With current uncertainty in phosphate rock supply, phosphorus recovery from sewage sludge ashes has become interesting. In the present work, ashes from incineration and gasification of the same sewage sludge were compared in terms of phosphorus extractability using electrodialytic (ED) methods. The results show that comparable recovery rates of phosphorus were achieved with a single ED step for incineration ashes and a sequential combination of two ED steps for gasification ashes, which was due to a higher influence of iron and/or aluminium in phosphorus solubility for the latter. A product with lower level of metallic impurities and comparable to wet process phosphoric acid was eventually obtained from gasification ashes. Thus, gasification becomes an interesting alternative to incineration also in terms of phosphorus separation.

Water vapor mass balance method for determining air infiltration rates in houses

Treesearch

David R. DeWalle; Gordon M. Heisler

1980-01-01

A water vapor mass balance technique that includes the use of common humidity-control equipment can be used to determine average air infiltration rates in buildings. Only measurements of the humidity inside and outside the home, the mass of vapor exchanged by a humidifier/dehumidifier, and the volume of interior air space are needed. This method gives results that...

Simultaneous multielement atomic absorption spectrometry with graphite furnace atomization

NASA Astrophysics Data System (ADS)

Harnly, James M.; Miller-Ihli, Nancy J.; O'Haver, Thomas C.

The extended analytical range capability of a simultaneous multielement atomic absorption continuum source spectrometer (SIMAAC) was tested for furnace atomization with respect to the signal measurement mode (peak height and area), the atomization mode (from the wall or from a platform), and the temperature program mode (stepped or ramped atomization). These parameters were evaluated with respect to the shapes of the analytical curves, the detection limits, carry-over contamination and accuracy. Peak area measurements gave more linear calibration curves. Methods for slowing the atomization step heating rate, the use of a ramped temperature program or a platform, produced similar calibration curves and longer linear ranges than atomization with a stepped temperature program. Peak height detection limits were best using stepped atomization from the wall. Peak area detection limits for all atomization modes were similar. Carry-over contamination was worse for peak area than peak height, worse for ramped atomization than stepped atomization, and worse for atomization from a platform than from the wall. Accurate determinations (100 ± 12% for Ca, Cu, Fe, Mn, and Zn in National Bureau of Standards' Standard Reference Materials Bovine Liver 1577 and Rice Flour 1568 were obtained using peak area measurements with ramped atomization from the wall and stepped atomization from a platform. Only stepped atomization from a platform gave accurate recoveries for K. Accurate recoveries, 100 ± 10%, with precisions ranging from 1 to 36 % (standard deviation), were obtained for the determination of Al, Co, Cr, Fe, Mn, Mo, Ni. Pb, V and Zn in Acidified Waters (NBS SRM 1643 and 1643a) using stepped atomization from a platform.

Heart rate measurement as a tool to quantify sedentary behavior.

PubMed

Åkerberg, Anna; Koshmak, Gregory; Johansson, Anders; Lindén, Maria

2015-01-01

Sedentary work is very common today. The aim of this pilot study was to attempt to differentiate between typical work situations and to investigate the possibility to break sedentary behavior, based on physiological measurement among office workers. Ten test persons used one heart rate based activity monitor (Linkura), one pulse oximeter device (Wrist) and one movement based activity wristband (Fitbit Flex), in different working situations. The results showed that both heart rate devices, Linkura and Wrist, were able to detect differences in heart rate between the different working situations (resting, sitting, standing, slow walk and medium fast walk). The movement based device, Fitbit Flex, was only able to separate differences in steps between slow walk and medium fast walk. It can be concluded that heart rate measurement is a promising tool for quantifying and separating different working situations, such as sitting, standing and walking.

Physical Activity During Recess Outdoors and Indoors Among Urban Public School Students, St. Louis, Missouri, 2010–2011

PubMed Central

Tran, Irene; Clark, B. Ruth

2013-01-01

We measured the quantity and intensity of physical activity in 106 urban public school students during recess outdoors, recess indoors in the gym, and recess indoors in the classroom. Students in grades 2 through 5 wore accelerometer pedometers for an average of 6.2 (standard deviation [SD], 1.4) recess periods over 8 weeks; a subsample of 26 also wore heart rate monitors. We determined, on the basis of 655 recess observations, that outdoor recess enabled more total steps per recess period (P < .0001), more steps in moderate-to-vigorous physical activity (P < .0001), and higher heart rates than recess in the gym or classroom. To maximize physical activity quantity and intensity, school policies should promote outdoor recess. PMID:24262028

Measurement of semiochemical release rates with a dedicated environmental control system

Treesearch

Heping Zhu; Harold W. Thistle; Christopher M. Ranger; Hongping Zhou; Brian L. Strom

2015-01-01

Insect semiochemical dispensers are commonly deployed under variable environmental conditions over a specified period. Predictions of their longevity are hampered by a lack of methods to accurately monitor and predict how primary variables affect semiochemical release rate. A system was constructed to precisely determine semiochemical release rates under...

Similarity of plant functional traits and aggregation pattern in a subtropical forest

USGS Publications Warehouse

Zhang, Bo; Lu, Xiaozhen; Jiang, Jiang; DeAngelis, Donald L.; Fu, Zhiyuan; Zhang, Jinchi

2017-01-01

The distribution of species and communities in relation to environmental heterogeneity is a central focus in ecology. Co-occurrence of species with similar functional traits is an indication that communities are determined in part by environmental filters. However, few studies have been designed to test how functional traits are selectively filtered by environmental conditions at local scales. Exploring the relationship between soil characteristics and plant traits is a step toward understanding the filtering hypothesis in determining plant distribution at local scale. Toward this end, we mapped all individual trees (diameter >1 cm) in a one-ha subtropical forest of China in 2007 and 2015. We measured topographic and detailed soil properties within the field site, as well as plant leaf functional traits and demographic rates of the seven most common tree species. A second one-ha study plot was established in 2015, to test and validate the general patterns that were drawn from first plot. We found that variation in species distribution at local scale can be explained by soil heterogeneity and plant functional traits. (From first plot). (1) Species dominant in habitats with high soil ammonium nitrogen and total phosphorus tended to have high specific leaf area (SLA) and relative growth rate (RGR). (2) Species dominant in low-fertility habitats tended to have high leaf dry matter content (LDMC), ratio of chlorophyll a and b (ratioab), and leaf thickness (LT). The hypothesis that functional traits are selected in part by environmental filters and determine plant distribution at local scale was confirmed by the data of the first plot and a second regional site showed similar species distribution patterns.

Metabolic responses to Wii Fit™ video games at different game levels.

PubMed

Worley, Jennifer R; Rogers, Sharon N; Kraemer, Robert R

2011-03-01

The Wii Fit™ is a form of interactive gaming designed to elicit health and fitness benefits to replace sedentary gaming. This study was designed to determine the effectiveness of Wii Fit™ fitness games. The purpose of the study was to determine the %VO2max and energy expenditure from different Wii Fit™ games at different levels including the step and hula games. Eight healthy young women completed a preliminary trial to determine VO2max and later played the Wii Fit™ during 2 separate counterbalanced trials. During each session, subjects played levels of Wii Fit™ games for 10 minutes each level. One session involved beginning and intermediate hula, and the other session involved beginning and intermediate steps. The VO2 was measured continuously via metabolic cart, and rating of perceived exertion (RPE) was assessed at the end of each game level. The lowest %VO2max, kcal·min, and RPE occurred during the beginning step game and the highest values occurred during the intermediate hula game. Respiratory exchange ratio was significantly higher in the intermediate hula than beginning hula game but was not significantly different between step game levels. The intermediate hula and step games produced the greatest energy expenditure with an equivalent effect of a walking speed of >5.63 km·h (>3.5 miles·h). This is the first study to determine the percentage of VO2max and caloric expenditure elicited by different Wii Fit™ video games at different game levels in adults. Findings suggest that the Wii Fit™ can be used as an effective activity for promoting physical health in this population.

Computing discharge using the index velocity method

USGS Publications Warehouse

Levesque, Victor A.; Oberg, Kevin A.

2012-01-01

Application of the index velocity method for computing continuous records of discharge has become increasingly common, especially since the introduction of low-cost acoustic Doppler velocity meters (ADVMs) in 1997. Presently (2011), the index velocity method is being used to compute discharge records for approximately 470 gaging stations operated and maintained by the U.S. Geological Survey. The purpose of this report is to document and describe techniques for computing discharge records using the index velocity method. Computing discharge using the index velocity method differs from the traditional stage-discharge method by separating velocity and area into two ratings—the index velocity rating and the stage-area rating. The outputs from each of these ratings, mean channel velocity (V) and cross-sectional area (A), are then multiplied together to compute a discharge. For the index velocity method, V is a function of such parameters as streamwise velocity, stage, cross-stream velocity, and velocity head, and A is a function of stage and cross-section shape. The index velocity method can be used at locations where stage-discharge methods are used, but it is especially appropriate when more than one specific discharge can be measured for a specific stage. After the ADVM is selected, installed, and configured, the stage-area rating and the index velocity rating must be developed. A standard cross section is identified and surveyed in order to develop the stage-area rating. The standard cross section should be surveyed every year for the first 3 years of operation and thereafter at a lesser frequency, depending on the susceptibility of the cross section to change. Periodic measurements of discharge are used to calibrate and validate the index rating for the range of conditions experienced at the gaging station. Data from discharge measurements, ADVMs, and stage sensors are compiled for index-rating analysis. Index ratings are developed by means of regression techniques in which the mean cross-sectional velocity for the standard section is related to the measured index velocity. Most ratings are simple-linear regressions, but more complex ratings may be necessary in some cases. Once the rating is established, validation measurements should be made periodically. Over time, validation measurements may provide additional definition to the rating or result in the creation of a new rating. The computation of discharge is the last step in the index velocity method, and in some ways it is the most straight-forward step. This step differs little from the steps used to compute discharge records for stage-discharge gaging stations. The ratings are entered into database software used for records computation, and continuous records of discharge are computed.

Hydraulic Design of Stepped Spillways Workshop

USDA-ARS?s Scientific Manuscript database

Stepped chutes and spillways are commonly used for routing discharges during flood events. In addition, stepped chutes are used for overtopping protection of earthen embankments. Stepped spillways provide significant energy dissipation due to its stepped feature; as a result, the stilling basin as...

Substrate Efflux Propensity Is the Key Determinant of Ca2+-independent Phospholipase A-β (iPLAβ)-mediated Glycerophospholipid Hydrolysis*

PubMed Central

Batchu, Krishna Chaithanya; Hokynar, Kati; Jeltsch, Michael; Mattonet, Kenny; Somerharju, Pentti

2015-01-01

The A-type phospholipases (PLAs) are key players in glycerophospholipid (GPL) homeostasis and in mammalian cells; Ca2+-independent PLA-β (iPLAβ) in particular has been implicated in this essential process. However, the regulation of this enzyme, which is necessary to avoid futile competition between synthesis and degradation, is not understood. Recently, we provided evidence that the efflux of the substrate molecules from the bilayer is the rate-limiting step in the hydrolysis of GPLs by some secretory (nonhomeostatic) PLAs. To study whether this is the case with iPLAβ as well, a mass spectrometric assay was employed to determine the rate of hydrolysis of multiple saturated and unsaturated GPL species in parallel using micelles or vesicle bilayers as the macrosubstrate. With micelles, the hydrolysis decreased with increasing acyl chain length independent of unsaturation, and modest discrimination between acyl positional isomers was observed, presumably due to the differences in the structure of the sn-1 and sn-2 acyl-binding sites of the protein. In striking contrast, no significant discrimination between positional isomers was observed with bilayers, and the rate of hydrolysis decreased with the acyl chain length logarithmically and far more than with micelles. These data provide compelling evidence that efflux of the substrate molecule from the bilayer, which also decreases monotonously with acyl chain length, is the rate-determining step in iPLAβ-mediated hydrolysis of GPLs in membranes. This finding is intriguing as it may help to understand how homeostatic PLAs are regulated and how degradation and biosynthesis are coordinated. PMID:25713085

Articulation Rate and Vowel Space Characteristics of Young Males with Fragile X Syndrome: Preliminary Acoustic Findings

ERIC Educational Resources Information Center

Zajac, David J.; Roberts, Joanne E.; Hennon, Elizabeth A.; Harris, Adrianne A.; Barnes, Elizabeth F.; Misenheimer, Jan

2006-01-01

Purpose: Increased speaking rate is a commonly reported perceptual characteristic among males with fragile X syndrome (FXS). The objective of this preliminary study was to determine articulation rate--one component of perceived speaking rate--and vowel space characteristics of young males with FXS. Method: Young males with FXS (n = 38), …

An Automated Method of Scanning Probe Microscopy (SPM) Data Analysis and Reactive Site Tracking for Mineral-Water Interface Reactions Observed at the Nanometer Scale

NASA Astrophysics Data System (ADS)

Campbell, B. D.; Higgins, S. R.

2008-12-01

Developing a method for bridging the gap between macroscopic and microscopic measurements of reaction kinetics at the mineral-water interface has important implications in geological and chemical fields. Investigating these reactions on the nanometer scale with SPM is often limited by image analysis and data extraction due to the large quantity of data usually obtained in SPM experiments. Here we present a computer algorithm for automated analysis of mineral-water interface reactions. This algorithm automates the analysis of sequential SPM images by identifying the kinetically active surface sites (i.e., step edges), and by tracking the displacement of these sites from image to image. The step edge positions in each image are readily identified and tracked through time by a standard edge detection algorithm followed by statistical analysis on the Hough Transform of the edge-mapped image. By quantifying this displacement as a function of time, the rate of step edge displacement is determined. Furthermore, the total edge length, also determined from analysis of the Hough Transform, combined with the computed step speed, yields the surface area normalized rate of the reaction. The algorithm was applied to a study of the spiral growth of the calcite(104) surface from supersaturated solutions, yielding results almost 20 times faster than performing this analysis by hand, with results being statistically similar for both analysis methods. This advance in analysis of kinetic data from SPM images will facilitate the building of experimental databases on the microscopic kinetics of mineral-water interface reactions.

Understanding Biological Rates and their Temperature Dependence, from Enzymes to Ecosystems

NASA Astrophysics Data System (ADS)

Prentice, E.; Arcus, V. L.

2017-12-01

Temperature responses over various scales in biological systems follow a similar pattern; negative curvature results in an optimum temperature (Topt) for activity/growth/turnover, with decreases in rates on either side of Topt. Previously this downturn in rates at high temperatures has been attributed to enzyme denaturation, where a failing of the basic driving units of metabolism was used to describe curvature at the enzyme and organism level. However, recent developments in our understanding of the factors governing enzyme rates at different temperatures have guided a new understanding of the responses of biological systems. Enzymes catalyse reactions by driving the substrate through a high energy species, which is tightly bound to the enzyme. Macromolecular rate theory (MMRT) has recently been developed to account for the changes in the system brought about by this tight binding, specifically the change in the physical parameter heat capacity (ΔCǂp), and the effect this has on the temperature dependence of enzyme reactions. A negative ΔCǂp imparts the signature negative curvature to rates in the absence of denaturation, and finds that Topt, ΔCǂp and curvature are all correlated, placing constraints on biological systems. The simplest of cells comprise thousands of enzymatically catalysed reactions, functioning in series and in parallel in metabolic pathways to determine the overall growth rate of an organism. Intuitively, the temperature effects of enzymes play a role in determining the overall temperature dependence of an organism, in tandem with cellular level regulatory responses. However, the effect of individual Topt values and curvature on overall pathway behaviour is less apparent. Here, this is investigated in the context of MMRT through the in vitro characterisation of a six-step metabolic pathway to understand the steps in isolation and functioning in series. Pathway behaviour is found to be approximately an average of the properties of the individual steps, indicating all enzymes have an influence on organism temperature dependence. This has implications for our understanding of how organisms respond to fluctuations in environmental temperature.

Noninvasive prenatal detection of sex chromosomal aneuploidies by sequencing circulating cell-free DNA from maternal plasma.

PubMed

Mazloom, Amin R; Džakula, Željko; Oeth, Paul; Wang, Huiquan; Jensen, Taylor; Tynan, John; McCullough, Ron; Saldivar, Juan-Sebastian; Ehrich, Mathias; van den Boom, Dirk; Bombard, Allan T; Maeder, Margo; McLennan, Graham; Meschino, Wendy; Palomaki, Glenn E; Canick, Jacob A; Deciu, Cosmin

2013-06-01

Whole-genome sequencing of circulating cell free (ccf) DNA from maternal plasma has enabled noninvasive prenatal testing for common autosomal aneuploidies. The purpose of this study was to extend the detection to include common sex chromosome aneuploidies (SCAs): [47,XXX], [45,X], [47,XXY], and [47,XYY] syndromes. Massively parallel sequencing was performed on ccf DNA isolated from the plasma of 1564 pregnant women with known fetal karyotype. A classification algorithm for SCA detection was constructed and trained on this cohort. Another study of 411 maternal samples from women with blinded-to-laboratory fetal karyotypes was then performed to determine the accuracy of the classification algorithm. In the training cohort, the new algorithm had a detection rate (DR) of 100% (95%CI: 82.3%, 100%), a false positive rate (FPR) of 0.1% (95%CI: 0%, 0.3%), and nonreportable rate of 6% (95%CI: 4.9%, 7.4%) for SCA determination. The blinded validation yielded similar results: DR of 96.2% (95%CI: 78.4%, 99.8%), FPR of 0.3% (95%CI: 0%, 1.8%), and nonreportable rate of 5% (95%CI: 3.2%, 7.7%) for SCA determination Noninvasive prenatal identification of the most common sex chromosome aneuploidies is possible using ccf DNA and massively parallel sequencing with a high DR and a low FPR. © 2013 John Wiley & Sons, Ltd.

Step-rate cut-points for physical activity intensity in patients with multiple sclerosis: The effect of disability status.

PubMed

Agiovlasitis, Stamatis; Sandroff, Brian M; Motl, Robert W

2016-02-15

Evaluating the relationship between step-rate and rate of oxygen uptake (VO2) may allow for practical physical activity assessment in patients with multiple sclerosis (MS) of differing disability levels. To examine whether the VO2 to step-rate relationship during over-ground walking differs across varying disability levels among patients with MS and to develop step-rate thresholds for moderate- and vigorous-intensity physical activity. Adults with MS (N=58; age: 51 ± 9 years; 48 women) completed one over-ground walking trial at comfortable speed, one at 0.22 m · s(-1) slower, and one at 0.22 m · s(-1) faster. Each trial lasted 6 min. VO2 was measured with portable spirometry and steps with hand-tally. Disability status was classified as mild, moderate, or severe based on Expanded Disability Status Scale scores. Multi-level regression indicated that step-rate, disability status, and height significantly predicted VO2 (p<0.05). Based on this model, we developed step-rate thresholds for activity intensity that vary by disability status and height. A separate regression without height allowed for development of step-rate thresholds that vary only by disability status. The VO2 during over-ground walking differs among ambulatory patients with MS based on disability level and height, yielding different step-rate thresholds for physical activity intensity. Copyright © 2015 Elsevier B.V. All rights reserved.

Method for measuring pollutant formation

NASA Technical Reports Server (NTRS)

Stickler, David B. (Inventor); Annen, Kurt (Inventor)

2001-01-01

Diagnostic methods for determining an instantaneous rate of pollutant formation in a combustion system are based on measurement of chemiluminescence intensity generated simultaneously with the formation of the pollutant. The chemiluminescent signal is generated by an analog reaction which occurs in parallel with a key step in the formation of a specific pollutant of interest. The connection between the analog reaction and the pollution reaction is such that the chemiluminescent signal indicates the local, instantaneous formation rate of the pollutant of interest.

Spray and Combustion of Gelled Hypergolic Propellants for Future Rocket and Missile Engines

DTIC Science & Technology

2014-08-13

Another aspect of the project was to develop cost- effective viscosity and surface tension determinations as a function of temperature up to 500 K. In...flow rates had an effect on the temperature observed in the stagnation zone with temperature trends from the numerical simulations being similar to...for the single step in the reaction mechanism was varied so as to provide information on the effect of reaction rates on the temperature 137 99

A stepwise approach to stroke surveillance in Brazil: the EMMA (Estudo de Mortalidade e Morbidade do Acidente Vascular Cerebral) study.

PubMed

Goulart, Alessandra C; Bustos, Iara R; Abe, Ivana M; Pereira, Alexandre C; Fedeli, Ligia M; Benseñor, Isabela M; Lotufo, Paulo A

2010-08-01

Stroke mortality rates in Brazil are the highest in the Americas. Deaths from cerebrovascular disease surpass coronary heart disease. To verify stroke mortality rates and morbidity in an area of São Paulo, Brazil, using the World Health Organization Stepwise Approach to Stroke Surveillance. We used the World Health Organization Stepwise Approach to Stroke Surveillance structure of stroke surveillance. The hospital-based data comprised fatal and nonfatal stroke (Step 1). We gathered stroke-related mortality data in the community using World Health Organization questionnaires (Step 2). The questionnaire determining stroke prevalence was activated door to door in a family-health-programme neighbourhood (Step 3). A total of 682 patients 18 years and above, including 472 incident cases, presented with cerebrovascular disease and were enrolled in Step 1 during April-May 2009. Cerebral infarction (84.3%) and first-ever stroke (85.2%) were the most frequent. In Step 2, 256 deaths from stroke were identified during 2006-2007. Forty-four per cent of deaths were classified as unspecified stroke, 1/3 as ischaemic stroke, and 1/4 due to haemorrhagic subtype. In Step 3, 577 subjects over 35 years old were evaluated at home, and 244 cases of stroke survival were diagnosed via a questionnaire, validated by a board-certified neurologist. The population demographic characteristics were similar in the three steps, except in terms of age and gender. By including data from all settings, World Health Organization stroke surveillance can provide data to help plan future resources that meet the needs of the public-health system.

Intracellular pH Recovery Rates in Bivalve Hemocytes Following Exposure to Acidic Environmental Conditions

NASA Astrophysics Data System (ADS)

Croxton, A.; Wikfors, G. H.

2012-12-01

Predictions of ocean acidification effects upon carbonate shell-forming species have caused great concern for the future of shellfisheries. Nevertheless, bivalve species inhabiting an estuarine environment have evolved in these environments with fluctuating pH levels. Previous experimental studies conducted in our laboratory have demonstrated the ability of oyster hemocytes to maintain intracellular homeostasis under acidic external conditions. However, little information is known of this homeostatic mechanism in other molluscan shellfish species present in these same habitats. In the current study we propose to determine if other bivalve species of aquaculture interest also possess this intracellular regulation by applying an in vitro hemocyte pH-recovery assay, previously developed for oysters, on the northern quahog, Mercenaria mercenaria, the blue mussel, Mytilus edulis, and the softshell clam, Mya arenaria. Preliminary results from the determination of initial intracellular pH levels, the initial step in the rate recovery assay, indicated a pH range between 7.0-7.4. This range was comparable to initial values measured in oysters, and consistent with data reported in the current literature. The second step of the hemocyte pH-recovery assay involves exposing oyster hemocytes to acidic external conditions and measuring the ability of the hemocyte intracellular pH to maintain homeostasis (i.e. recovery rate). Results from the recovery rate process will be presented.

What's your real cost of capital?

PubMed

McNulty, James J; Yeh, Tony D; Schulze, William S; Lubatkin, Michael H

2002-10-01

In valuing any investment project or corporate acquisition, executives must decide what discount rate to use in their estimates of future cash flows. The traditional approach is to apply the capital asset pricing model (CAPM), which has remained fundamentally unchanged for 40 years. But the formula--in particular, its beta element--has long been a source of frustration. In fact, corporate executives and investment bankers routinely fudge their CAPM estimates, say the authors, because experience and intuition tell them the model produces inappropriate discount rates. CAPM has three main problems: First, beta is a measure of both a stock's correlation and its volatility; second, beta is based on historical data; and third, CAPM rates don't take into account the term of the investment. These factors together result in discount rates that defy common sense. As an alternative to CAPM and its beta element, the authors developed a forward-looking approach to calculating a company's cost of capital, the market-derived capital pricing model (MCPM). It does not incorporate any measure of historical stock-to-market correlation, relying instead on estimates of future volatility derived from the options market. This is helpful since investor expectations from the options market are built into a company's current stock price. Using GE as an example, the authors give step-by-step instructions for how to calculate discount rates with MCPM. They also offer evidence from a range of industries to show that MCPM's discount rates are more realistic--especially from the corporate investor's perspective--than are CAPM's.

New rapid methods for determination of total LAS in sewage sludge by high performance liquid chromatography (HPLC) and capillary electrophoresis (CE).

PubMed

Villar, M; Callejón, M; Jiménez, J C; Alonso, E; Guiraúm, A

2009-02-23

Linear alkylbenzene sulfonates (LAS) are the most common synthetic anionic surfactant used in domestic and industrial detergents, with a global production of 2.4x10(6) t year(-1). After use and disposal, LAS may enter the environment by one of the several routes, including by direct discharge to surface water or discharge to water from sewage treatment plants. Sewage treatment plants break down LAS only partly: some of them remain in effluent and other fraction is adsorbed in sewage solid. New and rapid methods for determination of total LAS from sewage sludge based on microwave assisted extraction and HPLC-FL and CE-DAD determination are proposed. The extraction of total LAS is carried out by using microwaves energy, an extraction time of 10 min and 5 mL of methanol. For HPLC-FL determination, mobile phase acetonitrile-water was used, comprising 60% (v/v) from 0 to 1 min and a flow rate of 1 mL min(-1) programmed to 100% acetonitrile between 1 and 2 min and a flow rate of 2 mL min(-1). The final composition was maintained for a further 5 min. The determination of total LAS by CE-DAD was performed in a phosphate buffer (10 mM, pH 9). The separation voltage was 25 kV and the temperature of the capillary was 30 degrees C. Injections were performed in the pressure mode and the injection time was set at 12 s. The determination of total LAS is carried out in less than 5 min. The methods did not require clean-up or preconcentration steps. Detection limit for total LAS in the sludge was 3.03 mg kg(-1) using HPLC-FL and 21.0 mg kg(-1) using CE-DAD, and recoveries were >85% using both determination methods. Concentrations of total LAS obtained using both methods were compared with the sum of concentrations of homologues LAS C-10, LAS C-11, LAS C-12 and LAS C-13 obtained using microwaves assisted extraction and HPLC-FL and CE-DAD determination.

Which spike train distance is most suitable for distinguishing rate and temporal coding?

PubMed

Satuvuori, Eero; Kreuz, Thomas

2018-04-01

It is commonly assumed in neuronal coding that repeated presentations of a stimulus to a coding neuron elicit similar responses. One common way to assess similarity are spike train distances. These can be divided into spike-resolved, such as the Victor-Purpura and the van Rossum distance, and time-resolved, e.g. the ISI-, the SPIKE- and the RI-SPIKE-distance. We use independent steady-rate Poisson processes as surrogates for spike trains with fixed rate and no timing information to address two basic questions: How does the sensitivity of the different spike train distances to temporal coding depend on the rates of the two processes and how do the distances deal with very low rates? Spike-resolved distances always contain rate information even for parameters indicating time coding. This is an issue for reasonably high rates but beneficial for very low rates. In contrast, the operational range for detecting time coding of time-resolved distances is superior at normal rates, but these measures produce artefacts at very low rates. The RI-SPIKE-distance is the only measure that is sensitive to timing information only. While our results on rate-dependent expectation values for the spike-resolved distances agree with Chicharro et al. (2011), we here go one step further and specifically investigate applicability for very low rates. The most appropriate measure depends on the rates of the data being analysed. Accordingly, we summarize our results in one table that allows an easy selection of the preferred measure for any kind of data. Copyright © 2018 The Authors. Published by Elsevier B.V. All rights reserved.

Complexity Survey.

ERIC Educational Resources Information Center

Gordon, Sandra L.; Anderson, Beth C.

To determine whether consensus existed among teachers about the complexity of common classroom materials, a survey was administered to 66 pre-service and in-service kindergarten and prekindergarten teachers. Participants were asked to rate 14 common classroom materials as simple, complex, or super-complex. Simple materials have one obvious part,…

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

PubMed Central

2012-01-01

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

Substrate and Enzyme Specificity of the Kinetic Isotope Effects Associated with the Dioxygenation of Nitroaromatic Contaminants.

PubMed

Pati, Sarah G; Kohler, Hans-Peter E; Pabis, Anna; Paneth, Piotr; Parales, Rebecca E; Hofstetter, Thomas B

2016-07-05

Compound-specific isotope analysis (CSIA) is a promising approach for tracking biotransformation of organic pollutants, but isotope fractionation associated with aromatic oxygenations is only poorly understood. We investigated the dioxygenation of a series of nitroaromatic compounds to the corresponding catechols by two enzymes, namely, nitrobenzene and 2-nitrotoluene dioxygenase (NBDO and 2NTDO) to elucidate the enzyme- and substrate-specificity of C and H isotope fractionation. While the apparent (13)C- and (2)H-kinetic isotope effects of nitrobenzene, nitrotoluene isomers, 2,6-dinitrotoluene, and naphthalene dioxygenation by NBDO varied considerably, the correlation of C and H isotope fractionation revealed a common mechanism for nitrobenzene and nitrotoluenes. Similar observations were made for the dioxygenation of these substrates by 2NTDO. Evaluation of reaction kinetics, isotope effects, and commitment-to-catalysis based on experiment and theory showed that rates of dioxygenation are determined by the enzymatic O2 activation and aromatic C oxygenation. The contribution of enzymatic O2 activation to the reaction rate varies for different nitroaromatic substrates of NBDO and 2NTDO. Because aromatic dioxygenation by nonheme iron dioxygenases is frequently the initial step of biodegradation, O2 activation kinetics may also have been responsible for the minor isotope fractionation reported for the oxygenation of other aromatic contaminants.

A Systems Study to Determine the Attractiveness of Solar System Bodies and Sites for Eventual Human Exploration

NASA Technical Reports Server (NTRS)

Andringa, Jason M.; Gray, Andrew A.

2005-01-01

A pre-phase A idea-generation team at the Jet Propulsion Laboratory (JPL), has conducted a study to rank all locations in the solar system based on attractiveness for human exploration. The process used to perform the study was composed of the following primary steps: determination of criteria (including value, cost, and risk criteria) upon which to rate sites in the solar system; weighting of the criteria based upon importance to eventual human exploration; selection of sites to consider and assignment of team members to the task of advocating the benefits of particular sites; rating the sites in both the short- and longterm based on team member presentations and team discussions; compilation of a score based on criteria weights and individual ratings. Finally a comparison of the total scores of different sites was completed to determine a ranking of all the bodies and sites in the solar system. Sensitivity analysis was also performed to determine how weightings affect the rankings.

An intraorganizational model for developing and spreading quality improvement innovations.

PubMed

Kellogg, Katherine C; Gainer, Lindsay A; Allen, Adrienne S; OʼSullivan, Tatum; Singer, Sara J

Recent policy reforms encourage quality improvement (QI) innovations in primary care, but practitioners lack clear guidance regarding spread inside organizations. We designed this study to identify how large organizations can facilitate intraorganizational spread of QI innovations. We conducted ethnographic observation and interviews in a large, multispecialty, community-based medical group that implemented three QI innovations across 10 primary care sites using a new method for intraorganizational process development and spread. We compared quantitative outcomes achieved through the group's traditional versus new method, created a process model describing the steps in the new method, and identified barriers and facilitators at each step. The medical group achieved substantial improvement using its new method of intraorganizational process development and spread of QI innovations: standard work for rooming and depression screening, vaccine error rates and order compliance, and Pap smear error rates. Our model details nine critical steps for successful intraorganizational process development (set priorities, assess the current state, develop the new process, and measure and refine) and spread (develop support, disseminate information, facilitate peer-to-peer training, reinforce, and learn and adapt). Our results highlight the importance of utilizing preexisting organizational structures such as established communication channels, standardized roles, common workflows, formal authority, and performance measurement and feedback systems when developing and spreading QI processes inside an organization. In particular, we detail how formal process advocate positions in each site for each role can facilitate the spread of new processes. Successful intraorganizational spread is possible and sustainable. Developing and spreading new QI processes across sites inside an organization requires creating a shared understanding of the necessary process steps, considering the barriers that may arise at each step, and leveraging preexisting organizational structures to facilitate intraorganizational process development and spread.

An intraorganizational model for developing and spreading quality improvement innovations

PubMed Central

Kellogg, Katherine C.; Gainer, Lindsay A.; Allen, Adrienne S.; O'Sullivan, Tatum; Singer, Sara J.

2017-01-01

Background: Recent policy reforms encourage quality improvement (QI) innovations in primary care, but practitioners lack clear guidance regarding spread inside organizations. Purpose: We designed this study to identify how large organizations can facilitate intraorganizational spread of QI innovations. Methodology/Approach: We conducted ethnographic observation and interviews in a large, multispecialty, community-based medical group that implemented three QI innovations across 10 primary care sites using a new method for intraorganizational process development and spread. We compared quantitative outcomes achieved through the group’s traditional versus new method, created a process model describing the steps in the new method, and identified barriers and facilitators at each step. Findings: The medical group achieved substantial improvement using its new method of intraorganizational process development and spread of QI innovations: standard work for rooming and depression screening, vaccine error rates and order compliance, and Pap smear error rates. Our model details nine critical steps for successful intraorganizational process development (set priorities, assess the current state, develop the new process, and measure and refine) and spread (develop support, disseminate information, facilitate peer-to-peer training, reinforce, and learn and adapt). Our results highlight the importance of utilizing preexisting organizational structures such as established communication channels, standardized roles, common workflows, formal authority, and performance measurement and feedback systems when developing and spreading QI processes inside an organization. In particular, we detail how formal process advocate positions in each site for each role can facilitate the spread of new processes. Practice Implications: Successful intraorganizational spread is possible and sustainable. Developing and spreading new QI processes across sites inside an organization requires creating a shared understanding of the necessary process steps, considering the barriers that may arise at each step, and leveraging preexisting organizational structures to facilitate intraorganizational process development and spread. PMID:27428788

Ultrasound-assisted HCl-NaCl leaching of lead-rich and antimony-rich oxidizing slag.

PubMed

Zhang, Rong Liang; Zhang, Xiao Fei; Tang, Shu Zhen; Huang, Ai Dong

2015-11-01

Lead-rich and antimony-rich oxidizing slag was subjected to regular HCl-NaCl leaching, with the experimental conditions optimized under which ultrasound was introduced. After only 15 min of ultrasound-assisted leaching, the leaching rate of Sb resembled that after 45 min of regular leaching. Ultrasonic treatment considerably elevated the leaching rates of Sb and Pb, and shortened the leaching time. With the decrease of particle size, the leaching rate of Sb and Pb increased gradually. Especially, as the particle size of the slag was greater than 0.217 mm, the ultrasonic leaching effects of Sb and Pb were significantly higher than that of regular leaching effects. The temperature exhibited great effect on ultrasonic leaching performance. As the temperature increased, the leaching rates of Sb and Pb increased step by step. In case the temperature was higher than 85°C, the increasing speed of the leaching rates for Sb and Pb tended to be slow. Increasing ultrasonic power could augment the leaching rate or accelerate the procedure till the same leaching rate. However, since ultrasound failed to energize the formation of new reaction pathways, the maximum leaching rates of Sb and Pb were determined by their phase compositions rather than by ultrasonic field. Copyright © 2015 Elsevier B.V. All rights reserved.

12 CFR Appendix A to Part 230 - Annual Percentage Yield Calculation

Code of Federal Regulations, 2013 CFR

2013-01-01

... stepped interest rates, and to certain time accounts with a stated maturity greater than one year. A... calculated by the formula shown below. Institutions shall calculate the annual percentage yield based on the... determining the total interest figure to be used in the formula, institutions shall assume that all principal...

12 CFR Appendix A to Part 230 - Annual Percentage Yield Calculation

Code of Federal Regulations, 2011 CFR

2011-01-01

... stepped interest rates, and to certain time accounts with a stated maturity greater than one year. A... calculated by the formula shown below. Institutions shall calculate the annual percentage yield based on the... determining the total interest figure to be used in the formula, institutions shall assume that all principal...

12 CFR Appendix A to Part 230 - Annual Percentage Yield Calculation

Code of Federal Regulations, 2014 CFR

2014-01-01

... stepped interest rates, and to certain time accounts with a stated maturity greater than one year. A... calculated by the formula shown below. Institutions shall calculate the annual percentage yield based on the... determining the total interest figure to be used in the formula, institutions shall assume that all principal...

Flow Curve Analysis of 17-4 PH Stainless Steel under Hot Compression Test

NASA Astrophysics Data System (ADS)

Mirzadeh, Hamed; Najafizadeh, Abbas; Moazeny, Mohammad

2009-12-01

The hot compression behavior of a 17-4 PH stainless steel (AISI 630) has been investigated at temperatures of 950 °C to 1150 °C and strain rates of 10-3 to 10 s-1. Glass powder in the Rastegaev reservoirs of the specimen was used as a lubricant material. A step-by-step procedure for data analysis in the hot compression test was given. The work hardening rate analysis was performed to reveal if dynamic recrystallization (DRX) occurred. Many samples exhibited typical DRX stress-strain curves with a single peak stress followed by a gradual fall toward the steady-state stress. At low Zener-Hollomon ( Z) parameter, this material showed a new DRX flow behavior, which was called multiple transient steady state (MTSS). At high Z, as a result of adiabatic deformation heating, a drop in flow stress was observed. The general constitutive equations were used to determine the hot working constants of this material. Moreover, after a critical discussion, the deformation activation energy of 17-4 PH stainless steel was determined as 337 kJ/mol.

The importance of alcohol dehydrogenase in regulation of ethanol metabolism in rat liver cells.

PubMed Central

Page, R A; Kitson, K E; Hardman, M J

1991-01-01

We used titration with the inhibitors tetramethylene sulphoxide and isobutyramide to assess quantitatively the importance of alcohol dehydrogenase in regulation of ethanol oxidation in rat hepatocytes. In hepatocytes isolated from starved rats the apparent Flux Control Coefficient (calculated assuming a single-substrate irreversible reaction with non-competitive inhibition) of alcohol dehydrogenase is 0.3-0.5. Adjustment of this coefficient to allow for alcohol dehydrogenase being a two-substrate reversible enzyme increases the value by 1.3-1.4-fold. The final value of the Flux Control Coefficient of 0.5-0.7 indicates that alcohol dehydrogenase is a major rate-determining enzyme, but that other factors also have a regulatory role. In hepatocytes from fed rats the Flux Control Coefficient for alcohol dehydrogenase decreases with increasing acetaldehyde concentration. This suggests that, as acetaldehyde concentrations rise, control of the pathway shifts from alcohol dehydrogenase to other enzymes, particularly aldehyde dehydrogenase. There is not a single rate-determining step for the ethanol metabolism pathway and control is shared among several steps. PMID:1898355

Relative binding affinities of monolignols to horseradish peroxidase

DOE PAGES

Sangha, Amandeep K.; Petridis, Loukas; Cheng, Xiaolin; ...

2016-07-22

Monolignol binding to the peroxidase active site is the first step in lignin polymerization in plant cell walls. Using molecular dynamics, docking, and free energy perturbation calculations, we investigate the binding of monolignols to horseradish peroxidase C. Our results suggest that p-coumaryl alcohol has the strongest binding affinity followed by sinapyl and coniferyl alcohol. Stacking interactions between the monolignol aromatic rings and nearby phenylalanine residues play an important role in determining the calculated relative binding affinities. p-Coumaryl and coniferyl alcohols bind in a pose productive for reaction in which a direct H-bond is formed between the phenolic –OH group andmore » a water molecule (W2) that may facilitate proton transfer during oxidation. In contrast, in the case of sinapyl alcohol there is no such direct interaction, the phenolic –OH group instead interacting with Pro139. Furthermore, since proton and electron transfer is the rate-limiting step in monolignol oxidation by peroxidase, the binding pose (and thus the formation of near attack conformation) appears to play a more important role than the overall binding affinity in determining the oxidation rate.« less

Campylobacter in chicken carcasses and slaughterhouses in Malaysia.

PubMed

Rejab, Saira Banu Mohamed; Zessin, Karl-Hans; Fries, Reinhard; Patchanee, Prapas

2012-01-01

This study was conducted to determine the Campylobacter contamination rate of chicken carcasses and the processing lines of modern processing plants in Malaysia. Three hundred sixty samples were collected from 24 flocks of broiler chickens at 12 modern poultry processing plants in 6 states of Malaysia. Fresh fecal droppings were collected from crates in the arrival area. Neck skin samples were taken from processed chicken carcasses at 3 different processing stages: before inside-outside washing, after inside-outside washing and post chilling. Swab samples from the scalding tank, chilling tank and conveyer belt before chilling were also collected to determine contamination with Campylobacter in the slaughter house environment prior to slaughter. Isolation for Campylobacter was performed following ISO 10272-1:2006(E). The overall of contamination rate with Campylobacter at the 12 plants was 61.0% (220/360). Eighty point six percent of the samples from before the inside-outside wishing step were contaminated with Campylobacter, as were 62.5% of the samples after the inside washing and 38.9% after the post-chilling step. This study shows extensive contamination of chicken carcasses and slaughtering houses in Malaysia with Campylobacter.

Influence of frequency on shear fatigue strength of resin composite to enamel bonds using self-etch adhesives.

PubMed

Takamizawa, Toshiki; Scheidel, Donal D; Barkmeier, Wayne W; Erickson, Robert L; Tsujimoto, Akimasa; Latta, Mark A; Miyazaki, Masashi

2016-09-01

The purpose of this study was to determine the influence of different frequency rates on of bond durability of self-etch adhesives to enamel using shear fatigue strength (SFS) testing. A two-step self-etch adhesive (OX, OptiBond XTR), and two single step self-etch adhesives (GB, G-ӕnial Bond and SU, Scotchbond Universal) were used in this study. The shear fatigue strength (SFS) to enamel was obtained. A staircase method was used to determine the SFS values with 50,000 cycles or until failure occurred. Fatigue testing was performed at frequencies of 5Hz, 10Hz, and 20Hz. For each test condition, 30 specimens were prepared for the SFS testing. Regardless of the bond strength test method, OX showed significantly higher SFS values than the two single-step self-etch adhesives. For each of the three individual self-etch adhesives, there was no significant difference in SFS depending on the frequency rate, although 20Hz results tended to be higher. Regardless of the self-etch adhesive system, frequencies of 5Hz, 10Hz, and 20Hz produced similar results in fatigue strength of resin composite bonded to enamel using 50,000 cycles or until bond failure. Accelerated fatigue testing provides valuable information regarding the long term durability of resin composite to enamel bonding using self-etch adhesive system. Copyright © 2016 Elsevier Ltd. All rights reserved.

Theoretical study of methanol synthesis from CO2 and CO hydrogenation on the surface of ZrO2 supported In2O3 catalyst

NASA Astrophysics Data System (ADS)

Dou, Maobin; Zhang, Minhua; Chen, Yifei; Yu, Yingzhe

2018-06-01

The interactions between ZrO2 support and In2O3 catalyst play pivotal role in the catalytic conversion of CO2 to methanol. Herein, a density functional theory study has been conducted to research the mechanism of methanol synthesis from CO2 and CO hydrogenation on the defective ZrO2 supported In2O3(110) surface (D surface). The calculations reveal that methanol is produced mainly via the HCOO reaction pathway from CO2 hydrogenation on D surface, and the hydrogenation of HCOO to form H2COO species with an activation barrier of 1.21 eV plays the rate determining step for the HCOO reaction pathway. The direct dissociation of CO2 to CO on D surface is kinetically and energetically prohibited. Methanol synthesis from CO hydrogenation on D surface is much facile comparing with the elementary steps involved in CO2 hydrogenation. The rate determining step of CO hydrogenation to methanol is the formation of H3CO species on the vacancy site with a barrier of 0.51 eV. ZrO2 support has significant effect on the suppressing of the dissociation of CO2 and stabilization of H2COO species on the surface of In2O3 catalyst.

What determines catalyst functionality in molecular water oxidation? Dependence on ligands and metal nuclearity in cobalt clusters.

PubMed

Smith, Paul F; Kaplan, Christopher; Sheats, John E; Robinson, David M; McCool, Nicholas S; Mezle, Nicholas; Dismukes, G Charles

2014-02-17

The metal-oxo M4O4 "cubane" topology is of special significance to the field of water oxidation as it represents the merging of bioinspired structural principles derived from natural photosynthesis with successful artificial catalysts known to date. Herein, we directly compare the rates of water oxidation/O2 evolution catalyzed by six cobalt-oxo clusters including the Co4O4 cubanes, Co4O4(OAc)4(py)4 and [Co4O4(OAc)2(bpy)4](2+), using the common Ru(bpy)3(2+)/S2O8(2-) photo-oxidant assay. At pH 8, the first-order rate constants for these cubanes differ by 2-fold, 0.030 and 0.015 s(-1), respectively, reflecting the number of labile carboxylate sites that allow substrate water binding in a pre-equilibrium step before O2 release. Kinetic results reveal a deprotonation step occurs on this pathway and that two electrons are removed before O2 evolution occurs. The Co4O4 cubane core is shown to be the smallest catalytic unit for the intramolecular water oxidation pathway, as neither "incomplete cubane" trimers [Co3O(OH)3(OAc)2(bpy)3](2+) and [Co3O(OH)2(OAc)3(py)5](2+) nor "half cubane" dimers [Co2(OH)2(OAc)3(bpy)2](+) and [Co2(OH)2(OAc)3(py)4](+) were found capable of evolving O2, despite having the same ligand sets as their cubane counterparts. Electrochemical studies reveal that oxidation of both cubanes to formally Co4(3III,IV) (0.7 V vs Ag/AgCl) occurs readily, while neither dimers nor trimers are oxidized below 1.5 V, pointing to appreciably greater charge delocalization in the [Co4O4](5+) core. The origin of catalytic activity by Co4O4 cubanes illustrates three key features for water oxidation: (1) four one-electron redox metals, (2) efficient charge delocalization of the first oxidation step across the Co4O4 cluster, allowing for stabilization of higher oxidizing equivalents, and (3) terminal coordination site for substrate aquo/oxo formation.

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

Towards the run and walk activity classification through step detection--an android application.

PubMed

Oner, Melis; Pulcifer-Stump, Jeffry A; Seeling, Patrick; Kaya, Tolga

2012-01-01

Falling is one of the most common accidents with potentially irreversible consequences, especially considering special groups, such as the elderly or disabled. One approach to solve this issue would be an early detection of the falling event. Towards reaching the goal of early fall detection, we have worked on distinguishing and monitoring some basic human activities such as walking and running. Since we plan to implement the system mostly for seniors and the disabled, simplicity of the usage becomes very important. We have successfully implemented an algorithm that would not require the acceleration sensor to be fixed in a specific position (the smart phone itself in our application), whereas most of the previous research dictates the sensor to be fixed in a certain direction. This algorithm reviews data from the accelerometer to determine if a user has taken a step or not and keeps track of the total amount of steps. After testing, the algorithm was more accurate than a commercial pedometer in terms of comparing outputs to the actual number of steps taken by the user.

Erosion and deposition by supercritical density flows during channel avulsion and backfilling: Field examples from coarse-grained deepwater channel-levée complexes (Sandino Forearc Basin, southern Central America)

NASA Astrophysics Data System (ADS)

Lang, Jörg; Brandes, Christian; Winsemann, Jutta

2017-03-01

Erosion and deposition by supercritical density flows can strongly impact the facies distribution and architecture of submarine fans. Field examples from coarse-grained channel-levée complexes from the Sandino Forearc Basin (southern Central America) show that cyclic-step and antidune deposits represent common sedimentary facies of these depositional systems and relate to the different stages of avulsion, bypass, levée construction and channel backfilling. During channel avulsion, large-scale scour-fill complexes (18 to 29 m deep, 18 to 25 m wide, 60 to > 120 m long) were incised by supercritical density flows. The multi-storey infill of the large-scale scour-fill complexes comprises amalgamated massive, normally coarse-tail graded or widely spaced subhorizontally stratified conglomerates and pebbly sandstones, interpreted as deposits of the hydraulic-jump zone of cyclic steps. The large-scale scour-fill complexes can be distinguished from small-scale channel fills based on the preservation of a steep upper margin and a coarse-grained infill comprising mainly amalgamated hydraulic-jump zone deposits. Channel fills include repeated successions deposited by cyclic steps with superimposed antidunes. The deposits of the hydraulic-jump zone of cyclic steps comprise regularly spaced scours (0.2 to 2.6 m deep, 0.8 to 23 m long) infilled by intraclast-rich conglomerates or pebbly sandstones, displaying normal coarse-tail grading or backsets. These deposits are laterally and vertically associated with subhorizontally stratified, low-angle cross-stratified or sinusoidally stratified sandstones and pebbly sandstones, which were deposited by antidunes on the stoss side of the cyclic steps during flow re-acceleration. The field examples indicate that so-called spaced stratified deposits may commonly represent antidune deposits with varying stratification styles controlled by the aggradation rate, grain-size distribution and amalgamation. The deposits of small-scale cyclic steps with superimposed antidunes form fining-upwards successions with decreasing antidune wavelengths, indicating waning flows. Such cyclic step-antidune successions form the characteristic basal infill of mid-fan channels, and are inferred to be related to successive supercritical high-density turbidity flows triggered by retrogressive slope failures.

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

Isotalo, Aarno

A method referred to as tally nuclides is presented for accurately and efficiently calculating the time-step averages and integrals of any quantities that are weighted sums of atomic densities with constant weights during the step. The method allows all such quantities to be calculated simultaneously as a part of a single depletion solution with existing depletion algorithms. Some examples of the results that can be extracted include step-average atomic densities and macroscopic reaction rates, the total number of fissions during the step, and the amount of energy released during the step. Furthermore, the method should be applicable with several depletionmore » algorithms, and the integrals or averages should be calculated with an accuracy comparable to that reached by the selected algorithm for end-of-step atomic densities. The accuracy of the method is demonstrated in depletion calculations using the Chebyshev rational approximation method. Here, we demonstrate how the ability to calculate energy release in depletion calculations can be used to determine the accuracy of the normalization in a constant-power burnup calculation during the calculation without a need for a reference solution.« less

Calculating Time-Integral Quantities in Depletion Calculations

DOE PAGES

Isotalo, Aarno

2016-06-02

A method referred to as tally nuclides is presented for accurately and efficiently calculating the time-step averages and integrals of any quantities that are weighted sums of atomic densities with constant weights during the step. The method allows all such quantities to be calculated simultaneously as a part of a single depletion solution with existing depletion algorithms. Some examples of the results that can be extracted include step-average atomic densities and macroscopic reaction rates, the total number of fissions during the step, and the amount of energy released during the step. Furthermore, the method should be applicable with several depletionmore » algorithms, and the integrals or averages should be calculated with an accuracy comparable to that reached by the selected algorithm for end-of-step atomic densities. The accuracy of the method is demonstrated in depletion calculations using the Chebyshev rational approximation method. Here, we demonstrate how the ability to calculate energy release in depletion calculations can be used to determine the accuracy of the normalization in a constant-power burnup calculation during the calculation without a need for a reference solution.« less

Mechanistic Basis for High Stereoselectivity and Broad Substrate Scope in the (salen)Co(III)-Catalyzed Hydrolytic Kinetic Resolution

PubMed Central

Ford, David D.; Nielsen, Lars P. C.; Zuend, Stephan J.; Jacobsen, Eric N.

2013-01-01

In the (salen)Co(III)-catalyzed hydrolytic kinetic resolution (HKR) of terminal epoxides, the rate- and stereoselectivity-determining epoxide ring-opening step occurs by a cooperative bimetallic mechanism with one Co(III) complex acting as a Lewis acid and another serving to deliver the hydroxide nucleophile. In this paper, we analyze the basis for the extraordinarily high stereoselectivity and broad substrate scope observed in the HKR. We demonstrate that the stereochemistry of each of the two (salen)Co(III) complexes in the rate-determining transition structure is important for productive catalysis: a measurable rate of hydrolysis occurs only if the absolute stereochemistry of each of these (salen)Co(III) complexes is the same. Experimental and computational studies provide strong evidence that stereochemical communication in the HKR is mediated by the stepped conformation of the salen ligand, and not the shape of the chiral diamine backbone of the ligand. A detailed computational analysis reveals that the epoxide binds the Lewis acidic Co(III) complex in a well-defined geometry imposed by stereoelectronic, rather than steric effects. This insight serves as the basis of a complete stereochemical and transition structure model that sheds light on the reasons for the broad substrate generality of the HKR. PMID:24041239

Mechanistic basis for high stereoselectivity and broad substrate scope in the (salen)Co(III)-catalyzed hydrolytic kinetic resolution.

PubMed

Ford, David D; Nielsen, Lars P C; Zuend, Stephan J; Musgrave, Charles B; Jacobsen, Eric N

2013-10-16

In the (salen)Co(III)-catalyzed hydrolytic kinetic resolution (HKR) of terminal epoxides, the rate- and stereoselectivity-determining epoxide ring-opening step occurs by a cooperative bimetallic mechanism with one Co(III) complex acting as a Lewis acid and another serving to deliver the hydroxide nucleophile. In this paper, we analyze the basis for the extraordinarily high stereoselectivity and broad substrate scope observed in the HKR. We demonstrate that the stereochemistry of each of the two (salen)Co(III) complexes in the rate-determining transition structure is important for productive catalysis: a measurable rate of hydrolysis occurs only if the absolute stereochemistry of each of these (salen)Co(III) complexes is the same. Experimental and computational studies provide strong evidence that stereochemical communication in the HKR is mediated by the stepped conformation of the salen ligand, and not the shape of the chiral diamine backbone of the ligand. A detailed computational analysis reveals that the epoxide binds the Lewis acidic Co(III) complex in a well-defined geometry imposed by stereoelectronic rather than steric effects. This insight serves as the basis of a complete stereochemical and transition structure model that sheds light on the reasons for the broad substrate generality of the HKR.

Mechanistic insights into iron catalyzed dehydrogenation of formic acid: β-hydride elimination vs. direct hydride transfer.

PubMed

Yang, Xinzheng

2013-09-07

Density functional theory calculations reveal a complete reaction mechanism with detailed energy profiles and transition state structures for the dehydrogenation of formic acid catalyzed by an iron complex, [P(CH2CH2PPh2)3FeH](+). In the cationic reaction pathway, a β-hydride elimination process is confirmed to be the rate-determining step in this catalytic reaction. A potential reaction pathway starting with a direct hydride transfer from HCOO(-) to Fe is found to be possible, but slightly less favorable than the catalytic cycle with a β-hydride elimination step.

The Next Step in Understanding Impaired Reactive Balance Control in People With Stroke: The Role of Defective Early Automatic Postural Responses.

PubMed

de Kam, Digna; Roelofs, Jolanda M B; Bruijnes, Amber K B D; Geurts, Alexander C H; Weerdesteyn, Vivian

2017-08-01

Postural muscle responses are often impaired after stroke. We aimed to identify the contribution of deficits in very early postural responses to poorer reactive balance capacity, with a particular focus on reactive stepping as a key strategy for avoiding falls. A total of 34 chronic stroke survivors and 17 controls were subjected to translational balance perturbations in 4 directions. We identified the highest perturbation intensity that could be recovered without stepping (single stepping threshold [SST]) and with maximally 1 step (multiple stepping threshold [MST]). We determined onset latencies and response amplitudes of 7 leg muscles bilaterally and identified associations with balance capacity. People with stroke had a lower MST than controls in all directions. Side steps resulted in a higher lateral MST than crossover steps but were less common toward the paretic side. Postural responses were delayed and smaller in amplitude on the paretic side only. We observed the strongest associations between gluteus medius (GLUT) onset and amplitude and MST toward the paretic side ( R 2 = 0.33). Electromyographic variables were rather weakly associated with forward and backward MSTs ( R 2 = 0.10-0.22) and with SSTs ( R 2 = 0.08-0.15). Delayed and reduced paretic postural responses are associated with impaired reactive stepping after stroke. Particularly, fast and vigorous activity of the GLUT is imperative for overcoming large sideways perturbations, presumably because it facilitates the effective use of side steps. Because people with stroke often fall toward the paretic side, this finding indicates an important target for training.

The expanding role of fluoroquinolones.

PubMed

Schaeffer, Anthony J

2003-02-01

There has been a growing rate of resistance among common urinary tract pathogens, such as Escherichia coli, to traditional antimicrobial therapies including the "gold standard" trimethoprim-sulfamethoxazole (TMP-SMX). Consequently, fluoroquinolone antimicrobial agents have taken on an expanding management role for UTIs. In fact, the recent Infectious Diseases Society of America clinical management guidelines for UTI recommend fluoroquinolones as first-line therapy for uncomplicated UTI in areas where resistance is likely to be of concern. Fluoroquinolones have demonstrated high bacteriologic and clinical cure rates, as well as low rates of resistance, among most common uropathogens. There are currently 7 fluoroquinolones with indications for UTI in the United States. However, only 3 are commonly used: levofloxacin, ciprofloxacin, and, to a lesser extent, gatifloxacin. Many of the fluoroquinolone agents have once-daily dosing regimens, enhancing patient adherence. In addition, levofloxacin and gatifloxacin have same-dose bioequivalency between their intravenous and oral formulations, allowing for "switch" or step-down therapy from parenteral to oral formulations of the same agent at the same dose. Fluoroquinolones are indicated for the management of acute uncomplicated UTIs, as well as complicated and severe UTI and pyelonephritis, in adults. They are the first-line treatment of acute uncomplicated cystitis in patients who cannot tolerate sulfonamides or TMP, who live in geographic areas with known resistance >10% to 20% to TMP-SMX, or who have risk factors for such resistance. Fluoroquinolone properties include a broad spectrum of coverage, low rates of resistance, and good safety profiles.

Disparities in location of death of adolescents and young adults with cancer: A longitudinal, population study in California.

PubMed

Rajeshuni, Nitya; Johnston, Emily E; Saynina, Olga; Sanders, Lee M; Chamberlain, Lisa J

2017-11-01

Patients with a terminal illness should have access to their chosen location of death. Cancer is the leading cause of non-accidental death among adolescents and young adults (AYAs; those aged 15-39 years). Although surveys have suggested that a majority of these patients prefer a home death, to the authors' knowledge, little is known regarding their barriers to accessing their preferred location of death. As a first step, the authors sought to determine, across a large population, 20-year trends in the location of death among AYA patients with cancer. Using the Vital Statistics Death Certificate Database of the California Office of Statewide Health Planning and Development, the authors performed a retrospective, population-based analysis of California patients with cancer aged 15 to 39 years who died between 1989 and 2011. Sociodemographic and clinical factors associated with hospital death were examined using multivariable logistic regression. Of 30,573 AYA oncology decedents, 57% died in a hospital, 33% died at home, and 10% died in other locations (eg, hospice facility or nursing facility). Between 1989 and 1994, hospital death rates decreased from 68.3% to 53.6% and at-home death rates increased from 16.8% to 35.5%. Between 1995 and 2011, these rates were stable. Those individuals who were more likely to die in a hospital were those aged <30 years, of minority race, of Hispanic ethnicity, who lived ≤10 miles from a specialty center, and who had a diagnosis of leukemia or lymphoma. Overall, the majority of AYA cancer deaths occurred in a hospital, with a 5-year shift to more in-home deaths that abated after 1995. In-hospital deaths were more common among younger patients, patients of minority race/ethnicities, and those with a leukemia or lymphoma diagnosis. Further study is needed to determine whether these rates and disparities are consistent with patient preferences. Cancer 2017;123:4178-4184. © 2017 American Cancer Society. © 2017 American Cancer Society.

Kinetic dissection of individual steps in the poly(C)-directed oligoguanylate synthesis from guanosine 5'-monophosphate 2-methylimidazolide

NASA Technical Reports Server (NTRS)

Kanavarioti, A.; Bernasconi, C. F.; Alberas, D. J.; Baird, E. E.

1993-01-01

A kinetic study of oligoguanylate synthesis on a polycytidylate template, poly(C), as a function of the concentration of the activated monomer, guanosine 5'-monophosphate 2-methylimidazolide, 2-MeImpG, is reported. Reactions were run with 0.005-0.045 M 2-MeImpG in the presence of 0.05 M poly(C) at 23 degrees C. The kinetic results are consistent with a reaction scheme (eq 1) that consists of a series of consecutive steps, each step representing the addition of one molecule of 2-MeImpG to the growing oligomer. This scheme allows the calculation of second-order rate constants for every step by analyzing the time-dependent growth of each oligomer. Computer simulations of the course of reaction based on the determined rate constants and eq 1 are in excellent agreement with the product distributions seen in the HPLC profiles. In accord with an earlier study (Fakhrai, H.; Inoue, T.; Orgel, L. E. Tetrahedron 1984, 40, 39), rate constants, ki, for the formation of the tetramer and longer oligomers up to the 16-mer were found to be independent of length and somewhat higher than k3 (formation of trimer), which in turn is much higher than k2 (formation of dimer). The ki (i > or = 4), k3, and k2 values are not true second-order rate constants but vary with monomer concentration. Mechanistic models for the dimerization (Scheme I) and elongation reactions (Scheme II) are proposed that are consistent with our results. These models take into account that the monomer associates with the template in a cooperative manner. Our kinetic analysis allowed the determination of rate constants for the elementary processes of covalent bond formation between two monomers (dimerization) and between an oligomer and a monomer (elongation) on the template. A major conclusion from our study is that bond formation between two monomer units or between a primer and a monomer is assisted by the presence of additional next-neighbor monomer units. This is consistent with recent findings with hairpin oligonucleotides (Wu, T.; Orgel, L. E. J. Am. Chem. Soc. 1992, 114, 317). Our study is the first of its kind that shows the feasibility of a thorough kinetic analysis of a template-directed oligomerization and provides a detailed mechanistic model of these reactions.

Transhepatic Hilar Approach for Perihilar Cholangiocarcinoma: Significance of Early Judgment of Resectability and Safe Vascular Reconstruction.

PubMed

Kuriyama, Naohisa; Isaji, Shuji; Tanemura, Akihiro; Iizawa, Yusuke; Kato, Hiroyuki; Murata, Yasuhiro; Azumi, Yoshinori; Kishiwada, Masashi; Mizuno, Shugo; Usui, Masanobu; Sakurai, Hiroyuki

2017-03-01

In the most common surgical procedure for perihilar cholangiocarcinoma, the margin status of the proximal bile duct is determined at the final step. Our procedure, the transhepatic hilar approach, confirms a cancer-negative margin status of the proximal bile duct first. We first performed a partial hepatic parenchymal transection to expose the hilar plate, and then transected the proximal bile duct to confirm margin status. Then, divisions of the hepatic artery and portal vein of the future resected liver are performed, followed by the residual hepatic parenchymal transection. The transhepatic hilar approach offers a wide surgical field for safe resection and reconstruction of the portal vein in the middle of the hepatectomy. We reviewed 23 patients with perihilar cholangiocarcinoma who underwent major hepatectomy using our procedure from 2011 to 2015. A combined vascular resection and reconstruction was carried out in 14 patients (60.9%). R0 resection was achieved in 17 patients (73.9%), and the overall 3-year survival rate was 52.9% (median survival time 52.4 months). The transhepatic hilar approach is useful and practicable regardless of local tumor extension, enabling us to determine tumor resectability and perform safe resection and reconstruction of the portal vein early in the operation.

Verification of the Solar Dynamics Observatory High Gain Antenna Pointing Algorithm Using Flight Data

NASA Technical Reports Server (NTRS)

Bourkland, Kristin L.; Liu, Kuo-Chia

2011-01-01

The Solar Dynamics Observatory (SDO), launched in 2010, is a NASA-designed spacecraft built to study the Sun. SDO has tight pointing requirements and instruments that are sensitive to spacecraft jitter. Two High Gain Antennas (HGAs) are used to continuously send science data to a dedicated ground station. Preflight analysis showed that jitter resulting from motion of the HGAs was a cause for concern. Three jitter mitigation techniques were developed and implemented to overcome effects of jitter from different sources. These mitigation techniques include: the random step delay, stagger stepping, and the No Step Request (NSR). During the commissioning phase of the mission, a jitter test was performed onboard the spacecraft, in which various sources of jitter were examined to determine their level of effect on the instruments. During the HGA portion of the test, the jitter amplitudes from the single step of a gimbal were examined, as well as the amplitudes due to the execution of various gimbal rates. The jitter levels were compared with the gimbal jitter allocations for each instrument. The decision was made to consider implementing two of the jitter mitigating techniques on board the spacecraft: stagger stepping and the NSR. Flight data with and without jitter mitigation enabled was examined, and it is shown in this paper that HGA tracking is not negatively impacted with the addition of the jitter mitigation techniques. Additionally, the individual gimbal steps were examined, and it was confirmed that the stagger stepping and NSRs worked as designed. An Image Quality Test was performed to determine the amount of cumulative jitter from the reaction wheels, HGAs, and instruments during various combinations of typical operations. The HGA-induced jitter on the instruments is well within the jitter requirement when the stagger step and NSR mitigation options are enabled.

Calculation of trajectories and the rate of growth of curvilinear fatigue cracks in isotropic and composite plates

NASA Astrophysics Data System (ADS)

Pokhmurska, H.; Maksymovych, O.; Dzyubyk, A.; Dzyubyk, L.

2018-06-01

The methods of calculating the trajectories and the rate of growth of curvilinear fatigue cracks in isotropic and composite plate structure elements during cyclic loading along straight or curvilinear trajectories are developed. For isotropic and anisotropic materials, the methodes are developed on the basis of the force criterion of destruction with the additional application of the fatigue fracture diagrams. To find the change in the shape of the cracks in the loading process, the step-by-step method was used. At each stage, the direction of the growth of all vertices of cracks and the lengths of their arcs was found on the basis of determining the intensity coefficients of stresses by the method of singular integral equations. The results of calculations of the cracks system growth process are presented.

Identifying pleiotropic genes in genome-wide association studies from related subjects using the linear mixed model and Fisher combination function.

PubMed

Yang, James J; Williams, L Keoki; Buu, Anne

2017-08-24

A multivariate genome-wide association test is proposed for analyzing data on multivariate quantitative phenotypes collected from related subjects. The proposed method is a two-step approach. The first step models the association between the genotype and marginal phenotype using a linear mixed model. The second step uses the correlation between residuals of the linear mixed model to estimate the null distribution of the Fisher combination test statistic. The simulation results show that the proposed method controls the type I error rate and is more powerful than the marginal tests across different population structures (admixed or non-admixed) and relatedness (related or independent). The statistical analysis on the database of the Study of Addiction: Genetics and Environment (SAGE) demonstrates that applying the multivariate association test may facilitate identification of the pleiotropic genes contributing to the risk for alcohol dependence commonly expressed by four correlated phenotypes. This study proposes a multivariate method for identifying pleiotropic genes while adjusting for cryptic relatedness and population structure between subjects. The two-step approach is not only powerful but also computationally efficient even when the number of subjects and the number of phenotypes are both very large.

BEARKIMPE-2: A VBA Excel program for characterizing granular iron in treatability studies

NASA Astrophysics Data System (ADS)

Firdous, R.; Devlin, J. F.

2014-02-01

The selection of a suitable kinetic model to investigate the reaction rate of a contaminant with granular iron (GI) is essential to optimize the permeable reactive barrier (PRB) performance in terms of its reactivity. The newly developed Kinetic Iron Model (KIM) determines the surface rate constant (k) and sorption parameters (Cmax &J) which were not possible to uniquely identify previously. The code was written in Visual Basic (VBA), within Microsoft Excel, was adapted from earlier command line FORTRAN codes, BEARPE and KIMPE. The program is organized with several user interface screens (UserForms) that guide the user step by step through the analysis. BEARKIMPE-2 uses a non-linear optimization algorithm to calculate transport and chemical kinetic parameters. Both reactive and non-reactive sites are considered. A demonstration of the functionality of BEARKIMPE-2, with three nitroaromatic compounds showed that the differences in reaction rates for these compounds could be attributed to differences in their sorption behavior rather than their propensities to accept electrons in the reduction process.

Pressure-dependent decomposition kinetics of the energetic material HMX up to 3.6 GPa.

PubMed

Glascoe, Elizabeth A; Zaug, Joseph M; Burnham, Alan K

2009-12-03

The effect of pressure on the global thermal decomposition rate of the energetic material HMX was studied. HMX was precompressed in a diamond anvil cell (DAC) and heated at various rates. The parent species population was monitored as a function of time and temperature using Fourier transform infrared (FTIR) spectroscopy. Global decomposition rates were determined by fitting the fraction reacted to the extended-Prout-Tompkins nucleation-growth model and the Friedman isoconversional method. The results of these experiments and analysis indicate that pressure accelerates the decomposition at low-to-moderate pressures (i.e., between ambient pressure and 0.1 GPa) and decelerates the decomposition at higher pressures. The decomposition acceleration is attributed to pressure-enhanced autocatalysis, whereas the deceleration at high pressures is attributed to pressure-inhibiting bond homolysis step(s), which would result in an increase in volume. These results indicate that both the beta- and delta-polymorphs of HMX are sensitive to pressure in the thermally induced decomposition kinetics.

Mechanisms of ilmenite reduction and their impact on the design of effective reactor systems

NASA Technical Reports Server (NTRS)

Briggs, R. A.; Sacco, A.

1991-01-01

One of the first activities at a lunar base could be oxygen recovery from ilmenite (FeTiO3). Oxygen produced from lunar soils could be used to fuel transportation vehicles operating in near-earth space. The first step in developing a suitable reactor system for lunar operation is to determine the mechanisms and rates of oxygen removal from ilmenite. In-situ gravimetric measurements and microscopic examinations were used to determine the hydrogen reduction mechanisms of synthetic ilmenite discs between 823 to 1353 K. A shrinking core reaction model, modified to account for the growth of an iron film on the surface of discs, was capable of predicting experimentally observed conversion-time relationships. The observed reduction mechanism, kinetic rates, and associated activation energy established a base line from which comparisons could be made to improve oxygen yield and removal rates. One proposed technique to improve the rate and extent of oxygen removal was to preoxidize ilmenite. Preoxidation is commonly used during the reduction of ilmenite ores in the iron industry and has been employed for many years to lower operating temperatures and increase reduction rates. This technology could prove beneficial for oxygen production facilities on the Moon as less massive reactor vessels and/or less energy could be associated with a process including preoxidation. X ray diffraction and energy dispersive spectroscopy were utilized to follow the progression of ilmenite oxidation at 1123 and 1140 K and the reduction of pseudobrookite (Fe2TiO5) at 873 and 973 K. Structures formed during the progress of oxidation were related to the system's phase diagrams. Results indicated that after initially producing ilmenite-hematite solutions and rutile (TiO2), pseudobrookite was the end product of oxidation at all temperatures examined (1049 to 1273 K). Initial results from the reduction of pseudobrookite indicate a series of phases are produced including ferropseudobrookite (FeTi2O5), ulvospinel (Fe2TiO4), and ilmenite. Rates of pseudobrookite reduction were typically 50 to 200 times that of ilmenite.

Image analysis and mathematical modelling for the supervision of the dough fermentation process

NASA Astrophysics Data System (ADS)

Zettel, Viktoria; Paquet-Durand, Olivier; Hecker, Florian; Hitzmann, Bernd

2016-10-01

The fermentation (proof) process of dough is one of the quality-determining steps in the production of baking goods. Beside the fluffiness, whose fundaments are built during fermentation, the flavour of the final product is influenced very much during this production stage. However, until now no on-line measurement system is available, which can supervise this important process step. In this investigation the potential of an image analysis system is evaluated, that enables the determination of the volume of fermented dough pieces. The camera is moving around the fermenting pieces and collects images from the objects by means of different angles (360° range). Using image analysis algorithms the volume increase of individual dough pieces is determined. Based on a detailed mathematical description of the volume increase, which based on the Bernoulli equation, carbon dioxide production rate of yeast cells and the diffusion processes of carbon dioxide, the fermentation process is supervised. Important process parameters, like the carbon dioxide production rate of the yeast cells and the dough viscosity can be estimated just after 300 s of proofing. The mean percentage error for forecasting the further evolution of the relative volume of the dough pieces is just 2.3 %. Therefore, a forecast of the further evolution can be performed and used for fault detection.

A rapid and cost effective method for soil carbon mineralization under static incubations

USDA-ARS?s Scientific Manuscript database

Soil incubations with subsequent determination of carbon dioxide (CO2) are common soil assays used to estimate C mineralization rates and active organic C pools. Two common methods used to detect CO2 in laboratory incubations are gas chromatography (GC) and alkali absorption followed by titration (...

Tuning the reactivity of Fe(V)(O) toward C-H bonds at room temperature: effect of water.

PubMed

Singh, Kundan K; Tiwari, Mrityunjay k; Ghosh, Munmun; Panda, Chakadola; Weitz, Andrew; Hendrich, Michael P; Dhar, Basab B; Vanka, Kumar; Sen Gupta, Sayam

2015-02-16

The presence of an Fe(V)(O) species has been postulated as the active intermediate for the oxidation of both C-H and C═C bonds in the Rieske dioxygenase family of enzymes. Understanding the reactivity of these high valent iron-oxo intermediates, especially in an aqueous medium, would provide a better understanding of these enzymatic reaction mechanisms. The formation of an Fe(V)(O) complex at room temperature in an aqueous CH3CN mixture that contains up to 90% water using NaOCl as the oxidant is reported here. The stability of Fe(V)(O) decreases with increasing water concentration. We show that the reactivity of Fe(V)(O) toward the oxidation of C-H bonds, such as those in toluene, can be tuned by varying the amount of water in the H2O/CH3CN mixture. Rate acceleration of up to 60 times is observed for the oxidation of toluene upon increasing the water concentration. The role of water in accelerating the rate of the reaction has been studied using kinetic measurements, isotope labeling experiments, and density functional theory (DFT) calculations. A kinetic isotope effect of ∼13 was observed for the oxidation of toluene and d8-toluene showing that C-H abstraction was involved in the rate-determining step. Activation parameters determined for toluene oxidation in H2O/CH3CN mixtures on the basis of Eyring plots for the rate constants show a gain in enthalpy with a concomitant loss in entropy. This points to the formation of a more-ordered transition state involving water molecules. To further understand the role of water, we performed a careful DFT study, concentrating mostly on the rate-determining hydrogen abstraction step. The DFT-optimized structure of the starting Fe(V)(O) and the transition state indicates that the rate enhancement is due to the transition state's favored stabilization over the reactant due to enhanced hydrogen bonding with water.

Collection of social determinants of health in the community clinic setting: a cross-sectional study.

PubMed

Kusnoor, Sheila V; Koonce, Taneya Y; Hurley, Suzanne T; McClellan, Kalonji M; Blasingame, Mallory N; Frakes, Elizabeth T; Huang, Li-Ching; Epelbaum, Marcia I; Giuse, Nunzia B

2018-04-24

Addressing social and behavioral determinants of health (SBDs) may help improve health outcomes of community clinic patients. This cross-sectional study explored how assessing SBDs can be used to complement health data collection strategies and provide clinicians with a more in-depth understanding of their patients. Adult patients, ages 18 and older, at an urban community health care clinic in Tennessee, U.S.A., were asked to complete a questionnaire regarding health status, health history and SBDs while waiting for their clinic appointment. The SBD component included items from the National Academy of Medicine, the Protocol for Responding to and Assessing Patient Assets, Risks, and Experiences instrument, and the Survey of Household Economics and Decisionmaking. Data collection and analysis occurred in 2017. One hundred participants completed the study. The questionnaire took approximately 11 min to complete, and the response rate was 90% or higher for all items except annual household income (unanswered by 40 participants). The median number of negative SBDs was 4 (IQR 2.75-7.0), 96 participants had at least one unmet need, and the most common negative SBD was physical activity (75%; 75/100). The hybrid questionnaire provided insight into a community clinic population's SBDs and allowed for a more complete understanding than a single questionnaire alone. The brief questionnaire administration time and low non-response rate support the questionnaire's feasibility in the community clinic setting, and results can be used by clinicians to further the personalization goals of precision medicine. Next steps include evaluating how to connect patients with appropriate resources for addressing their SBDs.

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

Volker, Arno; Hunter, Alan

Anisotropic materials are being used increasingly in high performance industrial applications, particularly in the aeronautical and nuclear industries. Some important examples of these materials are composites, single-crystal and heavy-grained metals. Ultrasonic array imaging in these materials requires exact knowledge of the anisotropic material properties. Without this information, the images can be adversely affected, causing a reduction in defect detection and characterization performance. The imaging operation can be formulated in two consecutive and reciprocal focusing steps, i.e., focusing the sources and then focusing the receivers. Applying just one of these focusing steps yields an interesting intermediate domain. The resulting common focusmore » point gather (CFP-gather) can be interpreted to determine the propagation operator. After focusing the sources, the observed travel-time in the CFP-gather describes the propagation from the focus point to the receivers. If the correct propagation operator is used, the measured travel-times should be the same as the time-reversed focusing operator due to reciprocity. This makes it possible to iteratively update the focusing operator using the data only and allows the material to be imaged without explicit knowledge of the anisotropic material parameters. Furthermore, the determined propagation operator can also be used to invert for the anisotropic medium parameters. This paper details the proposed technique and demonstrates its use on simulated array data from a specimen of Inconel single-crystal alloy commonly used in the aeronautical and nuclear industries.« less

Mechanistic Study of the Oxidative Coupling of Styrene with 2-Phenylpyridine Derivatives Catalyzed by Cationic Rhodium( III) via C–H Activation

PubMed Central

Brasse, Mikaël; Cámpora, Juan; Ellman, Jonathan A.; Bergman, Robert G.

2013-01-01

The Rh(III) catalyzed oxidative coupling of alkenes with arenes provides a greener alternative to the classical Heck reaction for the synthesis of arene-functionalized alkenes. The present mechanistic study gives insights for the rational development of this key transformation. The catalyst resting states and the rate law of the reaction have been identified. The reaction rate is solely dependent on catalyst and alkene concentrations and the rate determining step is the migratory insertion of alkene into a Rh–C(aryl) bond. PMID:23590843

Performance efficiency of feed utilization, relative growth rate, and survival rate of common carp (Cyprinus carpio) through the addition of phytase in the feed

NASA Astrophysics Data System (ADS)

Rachmawati, D.; Samidjan, I.

2018-04-01

The purpose of this study was to determine the effect of adding phytase enzyme in the feed on digestibility of feed, efficiency of feed utilization, relative growth rate and survival rate of Common carp (Cyprinus carpio). Fish samples in this research were Common carp with an average - weight of 3.34 ± 0,16 g/fish. The treatments were adding the phytase enzyme in the feed with the different level of doses. Those were A (0 U kg-1 feed), B (500 U kg-1 feed), C (1.000 U kg-1 feed g) and D (1.500 U kg-1 feed). Observation was conducted on digestibility of protein (ADCP), digestibility of phosphor (ADCF), efficiency of feed utilization (EFU), relative growth rate (RGR), protein efficiency ratio (PER), feed conversion ratio (FCR), survival rate (SR) and water quality parameters. The results show that the addition of phytase enzyme significantly (P<0.01) affected on ADCP, ADCF, EFU, RGR, FCR, and PER, on the other hand it insignificantly (P>0.05) affected on SR of common carp. Based on results, it was concluded that optimum doses of phytase enzyme feed in terms of digestibility of feed, efficiency utilization of Feed and growth rate of Common carp ranges from 943 to 1100 U kg-1 feed

DFT investigations of phosphotriesters hydrolysis in aqueous solution: a model for DNA single strand scission induced by N-nitrosoureas.

PubMed

Liu, Tingting; Zhao, Lijiao; Zhong, Rugang

2013-02-01

DNA phosphotriester adducts are common alkylation products of DNA phosphodiester moiety induced by N-nitrosoureas. The 2-hydroxyethyl phosphotriester was reported to hydrolyze more rapidly than other alkyl phosphotriesters both in neutral and in alkaline conditions, which can cause DNA single strand scission. In this work, DFT calculations have been employed to map out the four lowest activation free-energy profiles for neutral and alkaline hydrolysis of triethyl phosphate (TEP) and diethyl 2-hydroxyethyl phosphate (DEHEP). All the hydrolysis pathways were illuminated to be stepwise involving an acyclic or cyclic phosphorane intermediate for TEP or DEHEP, respectively. The rate-limiting step for all the hydrolysis reactions was found to be the formation of phosphorane intermediate, with the exception of DEHEP hydrolysis in alkaline conditions that the decomposition process turned out to be the rate-limiting step, owing to the extraordinary low formation barrier of cyclic phosphorane intermediate catalyzed by hydroxide. The rate-limiting barriers obtained for the four reactions are all consistent with the available experimental information concerning the corresponding hydrolysis reactions of phosphotriesters. Our calculations performed on the phosphate triesters hydrolysis predict that the lower formation barriers of cyclic phosphorane intermediates compared to its acyclic counter-part should be the dominant factor governing the hydrolysis rate enhancement of DEHEP relative to TEP both in neutral and in alkaline conditions.

[Prospective assessment of medication errors in critically ill patients in a university hospital].

PubMed

Salazar L, Nicole; Jirón A, Marcela; Escobar O, Leslie; Tobar, Eduardo; Romero, Carlos

2011-11-01

Critically ill patients are especially vulnerable to medication errors (ME) due to their severe clinical situation and the complexities of their management. To determine the frequency and characteristics of ME and identify shortcomings in the processes of medication management in an Intensive Care Unit. During a 3 months period, an observational prospective and randomized study was carried out in the ICU of a university hospital. Every step of patient's medication management (prescription, transcription, dispensation, preparation and administration) was evaluated by an external trained professional. Steps with higher frequency of ME and their therapeutic groups involved were identified. Medications errors were classified according to the National Coordinating Council for Medication Error Reporting and Prevention. In 52 of 124 patients evaluated, 66 ME were found in 194 drugs prescribed. In 34% of prescribed drugs, there was at least 1 ME during its use. Half of ME occurred during medication administration, mainly due to problems in infusion rates and schedule times. Antibacterial drugs had the highest rate of ME. We found a 34% rate of ME per drug prescribed, which is in concordance with international reports. The identification of those steps more prone to ME in the ICU, will allow the implementation of an intervention program to improve the quality and security of medication management.

Possible Mechanism for Modulating Cardiovascular System During Running in Humans

DTIC Science & Technology

2001-10-25

odulated by rhythmic muscle contractions during running. It cillates when step rate and heart rate are not synchronised but abilises when they are... synchronised . A maximum cardiac output n be achieved by synchronising step rate with heart rate at an timal phase delay. eywords – Cardiovascular model...trained athletes. Researches from [3][4][5] suggest at synchronization between the heart rate and the step rate uring running may favor an athlete with

Factors affecting initial disability allowance rates for the Disability Insurance and Supplemental Security Income programs: the role of the demographic and diagnostic composition of applicants and local labor market conditions.

PubMed

Rupp, Kalman

2012-01-01

Various factors outside the control of decision makers may affect the rate at which disability applications are allowed or denied during the initial step of eligibility determination in the Social Security Disability Insurance (DI) and Supplemental Security Income (SSI) programs. In this article, using individual-level data on applications, I estimate the role of three important factors--the demographic characteristics of applicants, the diagnostic mix of applicants, and the local unemployment rate--in affecting the probability of an initial allowance and state allowance rates. I use a random sample of initial determinations from 1993 through 2008 and a fixed-effects multiple regression framework. The empirical results show that the demographic and diagnostic characteristics of applicants and the local unemployment rate substantially affect the initial allowance rate. An increase in the local unemployment rate tends to be associated with a decrease in the initial allowance rate. This negative relationship holds for adult DI and SSI applicants and for SSI childhood applicants.

Therapist Competence in Global Mental Health: Development of the Enhancing Assessment of Common Therapeutic Factors (ENACT) Rating Scale

PubMed Central

Kohrt, Brandon A.; Jordans, Mark J.D.; Rai, Sauharda; Shrestha, Pragya; Luitel, Nagendra P.; Ramaiya, Megan; Singla, Daisy; Patel, Vikram

2015-01-01

Lack of reliable and valid measures of therapist competence is a barrier to dissemination and implementation of psychological treatments in global mental health. We developed the ENhancing Assessment of Common Therapeutic factors (ENACT) rating scale for training and supervision across settings varied by culture and access to mental health resources. We employed a four-step process in Nepal: (1) Item generation: We extracted 1,081 items (grouped into 104 domains) from 56 existing tools; role-plays with Nepali therapists generated 11 additional domains. (2) Item relevance: From the 115 domains, Nepali therapists selected 49 domains of therapeutic importance and high comprehensibility. (3) Item utility: We piloted the ENACT scale through rating role-play videotapes, patient session transcripts, and live observations of primary care workers in trainings for psychological treatments and the Mental Health Gap Action Programme (mhGAP). (4) Inter-rater reliability was acceptable for experts (intraclass correlation coefficient, ICC(2,7)=0.88 (95% confidence interval (CI) 0.81—0.93), N=7) and non-specialists (ICC(1,3)=0.67 (95% CI 0.60—0.73), N=34). In sum, the ENACT scale is an 18-item assessment for common factors in psychological treatments, including task-sharing initiatives with non-specialists across cultural settings. Further research is needed to evaluate applications for therapy quality and association with patient outcomes. PMID:25847276

Atomic-Scale Design of Iron Fischer-Tropsch Catalysts; A Combined Computational Chemistry, Experimental, and Microkinetic Modeling Approach

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

Manos Mavrikakis; James Dumesic; Rahul Nabar

2008-09-29

This work focuses on (1) searching/summarizing published Fischer-Tropsch synthesis (FTS) mechanistic and kinetic studies of FTS reactions on iron catalysts; (2) preparation and characterization of unsupported iron catalysts with/without potassium/platinum promoters; (3) measurement of H{sub 2} and CO adsorption/dissociation kinetics on iron catalysts using transient methods; (3) analysis of the transient rate data to calculate kinetic parameters of early elementary steps in FTS; (4) construction of a microkinetic model of FTS on iron, and (5) validation of the model from collection of steady-state rate data for FTS on iron catalysts. Three unsupported iron catalysts and three alumina-supported iron catalysts weremore » prepared by non-aqueous-evaporative deposition (NED) or aqueous impregnation (AI) and characterized by chemisorption, BET, temperature-programmed reduction (TPR), extent-of-reduction, XRD, and TEM methods. These catalysts, covering a wide range of dispersions and metal loadings, are well-reduced and relatively thermally stable up to 500-600 C in H{sub 2} and thus ideal for kinetic and mechanistic studies. Kinetic parameters for CO adsorption, CO dissociation, and surface carbon hydrogenation on these catalysts were determined from temperature-programmed desorption (TPD) of CO and temperature programmed surface hydrogenation (TPSR), temperature-programmed hydrogenation (TPH), and isothermal, transient hydrogenation (ITH). A microkinetic model was constructed for the early steps in FTS on polycrystalline iron from the kinetic parameters of elementary steps determined experimentally in this work and from literature values. Steady-state rate data were collected in a Berty reactor and used for validation of the microkinetic model. These rate data were fitted to 'smart' Langmuir-Hinshelwood rate expressions derived from a sequence of elementary steps and using a combination of fitted steady-state parameters and parameters specified from the transient measurements. The results provide a platform for further development of microkinetic models of FTS on Fe and a basis for more precise modeling of FTS activity of Fe catalysts. Calculations using periodic, self-consistent Density Functional Theory (DFT) methods were performed on various realistic models of industrial, Fe-based FTS catalysts. Close-packed, most stable Fe(110) facet was analyzed and subsequently carbide formation was found to be facile leading to the choice of the FeC(110) model representing a Fe facet with a sub-surface C atom. The Pt adatom (Fe{sup Pt}(110)) was found to be the most stable model for our studies into Pt promotion and finally the role of steps was elucidated by recourse to the defected Fe(211) facet. Binding Energies(BEs), preferred adsorption sites and geometries for all FTS relevant stable species and intermediates were evaluated on each model catalyst facet. A mechanistic model (comprising of 32 elementary steps involving 19 species) was constructed and each elementary step therein was fully characterized with respect to its thermochemistry and kinetics. Kinetic calculations involved evaluation of the Minimum Energy Pathways (MEPs) and activation energies (barriers) for each step. Vibrational frequencies were evaluated for the preferred adsorption configuration of each species with the aim of evaluating entropy-changes, pre exponential factors and serving as a useful connection with experimental surface science techniques. Comparative analysis among these four facets revealed important trends in their relative behavior and roles in FTS catalysis. Overall the First Principles Calculations afforded us a new insight into FTS catalysis on Fe and modified-Fe catalysts.« less

Molecular mechanisms of cryptococcal meningitis

PubMed Central

Liu, Tong-Bao; Perlin, David; Xue, Chaoyang

2012-01-01

Fungal meningitis is a serious disease caused by a fungal infection of the central nervous system (CNS) mostly in individuals with immune system deficiencies. Fungal meningitis is often fatal without proper treatment, and the mortality rate remains unacceptably high even with antifungal drug interventions. Currently, cryptococcal meningitis is the most common fungal meningitis in HIV-1/AIDS, and its disease mechanism has been extensively studied. The key steps for fungi to infect brain and cause meningitis after establishment of local infection are the dissemination of fungal cells to the bloodstream and invasion through the blood brain barrier to reach the CNS. In this review, we use cryptococcal CNS infection as an example to describe the current molecular understanding of fungal meningitis, including the establishment of the infection, dissemination, and brain invasion. Host and microbial factors that contribute to these infection steps are also discussed. PMID:22460646

Modeling on-column reduction of trisulfide bonds in monoclonal antibodies during protein A chromatography.

PubMed

Ghose, Sanchayita; Rajshekaran, Rupshika; Labanca, Marisa; Conley, Lynn

2017-01-06

Trisulfides can be a common post-translational modification in many recombinant monoclonal antibodies. These are a source of product heterogeneity that add to the complexity of product characterization and hence, need to be reduced for consistent product quality. Trisulfide bonds can be converted to the regular disulfide bonds by incorporating a novel cysteine wash step during Protein A affinity chromatography. An empirical model is developed for this on-column reduction reaction to compare the reaction rates as a function of typical operating parameters such as temperature, cysteine concentration, reaction time and starting level of trisulfides. The model presented here is anticipated to assist in the development of optimal wash conditions for the Protein A step to effectively reduce trisulfides to desired levels. Copyright © 2016 Elsevier B.V. All rights reserved.

Improvement of bench life-tests for automotive batteries

NASA Astrophysics Data System (ADS)

Richter, G.

A common method for rating the endurance of automotive batteries is the bench life-test according to DIN, IEC, SAE or JIS. With an increasing number of maintenance-free batteries on the market, the application of these tests becomes more problematic. This is due to a step-by-step capacity decline during cycling if the content of autimony in the grid-alloy is decreased. The degradation in performance is caused by the phenomenon of acid stratification. Because this debilitating effect occurs only rarely in service (vehicle movement) if charging and discharging is well balanced, there is a need for a new bench life-test with conditions that are more representative of practical conditions. Research has shown that the main changes should be: (i) an accelerated (moved) battery during cycling; (ii) slightly lower charging or discharging capacity amplitude, also with a lower mean value.

Ab Initio ONIOM-Molecular Dynamics (MD) Study on the Deamination Reaction by Cytidine Deaminase

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

Matsubara, Toshiaki; Dupuis, Michel; Aida, Misako

2007-08-23

We applied the ONIOM-molecular dynamics (MD) method to the hydrolytic deamination of cytidine by cytidine deaminase, which is an essential step of the activation process of the anticancer drug inside the human body. The direct MD simulations were performed for the realistic model of cytidine deaminase calculating the energy and its gradient by the ab initio ONIOM method on the fly. The ONIOM-MD calculations including the thermal motion show that the neighboring amino acid residue is an important factor of the environmental effects and significantly affects not only the geometry and energy of the substrate trapped in the pocket ofmore » the active site but also the elementary step of the catalytic reaction. We successfully simulate the second half of the catalytic cycle, which has been considered to involve the rate-determining step, and reveal that the rate-determing step is the release of the NH3 molecule. TM and MA were supported in part by grants from the Ministry of Education, Culture, Sports, Science and Technology of Japan. MD was supported by the Division of Chemical Sciences, Office of Basic Energy Sciences, and by the Office of Biological and Environmental Research of the U.S. Department of Energy DOE. Battelle operates Pacific Northwest National Laboratory for DOE.« less

Automation and Optimization of Multipulse Laser Zona Drilling of Mouse Embryos During Embryo Biopsy.

PubMed

Wong, Christopher Yee; Mills, James K

2017-03-01

Laser zona drilling (LZD) is a required step in many embryonic surgical procedures, for example, assisted hatching and preimplantation genetic diagnosis. LZD involves the ablation of the zona pellucida (ZP) using a laser while minimizing potentially harmful thermal effects on critical internal cell structures. Develop a method for the automation and optimization of multipulse LZD, applied to cleavage-stage embryos. A two-stage optimization is used. The first stage uses computer vision algorithms to identify embryonic structures and determines the optimal ablation zone farthest away from critical structures such as blastomeres. The second stage combines a genetic algorithm with a previously reported thermal analysis of LZD to optimize the combination of laser pulse locations and pulse durations. The goal is to minimize the peak temperature experienced by the blastomeres while creating the desired opening in the ZP. A proof of concept of the proposed LZD automation and optimization method is demonstrated through experiments on mouse embryos with positive results, as adequately sized openings are created. Automation of LZD is feasible and is a viable step toward the automation of embryo biopsy procedures. LZD is a common but delicate procedure performed by human operators using subjective methods to gauge proper LZD procedure. Automation of LZD removes human error to increase the success rate of LZD. Although the proposed methods are developed for cleavage-stage embryos, the same methods may be applied to most types LZD procedures, embryos at different developmental stages, or nonembryonic cells.

5 CFR 531.405 - Waiting periods for within-grade increase.

Code of Federal Regulations, 2011 CFR

2011-01-01

... step 4-260 days of creditable service in a pay status over a period of not less than 52 calendar weeks... step 4-52 calendar weeks of creditable service; (ii) Rate of basic pay equal to or greater than the rate of basic pay at step 4 and less than the rate of basic pay at step 7-104 calendar weeks of...

Determining the rate of value increase for oaks

Treesearch

Paul S. DeBald; Joseph J. Mendel

1971-01-01

A method used to develop rate of value increase is described as an aid to management decision-making. Regional rates of value increase and financial maturity diameters for ten species common to the oak-hickory type are outlined, and the economic principles involved are explained to show how they apply to either individual trees or stands.

Novel guanidine-based inhibitors of inosine monophosphate dehydrogenase.

PubMed

Iwanowicz, Edwin J; Watterson, Scott H; Liu, Chunjian; Gu, Henry H; Mitt, Toomas; Leftheris, Katerina; Barrish, Joel C; Fleener, Catherine A; Rouleau, Katherine; Sherbina, N Z; Hollenbaugh, Diane L

2002-10-21

A series of novel guanidine-based small molecule inhibitors of inosine monophosphate dehydrogenase (IMPDH) was explored. IMPDH catalyzes the rate determining step in guanine nucleotide biosynthesis and is a target for anticancer, immunosuppressive and antiviral therapy. The synthesis and the structure-activity relationships (SARs), derived from in vitro studies, for this new series of inhibitors is given.

Effective Determination of Overhead Rates for Pricing Goods and Services.

ERIC Educational Resources Information Center

Smith, Christopher A.

This publication presents a system of gathering overhead data and describes several methods for assigning overhead costs to specific contract prices. It is intended to provide facility production supervisors with a means of ensuring adequate cost recovery in bid prices and gaining a measure of overhead cost control. The seven steps in the overhead…

76 FR 22324 - Energy Conservation Program: Energy Conservation Standards for Residential Clothes Dryers and...

Federal Register 2010, 2011, 2012, 2013, 2014

2011-04-21

...-step calculation process to convert the time- series of costs and benefits into annualized values... costs and savings, for the time-series of costs and benefits using discount rates of three and seven... that the time-series of costs and benefits from which the annualized values were determined would be a...

Making the Most of the "Daphnia" Heart Rate Lab: Optimizing the Use of Ethanol, Nicotine & Caffeine

ERIC Educational Resources Information Center

Corotto, Frank; Ceballos, Darrel; Lee, Adam; Vinson, Lindsey

2010-01-01

Students commonly test the effects of chemical agents on the heart rate of the crustacean "Daphnia" magna, but the procedure has never been optimized. We determined the effects of three concentrations of ethanol, nicotine, and caffeine and of a control solution on heart rate in "Daphnia." Ethanol at 5% and 10% (v/v) reduced mean heart rate to…

Are your students ready for anatomy and physiology? Developing tools to identify students at risk for failure.

PubMed

Gultice, Amy; Witham, Ann; Kallmeyer, Robert

2015-06-01

High failure rates in introductory college science courses, including anatomy and physiology, are common at institutions across the country, and determining the specific factors that contribute to this problem is challenging. To identify students at risk for failure in introductory physiology courses at our open-enrollment institution, an online pilot survey was administered to 200 biology students. The survey results revealed several predictive factors related to academic preparation and prompted a comprehensive analysis of college records of >2,000 biology students over a 5-yr period. Using these historical data, a model that was 91% successful in predicting student success in these courses was developed. The results of the present study support the use of surveys and similar models to identify at-risk students and to provide guidance in the development of evidence-based advising programs and pedagogies. This comprehensive approach may be a tangible step in improving student success for students from a wide variety of backgrounds in anatomy and physiology courses. Copyright © 2015 The American Physiological Society.

Reactivity of food phenols with iron and copper ions: binding, dioxygen activation and oxidation mechanisms.

PubMed

Nkhili, Ezzohra; Loonis, Michèle; Mihai, Simona; El Hajji, Hakima; Dangles, Olivier

2014-06-01

In this work, the affinity of common dietary phenols (gallic acid, caffeic acid, catechin, and rutin) for iron and copper ions was quantitatively investigated in neutral phosphate buffer as well as the reactivity of the complexes toward dioxygen. Contrasting behaviors were observed: because of the competing phosphate ions, Fe(III) binding is much slower than Fe(II) binding, which is rapidly followed by autoxidation of Fe(II) into Fe(III). With both ions, O2 consumption and H2O2 production are modest and the phenolic ligands are only slowly oxidized. By contrast, metal-phenol binding is fast with both Cu(I) and Cu(II). With Cu(I), O2 consumption and H2O2 production are very significant and the phenolic ligands are rapidly oxidized into a complex mixture of oligomers. The corresponding mechanism with Cu(II) is hampered by the preliminary rate-determining step of Cu(II) reduction by the phenols. The consequences of these findings for the stability and antioxidant activity of plant phenols are discussed.

Finding the missing link between ictal bradyarrhythmia, ictal asystole, and sudden unexpected death in epilepsy.

PubMed

Leung, H; Kwan, P; Elger, C E

2006-08-01

Basic science studies of the human brain have supported the cortical representation of cardiovascular responses, including heart rate variability. Clinical observations of ictal bradyarrhythmia may be mechanistically explained by the influence of the central autonomic network, although the localization and lateralization issues need to be considered in the light of patterns of seizure spread, hand dominance, and presence of lesions. Ictal bradyarrhythmia also offers a mechanistic explanation of sudden unexpected death in epilepsy (SUDEP), though it may explain only some but not all cases of SUDEP. The missing links are (1) clinical evidence of common factors shared by patients with ictal bradyarrhythmia and patients who die from SUDEP, (2) evidence of arrhythmia as a risk factor for SUDEP from epidemiological studies, and, (3) determination of the importance of ictal bradyarrhythmia in SUDEP with respect to other proposed mechanisms including apnea and intrinsic cardiac abnormalities. There remains a need to review the seizure mechanisms in cases of SUDEP and to step up the amount of concurrent ECG/intracranial EEG analysis in both ictal bradyarrhythmia and SUDEP cases.

Pyrolysis reaction models of waste tires: Application of Master-Plots method for energy conversion via devolatilization.

PubMed

Irmak Aslan, Dilan; Parthasarathy, Prakash; Goldfarb, Jillian L; Ceylan, Selim

2017-10-01

Land applied disposal of waste tires has far-reaching environmental, economic, and human health consequences. Pyrolysis represents a potential waste management solution, whereby the solid carbonaceous residue is heated in the absence of oxygen to produce liquid and gaseous fuels, and a solid char. The design of an efficient conversion unit requires information on the reaction kinetics of pyrolysis. This work is the first to probe the appropriate reaction model of waste tire pyrolysis. The average activation energy of pyrolysis was determined via iso-conversional methods over a mass fraction conversion range between 0.20 and 0.80 to be 162.8±23.2kJmol -1 . Using the Master Plots method, a reaction order of three was found to be the most suitable model to describe the pyrolytic decomposition. This suggests that the chemical reactions themselves (cracking, depolymerization, etc.), not diffusion or boundary layer interactions common with carbonaceous biomasses, are the rate-limiting steps in the pyrolytic decomposition of waste tires. Copyright © 2017 Elsevier Ltd. All rights reserved.

Social determinants of health and health equity policy research: exploring the use, misuse, and nonuse of policy analysis theory.

PubMed

Embrett, Mark G; Randall, G E

2014-05-01

Despite a dramatic growth in SDH/HE (social determinants of health/health equity) public policy research and demonstrated government interest in promoting equity in health policies, health inequities are actually growing among some populations and there is little evidence that "healthy public policies" are being adopted and implemented. Moreover, these issues are typically failing to even reach governments' policy agendas, which is a critical step towards serious debate and the identification of policy options. This systematic review pursues three main objectives. First, is to identify barriers to SDH/HE issues reaching the government policy agenda. Second, to evaluate the characteristics of peer-reviewed research articles that utilize common policy analysis theories. And third, to determine the extent to which the SDH/HE literature utilizes common policy analysis theories. Our systematic review, conducted in June 2012, identified 6200 SDH/HE related articles in the peer-reviewed literature; however, only seven articles explicitly used a commonly recognized policy analysis theory to inform their analysis. Our analysis revealed that the SDH/HE policy literature appears to be focused on advocacy rather than analysis and that the use of policy analysis theory is extremely limited. Our results also suggest that when such theories are incorporated into an analysis they are often not comprehensively employed. We propose explanations for this non-use and misuse of policy analysis theory, and conclude that researchers may have greater influence in helping to get SDH/HE issues onto government policy agendas if they gain a greater understanding of the policy process and the value of incorporating policy analysis theories into their research. Using a policy analysis lens to help identify why healthy public policies are typically not being adopted is an important step towards moving beyond advocacy to understanding and addressing some of the political barriers to reforms. Copyright © 2014 Elsevier Ltd. All rights reserved.

Reaction Mechanism of Organocatalytic Michael Addition of Nitromethane to Cinnamaldehyde: A Case Study on Catalyst Regeneration and Solvent Effects.

PubMed

Świderek, Katarzyna; Nödling, Alexander R; Tsai, Yu-Hsuan; Luk, Louis Y P; Moliner, Vicent

2018-01-11

The Michael addition of nitromethane to cinnamaldehyde has been computationally studied in the absence of a catalyst and the presence of a biotinylated secondary amine by a combined computational and experimental approach. The calculations were performed at the density functional theory (DFT) level with the M06-2X hybrid functional, and a polarizable continuum model has been employed to mimic the effect of two different solvents: dichloromethane (DCM) and water. Contrary to common assumption, the product-derived iminium intermediate was absent in both of the solvents tested. Instead, hydrating the C1-C2 double bond in the enamine intermediate directly yields the tetrahedral intermediate, which is key for forming the product and regenerating the catalyst. Enamine hydration is concerted and found to be rate-limiting in DCM but segregated into two non-rate-limiting steps when the solvent is replaced with water. However, further analysis revealed that the use of water as solvent also raises the energy barriers for other chemical steps, particularly the critical step of C-C bond formation between the iminium intermediate and nucleophile; this consequently lowers both the reaction yield and enantioselectivity of this LUMO-lowering reaction, as experimentally detected. These findings provide a logical explanation to why water often enhances organocatalysis when used as an additive but hampers the reaction progress when employed as a solvent.

Reaction Mechanism of Organocatalytic Michael Addition of Nitromethane to Cinnamaldehyde: A Case Study on Catalyst Regeneration and Solvent Effects

PubMed Central

2017-01-01

The Michael addition of nitromethane to cinnamaldehyde has been computationally studied in the absence of a catalyst and the presence of a biotinylated secondary amine by a combined computational and experimental approach. The calculations were performed at the density functional theory (DFT) level with the M06-2X hybrid functional, and a polarizable continuum model has been employed to mimic the effect of two different solvents: dichloromethane (DCM) and water. Contrary to common assumption, the product-derived iminium intermediate was absent in both of the solvents tested. Instead, hydrating the C1–C2 double bond in the enamine intermediate directly yields the tetrahedral intermediate, which is key for forming the product and regenerating the catalyst. Enamine hydration is concerted and found to be rate-limiting in DCM but segregated into two non-rate-limiting steps when the solvent is replaced with water. However, further analysis revealed that the use of water as solvent also raises the energy barriers for other chemical steps, particularly the critical step of C–C bond formation between the iminium intermediate and nucleophile; this consequently lowers both the reaction yield and enantioselectivity of this LUMO-lowering reaction, as experimentally detected. These findings provide a logical explanation to why water often enhances organocatalysis when used as an additive but hampers the reaction progress when employed as a solvent. PMID:29256614

Entry of Botulinum Neurotoxin Subtypes A1 and A2 into Neurons

PubMed Central

Kroken, Abby R.; Blum, Faith C.; Zuverink, Madison

2016-01-01

ABSTRACT Botulinum neurotoxins (BoNTs) are the most toxic proteins for humans but also are common therapies for neurological diseases. BoNTs are dichain toxins, comprising an N-terminal catalytic domain (LC) disulfide bond linked to a C-terminal heavy chain (HC) which includes a translocation domain (HN) and a receptor binding domain (HC). Recently, the BoNT serotype A (BoNT/A) subtypes A1 and A2 were reported to possess similar potencies but different rates of cellular intoxication and pathology in a mouse model of botulism. The current study measured HCA1 and HCA2 entry into rat primary neurons and cultured Neuro2A cells. We found that there were two sequential steps during the association of BoNT/A with neurons. The initial step was ganglioside dependent, while the subsequent step involved association with synaptic vesicles. HCA1 and HCA2 entered the same population of synaptic vesicles and entered cells at similar rates. The primary difference was that HCA2 had a higher degree of receptor occupancy for cells and neurons than HcA1. Thus, HCA2 and HCA1 share receptors and entry pathway but differ in their affinity for receptor. The initial interaction of HCA1 and HCA2 with neurons may contribute to the unique pathologies of BoNT/A1 and BoNT/A2 in mouse models. PMID:27795365

Theoretical studies on the Mo-catalyzed asymmetric intramolecular Pauson-Khand-type [2+2+1] cycloadditions of 3-allyloxy-1-propynylphosphonates.

PubMed

Meng, Qingxi; Li, Ming

2012-08-01

Density functional theory (DFT) was used to investigate the Mo-catalyzed intramolecular Pauson-Khand reaction of 3-allyloxy-1-propynylphosphonates. All intermediates and transition states were optimized completely at the B3LYP/6-31 G(d,p) level [LANL2DZ(f) for Mo]. In the Mo-catalyzed intramolecular Pauson-Khand reaction, the C–C oxidative cyclization reaction was the chirality-determining step, and the reductive elimination reaction was the rate-determining step. The carbonyl insertion reaction into the Mo–C(sp(3)) bondwas easier than into the Mo–C=C bond. And the dominant product predicted theoretically was of (S)-chirality, which agreed with experimental data. This reaction was solventd ependent, and toluene was the best among the three solvents toluene, CH3CN, and THF.

Determining next steps in a hand hygiene improvement initiative by examining variation in hand hygiene compliance rates.

PubMed

Homa, Karen; Kirkland, Kathryn B

2011-01-01

Health care worker hand hygiene (HH) is a major quality and safety concern since poor hand hygiene has been linked with hospital associated infections. Dartmouth-Hitchcock Medical Center has been involved in a 4-year initiative to improve hand hygiene. In 2006, HH compliance occurred 41% of the time and by 2009, it had improved to 91%. We wanted to understand some of the unexplained variability in HH to help determine where to target more specific strategies. To help determine where some of the variability in HH compliance rates occurred, an analysis of means chart was used to determine whether role type of the health care worker and hospital areas had significantly different HH rates compared with the overall HH rate. The overall HH rate between March 2008 and December 2009 was 87%. There was a wide and significant variation between the 16 groups of 2 types of health care workers in 8 hospital areas from the lowest rate of 64% to a high of 96%. Analysis of means revealed significant differences in HH rates relative to the type of worker and hospital areas. Although the method does not inform the organization of what type of intervention will work where and why, it allows high and low performing groups to be identified, so that organizations can learn from them to generate and test theories.

Genetic control of enhanced mutability of mitochondrial DNA and gamma-ray sensitivity in Saccharomyces cerevisiae.

PubMed Central

Foury, F; Goffeau, A

1979-01-01

Five nuclear mutants enhancing the spontaneous mutation rate of mtDNA have been isolated in Saccharomyces cerevisiae. These mutators fall into five complementation groups and are located at five genetic loci different from rad50 to rad57 loci. Three mutants (gam1, gam2, and gam4), insensitive or weakly sensitive to gamma-rays, exhibit increased frequency of spontaneous production of mutants with large deletions of the mtDNA (p-) and of all tested mitochondrial drug-resistant mutants. Two other mutants (gam3 and gam5), highly sensitive to gamma-rays, increase only the mutation rate of particular alleles of the mtDNA. The mutant gam5 enhances only the production of p- and erythromycin-resistant clones. The mutant gam3 exhibits an enhanced rate of oligomycin-resistant clones as well as a collateral increase of nuclear mutability. The existence of gam3 and gam5 mutants indicates that at least two common steps control both nuclear DNA repair and the mutability of particular alleles of the mtDNA. However, the general spontaneous mutability of the mtDNA includes at least three steps not involved in the repair of nuclear DNA, as revealed by the gam1, gam2, and gam4 mutations. PMID:392521

Evaluation of Second-Level Inference in fMRI Analysis

PubMed Central

Roels, Sanne P.; Loeys, Tom; Moerkerke, Beatrijs

2016-01-01

We investigate the impact of decisions in the second-level (i.e., over subjects) inferential process in functional magnetic resonance imaging on (1) the balance between false positives and false negatives and on (2) the data-analytical stability, both proxies for the reproducibility of results. Second-level analysis based on a mass univariate approach typically consists of 3 phases. First, one proceeds via a general linear model for a test image that consists of pooled information from different subjects. We evaluate models that take into account first-level (within-subjects) variability and models that do not take into account this variability. Second, one proceeds via inference based on parametrical assumptions or via permutation-based inference. Third, we evaluate 3 commonly used procedures to address the multiple testing problem: familywise error rate correction, False Discovery Rate (FDR) correction, and a two-step procedure with minimal cluster size. Based on a simulation study and real data we find that the two-step procedure with minimal cluster size results in most stable results, followed by the familywise error rate correction. The FDR results in most variable results, for both permutation-based inference and parametrical inference. Modeling the subject-specific variability yields a better balance between false positives and false negatives when using parametric inference. PMID:26819578

MEDEX2015: Greater Sea-Level Fitness Is Associated with Lower Sense of Effort During Himalayan Trekking Without Worse Acute Mountain Sickness.

PubMed

Rossetti, Gabriella M K; Macdonald, Jamie H; Smith, Matthew; Jackson, Anna R; Callender, Nigel; Newcombe, Hannah K; Storey, Heather M; Willis, Sebastian; van den Beukel, Jojanneke; Woodward, Jonathan; Pollard, James; Wood, Benjamin; Newton, Victoria; Virian, Jana; Haswell, Owen; Oliver, Samuel J

2017-06-01

Rossetti, Gabriella M.K., Jamie H. Macdonald, Matthew Smith, Anna R. Jackson, Nigel Callender, Hannah K. Newcombe, Heather M. Storey, Sebastian Willis, Jojanneke van den Beukel, Jonathan Woodward, James Pollard, Benjamin Wood, Victoria Newton, Jana Virian, Owen Haswell, and Samuel J. Oliver. MEDEX2015: Greater sea-level fitness is associated with lower sense of effort during Himalayan trekking without worse acute mountain sickness. High Alt Med Biol. 18:152-162, 2017.-This study examined the complex relationships of fitness and hypoxic sensitivity with submaximal exercise responses and acute mountain sickness (AMS) at altitude. Determining these relationships is necessary before fitness or hypoxic sensitivity tests can be recommended to appraise individuals' readiness for altitude. Forty-four trekkers (26 men; 18 women; 20-67 years) completed a loaded walking test and a fitness questionnaire in normoxia to measure and estimate sea-level maximal aerobic capacity (maximum oxygen consumption [[Formula: see text]O 2max ]), respectively. Participants also completed a hypoxic exercise test to determine hypoxic sensitivity (cardiac, ventilatory, and arterial oxygen saturation responses to acute hypoxia, fraction of inspired oxygen [Fio 2 ] = 0.112). One month later, all participants completed a 3-week trek to 5085 m with the same ascent profile. On ascent to 5085 m, ratings of perceived exertion (RPE ascent ), fatigue by Brunel Mood Scale, and AMS were recorded daily. At 5085 m, RPE during a fixed workload step test (RPE fixed ) and step rate during perceptually regulated exercise (STEP RPE35 ) were recorded. Greater sea-level [Formula: see text]O 2max was associated with, and predicted, lower sense of effort (RPE ascent ; r = -0.43; p < 0.001; RPE fixed ; r = -0.69; p < 0.001) and higher step rate (STEP RPE35 ; r = 0.62; p < 0.01), but not worse AMS (r = 0.13; p = 0.4) or arterial oxygen desaturation (r = 0.07; p = 0.7). Lower RPE ascent was also associated with better mood, including less fatigue (r = 0.57; p < 0.001). Hypoxic sensitivity was not associated with, and did not add to the prediction of submaximal exercise responses or AMS. In conclusion, participants with greater sea-level fitness reported less effort during simulated and actual trekking activities, had better mood (less fatigue), and chose a higher step rate during perceptually regulated exercise, but did not suffer from worse AMS or arterial oxygen desaturation. Simple sea-level fitness tests may be used to aid preparation for high-altitude travel.

A Common STEP in the Synaptic Pathology of Diverse Neuropsychiatric Disorders

PubMed Central

Johnson, Micah A.; Lombroso, Paul J.

2012-01-01

Synaptic function is critical for proper cognition, and synaptopathologies have been implicated in diverse neuropsychiatric disorders. STriatal-Enriched protein tyrosine Phosphatase (STEP) is a brain-enriched tyrosine phosphatase that normally opposes synaptic strengthening by dephosphorylating key neuronal signaling molecules. STEP targets include N-methyl D-aspartate receptors (NMDARs) and α-amino-3-hydroxy-5-methyl-4-isoxazolepropionic acid receptors (AMPARs), as well as extracellular signal-regulated kinase (ERK) and the tyrosine kinase Fyn. STEP-mediated dephosphorylation promotes the internalization of NMDARs and AMPARs and the inactivation of ERK and Fyn. Regulation of STEP is complex, and recent work has implicated STEP dysregulation in the pathophysiology of several neuropsychiatric disorders. Both high levels and low levels of STEP are found in a diverse group of illnesses. This review focuses on the role of STEP in three disorders in which STEP levels are elevated: Alzheimer’s disease, fragile X syndrome, and schizophrenia. The presence of elevated STEP in all three of these disorders raises the intriguing possibility that cognitive deficits resulting from diverse etiologies may share a common molecular pathway. PMID:23239949

Between-monitor differences in step counts are related to body size: implications for objective physical activity measurement.

PubMed

Pomeroy, Jeremy; Brage, Søren; Curtis, Jeffrey M; Swan, Pamela D; Knowler, William C; Franks, Paul W

2011-04-27

The quantification of the relationships between walking and health requires that walking is measured accurately. We correlated different measures of step accumulation to body size, overall physical activity level, and glucose regulation. Participants were 25 men and 25 women American Indians without diabetes (Age: 20-34 years) in Phoenix, Arizona, USA. We assessed steps/day during 7 days of free living, simultaneously with three different monitors (Accusplit-AX120, MTI-ActiGraph, and Dynastream-AMP). We assessed total physical activity during free-living with doubly labeled water combined with resting metabolic rate measured by expired gas indirect calorimetry. Glucose tolerance was determined during an oral glucose tolerance test. Based on observed counts in the laboratory, the AMP was the most accurate device, followed by the MTI and the AX120, respectively. The estimated energy cost of 1000 steps per day was lower in the AX120 than the MTI or AMP. The correlation between AX120-assessed steps/day and waist circumference was significantly higher than the correlation between AMP steps and waist circumference. The difference in steps per day between the AX120 and both the AMP and the MTI were significantly related to waist circumference. Between-monitor differences in step counts influence the observed relationship between walking and obesity-related traits.

Influence of the environment on the [4Fe-4S]2+ to [2Fe-2S]2+ cluster switch in the transcriptional regulator FNR.

PubMed

Crack, Jason C; Gaskell, Alisa A; Green, Jeffrey; Cheesman, Myles R; Le Brun, Nick E; Thomson, Andrew J

2008-02-06

In Escherichia coli, the switch between aerobic and anaerobic metabolism is primarily controlled by the fumarate and nitrate reduction transcriptional regulator FNR. In the absence of O2, FNR binds a [4Fe-4S]2+ cluster, generating a transcriptionally active dimeric form. Exposure to O2 results in the conversion of the cluster to a [2Fe-2S]2+ form, leading to dissociation of the protein into transcriptionally inactive monomers. The [4Fe-4S]2+ to [2Fe-2S]2+ cluster conversion proceeds in two steps. Step 1 involves the one-electron oxidation of the cluster, resulting in the release of Fe2+, generating a [3Fe-4S]1+ cluster intermediate, and a superoxide ion. In step 2, the cluster intermediate spontaneously rearranges to form the [2Fe-2S]2+ cluster, with the release of a Fe3+ ion and two sulfide ions. Here, we demonstrate that, in both native and reconstituted [4Fe-4S] FNR, the reaction environment and, in particular, the presence of Fe2+ and/or Fe3+ chelators can influence significantly the cluster conversion reaction. We demonstrate that while the rate of step 1 is largely insensitive to chelators, that of step 2 is significantly enhanced by both Fe2+ and Fe3+ chelators. We show that, for reactions in Fe3+-coordinating phosphate buffer, step 2 is enhanced to the extent that step 1 becomes the rate determining step and the [3Fe-4S]1+ intermediate is no longer detectable. Furthermore, Fe3+ released during this step is susceptible to reduction in the presence of Fe2+ chelators. This work, which may have significance for the in vivo FNR cluster conversion reaction in the cell cytoplasm, provides an explanation for apparently contradictory results reported from different laboratories.

Skill accreditation system for laparoscopic gastroenterologic surgeons in Japan.

PubMed

Mori, Toshiyuki; Kimura, Taizo; Kitajima, Masaki

2010-01-01

The Japan Society for Endoscopic Surgery (JSES) has established an Endoscopic Surgical Skill Qualification System and started examination in 2004. Non-edited videotapes were assessed by two judges in a double-blinded fashion with strict criteria. Two kinds of criteria, namely common and procedure-specific, were prepared. The common criteria were designed to evaluate set-ups, autonomy of the operator, display of the surgical field, recognition of surgical anatomy, co-operation of the surgical team. The procedure-specific criteria were made to assess the operation in a step-by-step fashion. In total, out of 1.114 surgeons who were assessed by this qualification system over a period of four years, 537 (48.2%) have been accredited. The qualification rate in each surgical field has remained at the same level of 40 to 50% to date. Inter-rater agreement of two judges was low at 0.31 in the first year, but improved with revision of the criteria and consensus meetings. Surgeons assessed by this system as qualified experienced less frequent complications when compared to those who failed. This system has impacted on the improvement and standardization of laparoscopic surgery in Japan.

Controlled crystallization of the lipophilic drug fenofibrate during freeze-drying: elucidation of the mechanism by in-line Raman spectroscopy.

PubMed

de Waard, Hans; De Beer, Thomas; Hinrichs, Wouter L J; Vervaet, Chris; Remon, Jean-Paul; Frijlink, Henderik W

2010-12-01

We developed a novel process, "controlled crystallization during freeze-drying" to produce drug nanocrystals of poorly water-soluble drugs. This process involves freeze-drying at a relatively high temperature of a drug and a matrix material from a mixture of tertiary butyl alcohol and water, resulting in drug nanocrystals incorporated in a matrix. The aim of this study was to elucidate the mechanisms that determine the size of the drug crystals. Fenofibrate was used as a model lipophilic drug. To monitor the crystallization during freeze-drying, a Raman probe was placed just above the sample in the freeze-dryer. These in-line Raman spectroscopy measurements clearly revealed when the different components crystallized during freeze-drying. The solvents crystallized only during the freezing step, while the solutes only crystallized after the temperature was increased, but before drying started. Although the solutes crystallized only after the freezing step, both the freezing rate and the shelf temperature were critical parameters that determined the final crystal size. At a higher freezing rate, smaller interstitial spaces containing the freeze-concentrated fraction were formed, resulting in smaller drug crystals (based on dissolution data). On the other hand, when the solutes crystallized at a lower shelf temperature, the degree of supersaturation is higher, resulting in a higher nucleation rate and consequently more and therefore smaller crystals. In conclusion, for the model drug fenofibrate, a high freezing rate and a relatively low crystallization temperature resulted in the smallest crystals and therefore the highest dissolution rate.

Halophilic mechanism of the enzymatic function of a moderately halophilic dihydrofolate reductase from Haloarcula japonica strain TR-1.

PubMed

Miyashita, Yurina; Ohmae, Eiji; Ikura, Teikichi; Nakasone, Kaoru; Katayanagi, Katsuo

2017-05-01

Dihydrofolate (DHF) reductase coded by a plasmid of the extremely halophilic archaeon Haloarcula japonica strain TR-1 (HjDHFR P1) shows moderate halophilicity on enzymatic activity at pH 6.0, although there is no significant effect of NaCl on its secondary structure. To elucidate the salt-activation and -inactivation mechanisms of this enzyme, we investigated the effects of pH and salt concentration, deuterium isotope effect, steady-state kinetics, and rapid-phase ligand-binding kinetics. Enzyme activity was increased eightfold by the addition of 500 mM NaCl at pH 6.0, fourfold by 250 mM at pH 8.0, and became independent of salt concentration at pH 10.0. Full isotope effects observed at pH 10.0 under 0-1000 mM NaCl indicated that the rate of hydride transfer, which was the rate-determining step at the basic pH region, was independent of salt concentration. Conversely, rapid-phase ligand-binding experiments showed that the amplitude of the DHF-binding reaction increased and the tetrahydrofolate (THF)-releasing rate decreased with increasing NaCl concentration. These results suggested that the salt-activation mechanism of HjDHFR P1 is via the population change of the anion-unbound and anion-bound conformers, which are binding-incompetent and -competent conformations for DHF, respectively, while that of salt inactivation is via deceleration of the THF-releasing rate, which is the rate-determining step at the neutral pH region.

Studies of certain sulfonamide drugs for use in juvenile chinook salmon

USGS Publications Warehouse

Amend, D.F.; Fryer, J.L.; Pilcher, K.S.

1969-01-01

In the work described in this paper, the efficacies of sulfisoxazole and sulfadimethoxine were compared to the efficacy of sulfamethazine. Experiments were designed to determine the rate of intestinal absorption, the rate of elimination from the blood, the effect on growth, and the toxicity of each drug in juvenile chinook salmon (Oncorhynchus tshawytscha). The comparative bacteriostatic activity against two common fish pathogens was also determined for each drug. 

Determination of the kinetics of guanine nucleotide exchange on EF-Tu and EF-Ts: continuing uncertainties.

PubMed

Manchester, Keith L

2004-01-30

An analysis is made of the rate constants for the reactions involving the interactions of EF-Tu, EF-Ts, GDP, and GTP recently derived by Gromadski et al. [Biochemistry 41 (2002) 162]. Though their measured values appear to allow a reasonable rate of nucleotide exchange sufficient to support rates of protein synthesis in vivo, their data underestimate the thermodynamic barrier involved in nucleotide exchange and therefore cannot be considered definitive. A kinetic scheme consistent with the thermodynamic barrier can be achieved by modification of various rate constants, particularly of those involving the release of EF-Ts from EF-Tu.GTP.EF-Ts, but such constants are markedly different from what are experimentally observed. It thus remains impossible at present satisfactorily to model guanine nucleotide exchange on EF-Tu, catalysed by EF-Ts by a double displacement mechanism, with experimentally derived rate constants. Metabolic control analysis has been applied to determine the degree of flux control of the different steps in the pathway.

Method of controlling injection of oxygen into hydrogen-rich fuel cell feed stream

DOEpatents

Meltser, Mark Alexander; Gutowski, Stanley; Weisbrod, Kirk

2001-01-01

A method of operating a H.sub.2 --O.sub.2 fuel cell fueled by hydrogen-rich fuel stream containing CO. The CO content is reduced to acceptable levels by injecting oxygen into the fuel gas stream. The amount of oxygen injected is controlled in relation to the CO content of the fuel gas, by a control strategy that involves (a) determining the CO content of the fuel stream at a first injection rate, (b) increasing the O.sub.2 injection rate, (c) determining the CO content of the stream at the higher injection rate, (d) further increasing the O.sub.2 injection rate if the second measured CO content is lower than the first measured CO content or reducing the O.sub.2 injection rate if the second measured CO content is greater than the first measured CO content, and (e) repeating steps a-d as needed to optimize CO consumption and minimize H.sub.2 consumption.

Broadband Acoustic Resonance Dissolution Spectroscopy (BARDS): A rapid test for enteric coating thickness and integrity of controlled release pellet formulations.

PubMed

Alfarsi, Anas; Dillon, Amy; McSweeney, Seán; Krüse, Jacob; Griffin, Brendan; Devine, Ken; Sherry, Patricia; Henken, Stephan; Fitzpatrick, Stephen; Fitzpatrick, Dara

2018-06-10

There are no rapid dissolution based tests for determining coating thickness, integrity and drug concentration in controlled release pellets either during production or post-production. The manufacture of pellets requires several coating steps depending on the formulation. The sub-coating and enteric coating steps typically take up to six hours each followed by additional drying steps. Post production regulatory dissolution testing also takes up to six hours to determine if the batch can be released for commercial sale. The thickness of the enteric coating is a key factor that determines the release rate of the drug in the gastro-intestinal tract. Also, the amount of drug per unit mass decreases with increasing thickness of the enteric coating. In this study, the coating process is tracked from start to finish on an hourly basis by taking samples of pellets during production and testing those using BARDS (Broadband Acoustic Resonance Dissolution Spectroscopy). BARDS offers a rapid approach to characterising enteric coatings with measurements based on reproducible changes in the compressibility of a solvent due to the evolution of air during dissolution. This is monitored acoustically via associated changes in the frequency of induced acoustic resonances. A steady state acoustic lag time is associated with the disintegration of the enteric coatings in basic solution. This lag time is pH dependent and is indicative of the rate at which the coating layer dissolves. BARDS represents a possible future surrogate test for conventional USP dissolution testing as its data correlates directly with the thickness of the enteric coating, its integrity and also with the drug loading as validated by HPLC. Copyright © 2018 Elsevier B.V. All rights reserved.

Voltammetric study of the boric acid-salicylaldehyde-H-acid ternary system and its application to the voltammetric determination of boron.

PubMed

Kajiwara, Mari; Ito, Yoshio N; Miyazaki, Yoshinobu; Fujimori, Takao; Takehara, Kô; Yoshimura, Kazuhisa

2015-02-14

The ternary system of boric acid, salicylaldehyde (SA) and H-acid (HA) was voltammetrically studied from kinetic and equilibrium points of view. The effect of the SA substituents was also studied by using two analogs, 5-fluorosalicylaldehyde (F-SA) and 5-methylsalicylaldehyde (Me-SA). The three cathodic peaks of Azomethine H (AzH), Azomethine H-boric acid complex (AzB), and free SA were observed in the solution containing boric acid, SA and HA. The peak potentials of AzH and SA were shifted to negative potentials with increasing pH, while the peak potential of AzB was pH-independent. This difference indicates that a proton participates in the charge-transfer steps of the AzH and SA reductions, but not in that of the AzB reduction. The formation constants for the AzB complexation were similar among all the examined analogs. In the kinetic study, the reaction rate was higher in an acidic condition for the AzH formation, but in a neutral condition for the AzB formation. The rate constants for the AzB complexes were in the order of F-SA > SA ≈ Me-SA, indicating that the fluoro group accelerates the F-AzB complexation. The AzB complexation mechanism is considered to consist of more than three steps, i.e., the pre-equilibrium of the salicylaldehyde-boric acid complex (SA-B) formation, the nucleophilic attack of HA on SA-B, and the remaining some steps to form AzB. Based on these results, the voltammetric determination method of boron using F-SA was optimized, which allowed the boron concentration to be determined within only 5 min with a 0.03 mg B dm(-3) detection limit.

Mechanistic Insights into Dye-Decolorizing Peroxidase Revealed by Solvent Isotope and Viscosity Effects

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

Shrestha, Ruben; Huang, Gaochao; Meekins, David A.

Dye-decolorizing peroxidases (DyPs) are a family of H2O2-dependent heme peroxidases that have shown potential applications in lignin degradation and valorization. However, the DyP kinetic mechanism remains underexplored. Using structural biology and solvent isotope (sKIE) and viscosity effects, many mechanistic characteristics have been determined for the B-class ElDyP from Enterobacter lignolyticus. Its structure revealed that a water molecule acts as the sixth axial ligand and two channels at diameters of ~3.0 and 8.0 Å lead to the heme center. A conformational change of ERS* to ERS, which have identical spectral characteristics, was proposed as the final step in DyPs’ bisubstrate Ping-Pongmore » mechanism. This step is also the rate-determining step in ABTS oxidation. The normal KIE of wild-type ElDyP with D2O2 at pD 3.5 suggested that compound 0 deprotonation by the distal aspartate is rate-limiting in the formation of compound I, which is more reactive under acidic pH than under neutral or alkaline pH. The viscosity effects and other biochemical methods implied that the reducing substrate binds with compound I instead of the free enzyme. The significant inverse sKIEs of kcat/KM and kERS* suggested that the aquo release in ElDyP is mechanistically important and may explain the enzyme’s adoption of two-electron reduction for compound I. The distal aspartate is catalytically more important than the distal arginine and plays key roles in determining ElDyP’s optimum acidic pH. The kinetic mechanism of D143H-ElDyP was also briefly studied. The results obtained will pave the way for future protein engineering to improve DyPs’ lignolytic activity.« less

Towards safe injection practices for prevention of hepatitis C transmission in South Asia: Challenges and progress.

PubMed

Janjua, Naveed Zafar; Butt, Zahid Ahmad; Mahmood, Bushra; Altaf, Arshad

2016-07-07

To summarize the available information about injection use and its determinants in the South Asian region. We searched published and unpublished literature on injection safety in South Asia published during 1995-2016 using the keywords "injection" "unsafe injection" and "immunization injection" and combined these with each of the countries and/or their respective states or provinces in South Asia. We used a standardized questionnaire to abstract the following data from the articles: the annual number of injections per capita, the proportion of injections administered with a reused syringe or needle, the distribution of injections with respect to prescribers and providers and determinants of injection use. Although information is very limited for certain countries (i.e., Bhutan, Maldives and Sri Lanka), healthcare injection use is very common across South Asia, with cross-country rates ranging from 2.4 to 13.6 injections/person/year. Furthermore, recent studies show that 5% to 50% of these injections are provided with reused syringes, thus creating potential to transmission of blood-borne pathogens. Qualified and unqualified practitioners, especially in the private sector, are the major drivers behind injection use, but patients also prefer injections, especially among the rural, poor or uneducated in certain countries. According to available data, Pakistan and India have recently taken steps towards achieving safe injection. Potential interventions include the introduction of reuse prevention devices, and patient-, community- and patient/community and provider-centered interventions to change population and practitioner behavior. Injection use is common in South Asian countries. Multilevel interventions aiming at patients, providers and the healthcare system are needed to reduce injection use and reuse.

Towards safe injection practices for prevention of hepatitis C transmission in South Asia: Challenges and progress

PubMed Central

Janjua, Naveed Zafar; Butt, Zahid Ahmad; Mahmood, Bushra; Altaf, Arshad

2016-01-01

AIM: To summarize the available information about injection use and its determinants in the South Asian region. METHODS: We searched published and unpublished literature on injection safety in South Asia published during 1995-2016 using the keywords “injection” “unsafe injection” and “immunization injection” and combined these with each of the countries and/or their respective states or provinces in South Asia. We used a standardized questionnaire to abstract the following data from the articles: the annual number of injections per capita, the proportion of injections administered with a reused syringe or needle, the distribution of injections with respect to prescribers and providers and determinants of injection use. RESULTS: Although information is very limited for certain countries (i.e., Bhutan, Maldives and Sri Lanka), healthcare injection use is very common across South Asia, with cross-country rates ranging from 2.4 to 13.6 injections/person/year. Furthermore, recent studies show that 5% to 50% of these injections are provided with reused syringes, thus creating potential to transmission of blood-borne pathogens. Qualified and unqualified practitioners, especially in the private sector, are the major drivers behind injection use, but patients also prefer injections, especially among the rural, poor or uneducated in certain countries. According to available data, Pakistan and India have recently taken steps towards achieving safe injection. Potential interventions include the introduction of reuse prevention devices, and patient-, community- and patient/community and provider-centered interventions to change population and practitioner behavior. CONCLUSION: Injection use is common in South Asian countries. Multilevel interventions aiming at patients, providers and the healthcare system are needed to reduce injection use and reuse. PMID:27433097

The epidemiology and cost analysis of patients presented to Emergency Department following traffic accidents.

PubMed

Akgül Karadana, Gökçe; Metin Aksu, Nalan; Akkaş, Meltem; Akman, Canan; Üzümcügil, Akın; Özmen, M Mahir

2013-12-09

Traffic accidents are ranked first as the cause of personal injury throughout the world. The high number of traffic accidents yielding injuries and fatalities makes them of great importance to Emergency Departments. Patients admitted to Hacettepe University Faculty of Medicine Adult Emergency Department due to traffic accidents were investigated epidemiologically. Differences between groups were evaluated by Kruskall-Wallis, Mann-Whitney, and Wilcoxon tests. A value of p<0.05 was accepted as statistically significant. We included 2003 patients over 16 years of age. The mean age was 39.6 ± 16.1 and 55% were males. Admissions by ambulance and due to motor vehicle accidents were the most common. In 2004 the rate of traffic accidents (15.3%) was higher than the other years, the most common month was May (10.8%), and the most common time period was 6 pm to 12 am (midnight). About half of the patients (51.5%) were admitted in the first 30 minutes. Life-threatening condition was present in 9.6% of the patients. Head trauma was the most common type of trauma, with the rate of 18.3%. Mortality rate was 81.8%. The average length of hospital stay was 403 minutes (6.7 hours) and the average cost per patient was 983 ± 4364 TL. Further studies are needed to compare the cost found in this study with the mean cost for Turkey. However, the most important step to reduce the direct and indirect costs due to traffic accidents is the prevention of these accidents.

Crystallographic control of surface structure on the sectoral zoning of iron in a diopside from Orford nickel mine (Quebec), Canada

NASA Astrophysics Data System (ADS)

Paquette, J.; Zangooi, A.; Thornton, K.

2004-05-01

The influence of surface structure on partitioning between mineral and melt (or solution) has been noted by other workers in a handful of minerals, including calcite, dolomite, apatite, topaz and diamond. Each one of these minerals displays at least one crystallographic face where steps present during crystal growth are not equivalent by symmetry. When this is the case, sectors grown at the edge of these steps commonly show differential incorporation of minor or trace elements. In the diopside investigated here, electron probe microanalyses performed on the as-grown (100) surface of several crystals show concentric and sectoral zoning defined by variations in Fe content. Atomic force microscopy (AFM) was used to study the surfaces of the three crystallographic forms present on the diopside crystals, with the goal of relating the compositional zoning to the surface structure of the faces. The dominant {100} faces are covered with growth hillocks consisting of four vicinal faces defined by steps parallel to [010] and [001]. The steps are often bunched into macrosteps and the resulting hillocks are visible optically. The steps along the two crystallographic directions show significant differences in straightness and smoothness that indicate non-equivalent kinetics. The wavier steps correspond to Fe-enriched areas within the {100} sectors. The {010} faces, next in morphological importance, are dominated by a single step orientation and show no differential incorporation. They display topography related to polysynthetic twinning. The {110} faces are much smaller and very few show resolvable steps. Sector zoning (i.e. diffential partitioning among non-equivalent crystallographic faces) has been described in the past from pyroxenes. Explanations have invoked either differences in surface structure among non-equivalent faces or their unequal growth rates. This particular occurrence indicates that trace element incorporation is, in fact, highly site-specific and that significant compositioinal zoning can be induced on a single face without invoking the effect of growth rate. The natural diopside crystals from the Orford nickel mine (Brompton, Quebec) show a unusual bladed habit flattened on {100} faces. Exceptional fluid chemistry during crystallization may therefore be required for the persistence of steps responsible for differential incorporation. Nevertheless, whenever this zoning is present, the trace element involved cannot be expected to reflect thermodynamic equilibrium between the solid and the fluid from which it crystallized.

A methodology for generating a tailored implementation blueprint: an exemplar from a youth residential setting.

PubMed

Lewis, Cara C; Scott, Kelli; Marriott, Brigid R

2018-05-16

Tailored implementation approaches are touted as more likely to support the integration of evidence-based practices. However, to our knowledge, few methodologies for tailoring implementations exist. This manuscript will apply a model-driven, mixed methods approach to a needs assessment to identify the determinants of practice, and pilot a modified conjoint analysis method to generate an implementation blueprint using a case example of a cognitive behavioral therapy (CBT) implementation in a youth residential center. Our proposed methodology contains five steps to address two goals: (1) identify the determinants of practice and (2) select and match implementation strategies to address the identified determinants (focusing on barriers). Participants in the case example included mental health therapists and operations staff in two programs of Wolverine Human Services. For step 1, the needs assessment, they completed surveys (clinician N = 10; operations staff N = 58; other N = 7) and participated in focus groups (clinician N = 15; operations staff N = 38) guided by the domains of the Framework for Diffusion [1]. For step 2, the research team conducted mixed methods analyses following the QUAN + QUAL structure for the purpose of convergence and expansion in a connecting process, revealing 76 unique barriers. Step 3 consisted of a modified conjoint analysis. For step 3a, agency administrators prioritized the identified barriers according to feasibility and importance. For step 3b, strategies were selected from a published compilation and rated for feasibility and likelihood of impacting CBT fidelity. For step 4, sociometric surveys informed implementation team member selection and a meeting was held to identify officers and clarify goals and responsibilities. For step 5, blueprints for each of pre-implementation, implementation, and sustainment phases were generated. Forty-five unique strategies were prioritized across the 5 years and three phases representing all nine categories. Our novel methodology offers a relatively low burden collaborative approach to generating a plan for implementation that leverages advances in implementation science including measurement, models, strategy compilations, and methods from other fields.

Aquifer response to stream-stage and recharge variations. II. Convolution method and applications

USGS Publications Warehouse

Barlow, P.M.; DeSimone, L.A.; Moench, A.F.

2000-01-01

In this second of two papers, analytical step-response functions, developed in the companion paper for several cases of transient hydraulic interaction between a fully penetrating stream and a confined, leaky, or water-table aquifer, are used in the convolution integral to calculate aquifer heads, streambank seepage rates, and bank storage that occur in response to streamstage fluctuations and basinwide recharge or evapotranspiration. Two computer programs developed on the basis of these step-response functions and the convolution integral are applied to the analysis of hydraulic interaction of two alluvial stream-aquifer systems in the northeastern and central United States. These applications demonstrate the utility of the analytical functions and computer programs for estimating aquifer and streambank hydraulic properties, recharge rates, streambank seepage rates, and bank storage. Analysis of the water-table aquifer adjacent to the Blackstone River in Massachusetts suggests that the very shallow depth of water table and associated thin unsaturated zone at the site cause the aquifer to behave like a confined aquifer (negligible specific yield). This finding is consistent with previous studies that have shown that the effective specific yield of an unconfined aquifer approaches zero when the capillary fringe, where sediment pores are saturated by tension, extends to land surface. Under this condition, the aquifer's response is determined by elastic storage only. Estimates of horizontal and vertical hydraulic conductivity, specific yield, specific storage, and recharge for a water-table aquifer adjacent to the Cedar River in eastern Iowa, determined by the use of analytical methods, are in close agreement with those estimated by use of a more complex, multilayer numerical model of the aquifer. Streambank leakance of the semipervious streambank materials also was estimated for the site. The streambank-leakance parameter may be considered to be a general (or lumped) parameter that accounts not only for the resistance of flow at the river-aquifer boundary, but also for the effects of partial penetration of the river and other near-stream flow phenomena not included in the theoretical development of the step-response functions.Analytical step-response functions, developed for several cases of transient hydraulic interaction between a fully penetrating stream and a confined, leaky, or water-table aquifer, are used in the convolution integral to calculate aquifer heads, streambank seepage rates, and bank storage that occur in response to stream-stage fluctuations and basinwide recharge or evapotranspiration. Two computer programs developed on the basis of these step-response functions and the convolution integral are applied to the analysis of hydraulic interaction of two alluvial stream-aquifer systems. These applications demonstrate the utility of the analytical functions and computer programs for estimating aquifer and streambank seepage rates and bank storage.

Modeling the effect of adsorption on the degradation rate of propiconazole in profiles of Polish Luvisols.

PubMed

Paszko, Tadeusz; Jankowska, Monika

2018-06-18

Laboratory adsorption and degradation studies were carried out to determine the effect of time-dependent adsorption on propiconazole degradation rates in samples from three Polish Luvisols. Strong propiconazole adsorption (organic carbon normalized adsorption coefficients K oc in the range of 1217-7777 mL/g) was observed in batch experiments, with a typical biphasic mechanism with a fast initial step followed by the time-dependent step, which finished within 48 h in the majority of soils. The time-dependent step observed in incubation experiments was longer (duration from 5 to 23 d), and its contribution to total adsorption was from 20% to 34%. The half-lives obtained at 25 °C and 40% maximum water holding capacity of soil, were in the range of 34.7-112.9 d in the Ap horizon and in the range of 42.3-448.8 d for subsoils. The very strong correlations, between degradation rates in pore water and soil organic carbon and soil microbial activity, indicated that microbial degradation of propiconazole was most likely the only significant process responsible for the decay of this compound under aerobic conditions for the whole of the examined soil profiles. Modeling of the processes showed that only models coupling adsorption and degradation were able to correctly describe the experimental data. The analysis of the bioavailability factor values showed that degradation was not limited by the rate of propiconazole desorption from soil, but sorption affected the degradation rate by decreasing its availability for microorganisms. Copyright © 2018. Published by Elsevier Inc.

ATLAS trigger operations: Upgrades to ``Xmon'' rate prediction system

NASA Astrophysics Data System (ADS)

Myers, Ava; Aukerman, Andrew; Hong, Tae Min; Atlas Collaboration

2017-01-01

We present ``Xmon,'' a tool to monitor trigger rates in the Control Room of the ATLAS Experiment. We discuss Xmon's recent (1) updates, (2) upgrades, and (3) operations. (1) Xmon was updated to modify the tool written for the three-level trigger architecture in Run-1 (2009-2012) to adapt to the new two-level system for Run-2 (2015-current). The tool takes as input the beam luminosity to make a rate prediction, which is compared with incoming rates to detect anomalies that occur both globally throughout a run and locally within a run. Global offsets are more commonly caught by the predictions based upon past runs, where offline processing allows for function adjustments and fit quality through outlier rejection. (2) Xmon was upgraded to detect local offsets using on-the-fly predictions, which uses a sliding window of in-run rates to make predictions. (3) Xmon operations examples are given. Future work involves further automation of the steps to provide the predictive functions and for alerting shifters.

Objective assessment of activity in older adults at risk for mobility disability.

PubMed

Marsh, Anthony P; Vance, Rachel M; Frederick, Tera L; Hesselmann, Sarah A; Rejeski, W Jack

2007-06-01

The purpose of this study was to evaluate the validity of three objective measures of physical activity (Accusplit Eagle 120 mechanical pedometer (AE120), NL-2000 electronic pedometer, and IDEEA pattern-recognition device) that varied in their levels of sophistication, among older adults at risk for mobility disability. In addition, we examined the potential influences of gait speed and body mass index (BMI) on step count accuracy. Step counts recorded on the three devices were compared against manual step counts made by two investigators as each participant walked 131 m around an indoor track at their preferred walking speed (N=29; 75.8+/-4.2 yr). Gait speed was determined by dividing total distance walked by time to completion. BMI was calculated from height and body mass measurements. All three devices significantly underestimated steps taken (AE120=22.8+/-53.9 steps; NL-2000=4.0+/-5.8 steps; IDEEA=5.6+/-7.8 steps), but there was no significant difference between devices (P=0.084). Steps counted by the AE120, NL-2000, and IDEEA were significantly correlated with manual step counts (r=0.508, 0.980, and 0.965, respectively; P

Measuring individual work performance: identifying and selecting indicators.

PubMed

Koopmans, Linda; Bernaards, Claire M; Hildebrandt, Vincent H; de Vet, Henrica C W; van der Beek, Allard J

2014-01-01

Theoretically, individual work performance (IWP) can be divided into four dimensions: task performance, contextual performance, adaptive performance, and counterproductive work behavior. However, there is no consensus on the indicators used to measure these dimensions. This study was designed to (1) identify indicators for each dimension, (2) select the most relevant indicators, and (3) determine the relative weight of each dimension in ratings of work performance. IWP indicators were identified from multiple research disciplines, via literature, existing questionnaires, and expert interviews. Subsequently, experts selected the most relevant indicators per dimension and scored the relative weight of each dimension in ratings of IWP. In total, 128 unique indicators were identified. Twenty-three of these indicators were selected by experts as most relevant for measuring IWP. Task performance determined 36% of the work performance rating, while the other three dimensions respectively determined 22%, 20% and 21% of the rating. Notable consensus was found on relevant indicators of IWP, reducing the number from 128 to 23 relevant indicators. This provides an important step towards the development of a standardized, generic and short measurement instrument for assessing IWP.

Fundamental mechanisms in premixed flame propagation via vortex-flame interactions: Numerical simulations

NASA Technical Reports Server (NTRS)

Mantel, Thierry

1994-01-01

The goal of the present study is to assess numerically the ability of single-step and two-step chemical models to describe the main features encountered during the interaction between a two-dimensional vortex pair and a premixed laminar flame. In the two-step mechanism, the reaction kinetics are represented by a first chain branching reaction A + X yields 2X and a second chain termination reaction X + X yields P. This paper presents the fundamental mechanisms occurring during vortex-flame interactions and the relative impact of the major parameters encountered in turbulent premixed flames and suspected of playing a role in quenching mechanism: (1) Influence of stretch is investigated by analyzing the contribution of curvature and tangential strain on the local structure of the flame. The effect of Lewis number on the flame response to a strained field is analyzed. (2) Radiative heat losses which are suspected to be partially or totally responsible for quenching are also investigated. (3) The effect of the diffusion of the radicals is studied using a two-step mechanism in which an intermediate species is present. The parameters of the two-step mechanism are entirely determined from physical arguments. (4) Precise quantitative comparisons between the DNS and the experimental results of Samaniego et al are performed. These comparisons concern the evolution of the minimum heat release rate found along the flame front during the interaction and the distribution of the heat release rate along the flame front.

Using performance measurement to drive improvement: a road map for change.

PubMed

Galvin, Robert S; McGlynn, Elizabeth A

2003-01-01

Performance measures and reporting have not been adopted throughout the US health care system despite their central role in encouraging increased participation by consumers in decision-making. Understanding whether the failure of measurement and reporting to diffuse throughout the health system can be overcome is critical for determining future policy in this area. To create a conceptual framework for analyzing the current rate of adoption and evaluating alternatives for accelerating adoption, and to recommend a set of concrete steps that can be taken to increase the use of performance measurement and reporting. Review of three theoretic models (Rogers, Prochaska/DiClemente, Gladwell), examination of the literature on previous experiences with quality measurement and reporting, and interviews with select stakeholders. The three theoretic models provide a valuable framework for understanding why the use of performance measures is stalled ("the circle of unaccountability") and for generating ideas about concrete steps that could be taken to accelerate adoption. Six steps are recommended: (1) raise public awareness, (2) redesign measures and reports, (3) make the delivery of information timely, (4) require public reporting, (5) develop and implement systems to reward quality, and (6) actively court leaders. The recommended six steps are interconnected; action on all will be required to drive significant acceleration in rates of adoption of performance measurement and reporting. Leadership and coordination are necessary to ensure these steps are taken and that they work in concert with one another.

On the Least-Squares Fitting of Correlated Data: a Priorivs a PosterioriWeighting

NASA Astrophysics Data System (ADS)

Tellinghuisen, Joel

1996-10-01

One of the methods in common use for analyzing large data sets is a two-step procedure, in which subsets of the full data are first least-squares fitted to a preliminary set of parameters, and the latter are subsequently merged to yield the final parameters. The second step of this procedure is properly a correlated least-squares fit and requires the variance-covariance matrices from the first step to construct the weight matrix for the merge. There is, however, an ambiguity concerning the manner in which the first-step variance-covariance matrices are assessed, which leads to different statistical properties for the quantities determined in the merge. The issue is one ofa priorivsa posterioriassessment of weights, which is an application of what was originally calledinternalvsexternal consistencyby Birge [Phys. Rev.40,207-227 (1932)] and Deming ("Statistical Adjustment of Data." Dover, New York, 1964). In the present work the simplest case of a merge fit-that of an average as obtained from a global fit vs a two-step fit of partitioned data-is used to illustrate that only in the case of a priori weighting do the results have the usually expected and desired statistical properties: normal distributions for residuals,tdistributions for parameters assessed a posteriori, and χ2distributions for variances.

Step width alters iliotibial band strain during running.

PubMed

Meardon, Stacey A; Campbell, Samuel; Derrick, Timothy R

2012-11-01

This study assessed the effect of step width during running on factors related to iliotibial band (ITB) syndrome. Three-dimensional (3D) kinematics and kinetics were recorded from 15 healthy recreational runners during overground running under various step width conditions (preferred and at least +/- 5% of their leg length). Strain and strain rate were estimated from a musculoskeletal model of the lower extremity. Greater ITB strain and strain rate were found in the narrower step width condition (p < 0.001, p = 0.040). ITB strain was significantly (p < 0.001) greater in the narrow condition than the preferred and wide conditions and it was greater in the preferred condition than the wide condition. ITB strain rate was significantly greater in the narrow condition than the wide condition (p = 0.020). Polynomial contrasts revealed a linear increase in both ITB strain and strain rate with decreasing step width. We conclude that relatively small decreases in step width can substantially increase ITB strain as well as strain rates. Increasing step width during running, especially in persons whose running style is characterized by a narrow step width, may be beneficial in the treatment and prevention of running-related ITB syndrome.

Validity of Different Activity Monitors to Count Steps in an Inpatient Rehabilitation Setting.

PubMed

Treacy, Daniel; Hassett, Leanne; Schurr, Karl; Chagpar, Sakina; Paul, Serene S; Sherrington, Catherine

2017-05-01

Commonly used activity monitors have been shown to be accurate in counting steps in active people; however, further validation is needed in slower walking populations. To determine the validity of activity monitors for measuring step counts in rehabilitation inpatients compared with visually observed step counts. To explore the influence of gait parameters, activity monitor position, and use of walkers on activity monitor accuracy. One hundred and sixty-six inpatients admitted to a rehabilitation unit with an average walking speed of 0.4 m/s (SD 0.2) wore 16 activity monitors (7 different devices in different positions) simultaneously during 6-minute and 6-m walks. The number of steps taken during the tests was also counted by a physical therapist. Gait parameters were assessed using the GAITRite system. To analyze the influence of different gait parameters, the percentage accuracy for each monitor was graphed against various gait parameters for each activity monitor. The StepWatch, Fitbit One worn on the ankle and the ActivPAL showed excellent agreement with observed step count (ICC 2,1 0.98; 0.92; 0.78 respectively). Other devices (Fitbit Charge, Fitbit One worn on hip, G-Sensor, Garmin Vivofit, Actigraph) showed poor agreement with the observed step count (ICC 2,1 0.12-0.40). Percentage agreement with observed step count was highest for the StepWatch (mean 98%). The StepWatch and the Fitbit One worn on the ankle maintained accuracy in individuals who walked more slowly and with shorter strides but other devices were less accurate in these individuals. There were small numbers of participants for some gait parameters. The StepWatch showed the highest accuracy and closest agreement with observed step count. This device can be confidently used by researchers for accurate measurement of step counts in inpatient rehabilitation in individuals who walk slowly. If immediate feedback is desired, the Fitbit One when worn on the ankle would be the best choice for this population. © 2017 American Physical Therapy Association

Homogeneous and heterogenized iridium water oxidation catalysts

NASA Astrophysics Data System (ADS)

Macchioni, Alceo

2014-10-01

The development of an efficient catalyst for the oxidative splitting of water into molecular oxygen, protons and electrons is of key importance for producing solar fuels through artificial photosynthesis. We are facing the problem by means of a rational approach aimed at understanding how catalytic performance may be optimized by the knowledge of the reaction mechanism of water oxidation and the fate of the catalytic site under the inevitably harsh oxidative conditions. For the purposes of our study we selected iridium water oxidation catalysts, exhibiting remarkable performance (TOF > 5 s-1 and TON > 20000). In particular, we recently focused our attention on [Cp*Ir(N,O)X] (N,O = 2-pyridincarboxylate; X = Cl or NO3) and [IrCl(Hedta)]Na water oxidation catalysts. The former exhibited a remarkable TOF whereas the latter showed a very high TON. Furthermore, [IrCl(Hedta)]Na was heterogenized onto TiO2 taking advantage of the presence of a dandling -COOH functionality. The heterogenized catalyst maintained approximately the same catalytic activity of the homogeneous analogous with the advantage that could be reused many times. Mechanistic studies were performed in order to shed some light on the rate-determining step and the transformation of catalysts when exposed to "oxidative stress". It was found that the last oxidative step, preceding oxygen liberation, is the rate-determining step when a small excess of sacrificial oxidant is used. In addition, several intermediates of the oxidative transformation of the catalyst were intercepted and characterized by NMR, X-Ray diffractometry and ESI-MS.

Fracture Behavior in Nylon 6 Fibers. Ph.D. Thesis

NASA Technical Reports Server (NTRS)

Lloyd, B. A.

1972-01-01

Electron paramagnetic resonance (EPR) techniques are used to determine the number of free radicals produced during deformation leading to fracture of nylon 6 fibers. A reaction rate molecular model is proposed to explain some of the deformation and bond rupture behavior leading to fracture. High-strength polymer fibers are assumed to consist of a sandwich structure of disordered and ordered regions along the fiber axis. In the disordered or critical flaw regions, tie chains connecting the ordered or crystalline block regions are assumed to have a statistical distribution in length. These chains are, therefore, subjected to different stresses. The effective length distribution was determined by EPR. The probability of bond rupture was assumed to be controlled by reaction-rate theory with a stress-aided activation energy and behavior of various loadings determined by numerical techniques. The model is successfully correlated with experimental stress, strain, and bond rupture results for creep, constant rate loadings, cyclic stress, stress relaxation and step strain tests at room temperature.

Gait Coordination in Parkinson Disease: Effects of Step Length and Cadence Manipulations

PubMed Central

Williams, April J.; Peterson, Daniel S.; Earhart, Gammon M.

2013-01-01

Background Gait impairments are well documented in those with PD. Prior studies suggest that gait impairments may be worse and ongoing in those with PD who demonstrate FOG compared to those with PD who do not. Purpose Our aim was to determine the effects of manipulating step length and cadence individually, and together, on gait coordination in those with PD who experience FOG, those with PD who do not experience FOG, healthy older adults, and healthy young adults. Methods Eleven participants with PD and FOG, 16 with PD and no FOG, 18 healthy older, and 19 healthy young adults walked across a GAITRite walkway under four conditions: Natural, Fast (+50% of preferred cadence), Small (−50% of preferred step length), and SmallFast (+50% cadence and −50% step length). Coordination (i.e. phase coordination index) was measured for each participant during each condition and analyzed using mixed model repeated measure ANOVAs. Results FOG was not elicited. Decreasing step length or decreasing step length and increasing cadence together affected coordination. Small steps combined with fast cadence resulted in poorer coordination in both groups with PD compared to healthy young adults and in those with PD and FOG compared to healthy older adults. Conclusions Coordination deficits can be identified in those with PD by having them walk with small steps combined with fast cadence. Short steps produced at high rate elicit worse coordination than short steps or fast steps alone. PMID:23333356

Genetic parameters of product quality and hepatic metabolism in fattened mule ducks.

PubMed

Marie-Etancelin, C; Basso, B; Davail, S; Gontier, K; Fernandez, X; Vitezica, Z G; Bastianelli, D; Baéza, E; Bernadet, M-D; Guy, G; Brun, J-M; Legarra, A

2011-03-01

Genetic parameters of traits related to hepatic lipid metabolism, carcass composition, and product quality of overfed mule ducks were estimated on both parental lines of this hybrid: the common duck line for the maternal side and the Muscovy line for the paternal side. The originality of the statistical model was to include simultaneously the additive genetic effect of the common ducks and that of the Muscovy ducks, revealing a greater genetic determinism in common than in Muscovy. Plasma metabolic indicators (glucose, triglyceride, and cholesterol contents) were heritable, in particular at the end of the overfeeding period, and heritabilities increased with the overfeeding stage. Carcass composition traits were highly heritable in the common line, with values ranging from 0.15 for liver weight, 0.21 for carcass weight, and 0.25 for abdominal fat weight to 0.32 for breast muscle weight. Heritabilities of technological outputs were greater for the fatty liver (0.19 and 0.08, respectively, on common and Muscovy sides for liver melting rate) than for the pectoralis major muscle (between 0.02 and 0.05 on both parental sides for cooking losses). Fortunately, the processing industry is mainly facing problems in liver quality, such as too high of a melting rate, than in meat quality. The meat quality appraisal criteria (such as texture and cooking losses), usually dependent on pH and the rate of decline of pH, were also very lowly heritable. This study demonstrated that genetic determinism of meat quality and ability of overfeeding is not similar in the common population and in the Muscovy population; traits related to fattening, muscle development, and BW have heritability values from 2 to 4 times greater on the common line than on the Muscovy line, which is relevant for considering different selection strategies.

Quartermaster 1 and C, Rate Training Manual.

ERIC Educational Resources Information Center

Naval Personnel Program Support Activity, Washington, DC.

The technical subject matter of the Quartermaster rating is presented in this training manual written to prepare men of the Navy and Naval Reserve for advancement examinations. The manual includes eleven chapters. Discussed are commonly used methods and procedures of operating magnetic compasses and gyrocompasses, determining a ship's position,…

Texting during stair negotiation and implications for fall risk.

PubMed

Hashish, Rami; Toney-Bolger, Megan E; Sharpe, Sarah S; Lester, Benjamin D; Mulliken, Adam

2017-10-01

Walking requires the integration of the sensory and motor systems. Cognitive distractions have been shown to interfere with negotiation of complex walking environments, especially in populations at greater risk for falls (e.g. the elderly). With the pervasiveness of mobile messaging and the recent introduction of augmented reality mobile gaming, it is increasingly important to understand how distraction associated with the simultaneous use of a mobile device impacts navigation of the complex walking environments experienced in daily life. In this study, we investigated how gait kinematics were altered when participants performed a texting task during step negotiation. Twenty participants (13 female, 7 males) performed a series of walking trials involving a step-deck obstacle, consisting of at least 3 texting trials and 3 non-texting trials. When texting, participants ascended more slowly and demonstrated reduced dual-step foot toe clearance. Participants similarly descended more slowly when texting and demonstrated reduced single-step foot heel clearance as well as reduced dual-step foot fore-aft heel clearance. These data support the conclusion that texting during stair negotiation results in changes to gait kinematics that may increase the potential for gait disruptions, falls, and injury. Further research should examine the effect texting has on performing other common complex locomotor tasks, actual fall risk, and the patterns of resulting injury rate and severity when negotiating complex environments. Copyright © 2017 Elsevier B.V. All rights reserved.

Utilizing Infant Cry Acoustics to Determine Gestational Age.

PubMed

Sahin, Mustafa; Sahin, Suzan; Sari, Fatma N; Tatar, Emel C; Uras, Nurdan; Oguz, Suna S; Korkmaz, Mehmet H

2017-07-01

The date of last menstruation period and ultrasonography are the most commonly used methods to determine gestational age (GA). However, if these data are not clear, some scoring systems performed after birth can be used. New Ballard Score (NBS) is a commonly used method in estimation of GA. Cry sound may reflect the developmental integrity of the infant. The aim of this study was to evaluate the connection between the infants' GA and some acoustic parameters of the infant cry. A prospective single-blind study was carried out. In this prospective study, medically stable infants without any congenital craniofacial anomalies were evaluated. During routine blood sampling, cry sounds were recorded and acoustic analysis was performed. Step-by-step multiple linear regression analysis was performed. The data of 116 infants (57 female, 59 male) with the known GA (34.6 ± 3.8 weeks) were evaluated and with Apgar score of higher than 5. The real GA was significantly and well correlated with the estimated GA according to the NBS, F0, Int, Jitt, and latency parameters. The obtained stepwise linear regression analysis model was formulized as GA=(31.169) - (0.020 × F0)+(0.286 × GA according to NBS) - (0.003 × Latency)+(0.108 × Int) - (0.367 × Jitt). The real GA could be determined with a ratio of 91.7% using this model. We have determined that after addition of F0, Int, Jitt, and latency to NBS, the power of GA estimation would be increased. This simple formula can be used to determine GA in clinical practice but validity of such prediction formulas needs to be further tested. Copyright © 2017 The Voice Foundation. Published by Elsevier Inc. All rights reserved.

Physical Activity Assessment with the ActiGraph GT3X and Doubly Labeled Water.

PubMed

Chomistek, Andrea K; Yuan, Changzheng; Matthews, Charles E; Troiano, Richard P; Bowles, Heather R; Rood, Jennifer; Barnett, Junaidah B; Willett, Walter C; Rimm, Eric B; Bassett, David R

2017-09-01

To compare the degree to which four accelerometer metrics-total activity counts per day (TAC per day), steps per day (steps per day), physical activity energy expenditure (PAEE) (kcal·kg·d), and moderate- to vigorous-intensity physical activity (MVPA) (min·d)-were correlated with PAEE measured by doubly labeled water (DLW). Additionally, accelerometer metrics based on vertical axis counts and triaxial counts were compared. This analysis included 684 women and 611 men age 43 to 83 yr. Participants wore the Actigraph GT3X on the hip for 7 d twice during the study and the average of the two measurements was used. Each participant also completed one DLW measurement, with a subset having a repeat. PAEE was estimated by subtracting resting metabolic rate and the thermic effect of food from total daily energy expenditure estimated by DLW. Partial Spearman correlations were used to estimate associations between PAEE and each accelerometer metric. Correlations between the accelerometer metrics and DLW-determined PAEE were higher for triaxial counts than vertical axis counts. After adjusting for weight, age, accelerometer wear time, and fat free mass, the correlation between TAC per day based on triaxial counts and DLW-determined PAEE was 0.44 in women and 0.41 in men. Correlations for steps per day and accelerometer-estimated PAEE with DLW-determined PAEE were similar. After adjustment for within-person variation in DLW-determined PAEE, the correlations for TAC per day increased to 0.61 and 0.49, respectively. Correlations between MVPA and DLW-determined PAEE were lower, particularly for modified bouts of ≥10 min. Accelerometer measures that represent total activity volume, including TAC per day, steps per day, and PAEE, were more highly correlated with DLW-determined PAEE than MVPA using traditional thresholds and should be considered by researchers seeking to reduce accelerometer data to a single metric.

Do Residency Selection Factors Predict Radiology Resident Performance?

PubMed

Agarwal, Vikas; Bump, Gregory M; Heller, Matthew T; Chen, Ling-Wan; Branstetter, Barton F; Amesur, Nikhil B; Hughes, Marion A

2018-03-01

The purpose of our study is to determine what information in medical student residency applications predicts radiology residency success as defined by objective clinical performance data. We performed a retrospective cohort study of residents who entered our institution's residency program through the National Resident Matching Program as postgraduate year 2 residents and completed the program over the past 2 years. Medical school grades, selection to Alpha Omega Alpha (AOA) Honor Society, United States Medical Licensing Examination (USMLE) scores, publication in peer-reviewed journals, and whether the applicant was from a peer institution were the variables examined. Clinical performance was determined by calculating each resident's cumulative major discordance rate for on-call cases the resident read and gave a preliminary interpretation. A major discordance was defined as a difference between the preliminary resident and the final attending interpretations that could immediately impact the care of the patient. A multivariate logistic regression was performed to determine significant variables. Twenty-seven residents provided preliminary reports on call for 67,145 studies. The mean major discordance rate was 1.08% (range 0.34%-2.54%). Higher USMLE Step 1 scores, publication before residency, and election to AOA Honor Society were all statistically significant predictors of lower major discordance rates (P values 0.01, 0.01,  and <0.001, respectively). Overall resident performance was excellent. There are predictors that help select the better performing residents, namely higher USMLE Step 1 scores, one to two publications during medical school, and election to AOA in the junior year of medical school. Copyright © 2018 The Association of University Radiologists. Published by Elsevier Inc. All rights reserved.

Why Not Wait? Eight Institutions Share Their Experiences Moving United States Medical Licensing Examination Step 1 After Core Clinical Clerkships.

PubMed

Daniel, Michelle; Fleming, Amy; Grochowski, Colleen O'Conner; Harnik, Vicky; Klimstra, Sibel; Morrison, Gail; Pock, Arnyce; Schwartz, Michael L; Santen, Sally

2017-11-01

The majority of medical students complete the United States Medical Licensing Examination Step 1 after their foundational sciences; however, there are compelling reasons to examine this practice. This article provides the perspectives of eight MD-granting medical schools that have moved Step 1 after the core clerkships, describing their rationale, logistics of the change, outcomes, and lessons learned. The primary reasons these institutions cite for moving Step 1 after clerkships are to foster more enduring and integrated basic science learning connected to clinical care and to better prepare students for the increasingly clinical focus of Step 1. Each school provides key features of the preclerkship and clinical curricula and details concerning taking Steps 1 and 2, to allow other schools contemplating change to understand the landscape. Most schools report an increase in aggregate Step 1 scores after the change. Despite early positive outcomes, there may be unintended consequences to later scheduling of Step 1, including relatively late student reevaluations of their career choice if Step 1 scores are not competitive in the specialty area of their choice. The score increases should be interpreted with caution: These schools may not be representative with regard to mean Step 1 scores and failure rates. Other aspects of curricular transformation and rising national Step 1 scores confound the data. Although the optimal timing of Step 1 has yet to be determined, this article summarizes the perspectives of eight schools that changed Step 1 timing, filling a gap in the literature on this important topic.

Exome-wide Sequencing Shows Low Mutation Rates and Identifies Novel Mutated Genes in Seminomas.

PubMed

Cutcutache, Ioana; Suzuki, Yuka; Tan, Iain Beehuat; Ramgopal, Subhashini; Zhang, Shenli; Ramnarayanan, Kalpana; Gan, Anna; Lee, Heng Hong; Tay, Su Ting; Ooi, Aikseng; Ong, Choon Kiat; Bolthouse, Jonathan T; Lane, Brian R; Anema, John G; Kahnoski, Richard J; Tan, Patrick; Teh, Bin Tean; Rozen, Steven G

2015-07-01

Testicular germ cell tumors are the most common cancer diagnosed in young men, and seminomas are the most common type of these cancers. There have been no exome-wide examinations of genes mutated in seminomas or of overall rates of nonsilent somatic mutations in these tumors. The objective was to analyze somatic mutations in seminomas to determine which genes are affected and to determine rates of nonsilent mutations. Eight seminomas and matched normal samples were surgically obtained from eight patients. DNA was extracted from tissue samples and exome sequenced on massively parallel Illumina DNA sequencers. Single-nucleotide polymorphism chip-based copy number analysis was also performed to assess copy number alterations. The DNA sequencing read data were analyzed to detect somatic mutations including single-nucleotide substitutions and short insertions and deletions. The detected mutations were validated by independent sequencing and further checked for subclonality. The rate of nonsynonymous somatic mutations averaged 0.31 mutations/Mb. We detected nonsilent somatic mutations in 96 genes that were not previously known to be mutated in seminomas, of which some may be driver mutations. Many of the mutations appear to have been present in subclonal populations. In addition, two genes, KIT and KRAS, were affected in two tumors each with mutations that were previously observed in other cancers and are presumably oncogenic. Our study, the first report on exome sequencing of seminomas, detected somatic mutations in 96 new genes, several of which may be targetable drivers. Furthermore, our results show that seminoma mutation rates are five times higher than previously thought, but are nevertheless low compared to other common cancers. Similar low rates are seen in other cancers that also have excellent rates of remission achieved with chemotherapy. We examined the DNA sequences of seminomas, the most common type of testicular germ cell cancer. Our study identified 96 new genes in which mutations occurred during seminoma development, some of which might contribute to cancer development or progression. The study also showed that the rates of DNA mutations during seminoma development are higher than previously thought, but still lower than for other common solid-organ cancers. Such low rates are also observed among other cancers that, like seminomas, show excellent rates of disease remission after chemotherapy. Copyright © 2015 European Association of Urology. Published by Elsevier B.V. All rights reserved.

The Determination of Rate-Limiting Steps during Soot Formation

DTIC Science & Technology

1989-04-27

acceleration in chemistry due to the presence of oxygen . Quantitative prediction of soot production , should it become a reality, will require knowledge of...PAH ..... ... ..................... 7 Fig. 4 1.25% Benzene/1% Oxygen - Light Products ........ .................... 8 Fig. 5 1.25% Benzene/0.3% Oxygen ...Benzene/0.3% Oxygen - PAH Production ....... .................. 11 Fig. 8 Evolution of Closed Ring Aromatics (t(source) = oo) .................... .15 Fig

75 FR 73047 - Agency Information Collection Activities; Proposed Collection; Comment Request; Prize...

Federal Register 2010, 2011, 2012, 2013, 2014

2010-11-29

... approximately six hours per work week for six months on such contest or award activities. Of the ten staff... annual cost to the Federal government is determined as follows: Seven employees x (six hours/week/employee x 24 weeks) = 1,008 hours. Assuming the employees are at the GS-15, Step 5 level, the hourly rate...

Weathering of almandine garnet: influence of secondary minerals on the rate-determining step, and implications for regolith-scale Al mobilization

Treesearch

Jason R. Price; Debra S. Bryan-Ricketts; Diane Anderson; Michael A. Velbel

2013-01-01

Secondary surface layers form by replacement of almandine garnet during chemical weathering. This study tested the hypothesis that the kinetic role of almandine's weathering products, and the consequent relationships of primary-mineral surface texture and specific assemblages of secondary minerals, both vary with the solid-solution-controlled variations in Fe and...

The use of maxillary sinus dimensions in gender determination: a thin-slice multidetector computed tomography assisted morphometric study.

PubMed

Ekizoglu, Oguzhan; Inci, Ercan; Hocaoglu, Elif; Sayin, Ibrahim; Kayhan, Fatma Tulin; Can, Ismail Ozgur

2014-05-01

Gender determination is an important step in identification. For gender determination, anthropometric evaluation is one of the main forensic evaluations. In the present study, morphometric analysis of maxillary sinuses was performed to determine gender. For morphometric analysis, coronal and axial paranasal sinus computed tomography (CT) scan with 1-mm slice thickness was used. For this study, 140 subjects (70 women and 70 men) were enrolled (age ranged between 18 and 63). The size of each subject's maxillary sinuses was measured in anteroposterior, transverse, cephalocaudal, and volume directions. In each measurement, the size of the maxillary sinus is significantly small in female gender (P < 0.001). When discrimination analysis was performed, the accuracy rate was detected as 80% for women and 74.3% for men with an overall rate of 77.15%. With the use of 1-mm slice thickness CT, morphometric analysis of maxillary sinuses will be helpful for gender determination.

Toward intensifying design of experiments in upstream bioprocess development: An industrial Escherichia coli feasibility study.

PubMed

von Stosch, Moritz; Hamelink, Jan-Martijn; Oliveira, Rui

2016-09-01

In this study, step variations in temperature, pH, and carbon substrate feeding rate were performed within five high cell density Escherichia coli fermentations to assess whether intraexperiment step changes, can principally be used to exploit the process operation space in a design of experiment manner. A dynamic process modeling approach was adopted to determine parameter interactions. A bioreactor model was integrated with an artificial neural network that describes biomass and product formation rates as function of varied fed-batch fermentation conditions for heterologous protein production. A model reliability measure was introduced to assess in which process region the model can be expected to predict process states accurately. It was found that the model could accurately predict process states of multiple fermentations performed at fixed conditions within the determined validity domain. The results suggest that intraexperimental variations of process conditions could be used to reduce the number of experiments by a factor, which in limit would be equivalent to the number of intraexperimental variations per experiment. © 2016 American Institute of Chemical Engineers Biotechnol. Prog., 32:1343-1352, 2016. © 2016 American Institute of Chemical Engineers.

Early Onset of Kinetic Roughening due to a Finite Step Width in Hematin Crystallization

NASA Astrophysics Data System (ADS)

Olafson, Katy N.; Rimer, Jeffrey D.; Vekilov, Peter G.

2017-11-01

The structure of the interface of a growing crystal with its nutrient phase largely determines the growth dynamics. We demonstrate that hematin crystals, crucial for the survival of malaria parasites, transition from faceted to rough growth interfaces at increasing thermodynamic supersaturation Δ μ . Contrary to theoretical predictions and previous observations, this transition occurs at moderate values of Δ μ . Moreover, surface roughness varies nonmonotonically with Δ μ , and the rate constant for rough growth is slower than that resulting from nucleation and spreading of layers. We attribute these unexpected behaviors to the dynamics of step growth dominated by surface diffusion and the loss of identity of nuclei separated by less than the step width w . We put forth a general criterion for the onset of kinetic roughening using w as a critical length scale.

A study of video frame rate on the perception of moving imagery detail

NASA Technical Reports Server (NTRS)

Haines, Richard F.; Chuang, Sherry L.

1993-01-01

The rate at which each frame of color moving video imagery is displayed was varied in small steps to determine what is the minimal acceptable frame rate for life scientists viewing white rats within a small enclosure. Two, twenty five second-long scenes (slow and fast animal motions) were evaluated by nine NASA principal investigators and animal care technicians. The mean minimum acceptable frame rate across these subjects was 3.9 fps both for the slow and fast moving animal scenes. The highest single trial frame rate averaged across all subjects for the slow and the fast scene was 6.2 and 4.8, respectively. Further research is called for in which frame rate, image size, and color/gray scale depth are covaried during the same observation period.

Lateral and vertical facies relationships of bedforms deposited by aggrading supercritical flows: From cyclic steps to humpback dunes

NASA Astrophysics Data System (ADS)

Lang, Jörg; Winsemann, Jutta

2013-10-01

The preservation of bedforms related to supercritical flows and hydraulic jumps is commonly considered to be rare in the geologic record, although these bedforms are known from a variety of depositional environments. This field-based study presents a detailed analysis of the sedimentary facies and stacking pattern of deposits of cyclic steps, chutes-and-pools, antidunes and humpback dunes from three-dimensional outcrops. The well exposed Middle Pleistocene successions from northern Germany comprise glacilacustrine ice-contact subaqueous fan and glacial lake-outburst flood deposits. The studied successions give new insights into the depositional architecture of bedforms related to supercritical flows and may serve as an analogue for other high-energy depositional environments such as fluvial settings, coarse-grained deltas or turbidite systems. Deposits of cyclic steps occur within the glacial lake-outburst flood succession and are characterised by lenticular scours infilled by gently to steeply dipping backsets. Cyclic steps formed due to acceleration and flow thinning when the glacial lake-outburst flood spilled over a push-moraine ridge. These bedforms are commonly laterally and vertically truncated and alternate with deposits of chutes-and-pools and antidunes. The subaqueous fan successions are dominated by laterally extensive sinusoidal waveforms, which are interpreted as deposits of aggrading stationary antidunes, which require quasi-steady flows at the lower limit of the supercritical flow stage and high rates of sedimentation. Humpback dunes are characterised by downflow divergent cross-stratification, displaying differentiation into topsets, foresets and bottomsets, and are interpreted as deposited at the transition from subcritical to supercritical flow conditions or vice versa. Gradual lateral and vertical transitions between humpback dunes and antidune deposits are very common. The absence of planar-parallel stratification in all studied successions suggests that the formation of these bedforms is suppressed in flows characterised by hydraulic jumps under highly aggradational conditions. The large-scale lateral and vertical successions of bedforms are interpreted as representing the temporal and spatial evolution of the initial supercritical flows, which was strongly affected by the occurrence of hydraulic jumps. Small-scale facies changes and the formation of individual bedforms are interpreted as controlled by fluctuating discharge, bed topography and pulsating unstable flows.

External and Intraparticle Diffusion of Coumarin 102 with Surfactant in the ODS-silica Gel/water System by Single Microparticle Injection and Confocal Fluorescence Microspectroscopy.

PubMed

Nakatani, Kiyoharu; Matsuta, Emi

2015-01-01

The release mechanism of coumarin 102 from a single ODS-silica gel microparticle into the water phase in the presence of Triton X-100 was investigated by confocal fluorescence microspectroscopy combined with the single microparticle injection technique. The release rate significantly depended on the Triton X-100 concentration in the water phase and was not limited by diffusion in the pores of the microparticle. The release rate constant was inversely proportional to the microparticle radius squared, indicating that the rate-determining step is the external diffusion between the microparticle and the water phase.

A first step to compare geodynamical models and seismic observations of the inner core

NASA Astrophysics Data System (ADS)

Lasbleis, M.; Waszek, L.; Day, E. A.

2016-12-01

Seismic observations have revealed a complex inner core, with lateral and radial heterogeneities at all observable scales. The dominant feature is the east-west hemispherical dichotomy in seismic velocity and attenuation. Several geodynamical models have been proposed to explain the observed structure: convective instabilities, external forces, crystallisation processes or influence of outer core convection. However, interpreting such geodynamical models in terms of the seismic observations is difficult, and has been performed only for very specific models (Geballe 2013, Lincot 2014, 2016). Here, we propose a common framework to make such comparisons. We have developed a Python code that propagates seismic ray paths through kinematic geodynamical models for the inner core, computing a synthetic seismic data set that can be compared to seismic observations. Following the method of Geballe 2013, we start with the simple model of translation. For this, the seismic velocity is proposed to be function of the age or initial growth rate of the material (since there is no deformation included in our models); the assumption is reasonable when considering translation, growth and super rotation of the inner core. Using both artificial (random) seismic ray data sets and a real inner core data set (from Waszek et al. 2011), we compare these different models. Our goal is to determine the model which best matches the seismic observations. Preliminary results show that super rotation successfully creates an eastward shift in properties with depth, as has been observed seismically. Neither the growth rate of inner core material nor the relationship between crystal size and seismic velocity are well constrained. Consequently our method does not directly compute the seismic travel times. Instead, here we use age, growth rate and other parameters as proxies for the seismic properties, which represent a good first step to compare geodynamical and seismic observations.Ultimately we aim to release our codes to broader scientific community, allowing researchers from all disciplines to test their models of inner core growth against seismic observations or create a kinematic model for the evolution of the inner core which matches new geophysical observations.

Common path point diffraction interferometer using liquid crystal phase shifting

NASA Technical Reports Server (NTRS)

Mercer, Carolyn R. (Inventor)

1997-01-01

A common path point diffraction interferometer uses dyed, parallel nematic liquid crystals which surround an optically transparent microsphere. Coherent, collimated and polarized light is focused on the microsphere at a diameter larger than that of the microsphere. A portion of the focused light passes through the microsphere to form a spherical wavefront reference beam and the rest of the light is attenuated by the dyed liquid crystals to form an object beam. The two beams form an interferogram which is imaged by a lens onto an electronic array sensor and into a computer which determines the wavefront of the object beam. The computer phase shifts the interferogram by stepping up an AC voltage applied across the liquid crystals without affecting the reference beam.

One size fits all electronics for insole-based activity monitoring.

PubMed

Hegde, Nagaraj; Bries, Matthew; Melanson, Edward; Sazonov, Edward

2017-07-01

Footwear based wearable sensors are becoming prominent in many areas of monitoring health and wellness, such as gait and activity monitoring. In our previous research we introduced an insole based wearable system SmartStep, which is completely integrated in a socially acceptable package. From a manufacturing perspective, SmartStep's electronics had to be custom made for each shoe size, greatly complicating the manufacturing process. In this work we explore the possibility of making a universal electronics platform for SmartStep - SmartStep 3.0, which can be used in the most common insole sizes without modifications. A pilot human subject experiments were run to compare the accuracy between the one-size fits all (SmartStep 3.0) and custom size SmartStep 2.0. A total of ~10 hours of data was collected in the pilot study involving three participants performing different activities of daily living while wearing SmartStep 2.0 and SmartStep 3.0. Leave one out cross validation resulted in a 98.5% average accuracy from SmartStep 2.0, while SmartStep 3.0 resulted in 98.3% accuracy, suggesting that the SmartStep 3.0 can be as accurate as SmartStep 2.0, while fitting most common shoe sizes.

Improving the effectiveness of psychotherapy in two public hospitals in Nairobi

PubMed Central

Falkenström, Fredrik; Gee, Matthew David; Kuria, Mary Wangari; Othieno, Caleb Joseph; Kumar, Manasi

2017-01-01

This paper is the first in a planned series of papers studying the effectiveness of psychotherapy and counselling in Nairobi. It describes a method for checking the effectiveness of psychotherapy and improving service quality in a Kenyan context. Rather than prematurely imposing psychotherapy protocols developed in Western countries in another cultural context, we believe that first studying psychological interventions as they are practised may generate understanding of which psychological problems are common, what interventions therapists use, and what seems to be effective in reducing psychiatric problems. The initial step is to assess outcome of psychological treatments as they are conducted. This is followed by statistical analyses aimed at identifying patient groups who are not improving at acceptable rates. Therapists will then be trained in a ‘best practice’ approach, and controlled trials are used in a final step, testing new interventions specifically targeted at patient groups with sub-optimal outcomes. PMID:29093948

Improving the effectiveness of psychotherapy in two public hospitals in Nairobi.

PubMed

Falkenström, Fredrik; Gee, Matthew David; Kuria, Mary Wangari; Othieno, Caleb Joseph; Kumar, Manasi

2017-08-01

This paper is the first in a planned series of papers studying the effectiveness of psychotherapy and counselling in Nairobi. It describes a method for checking the effectiveness of psychotherapy and improving service quality in a Kenyan context. Rather than prematurely imposing psychotherapy protocols developed in Western countries in another cultural context, we believe that first studying psychological interventions as they are practised may generate understanding of which psychological problems are common, what interventions therapists use, and what seems to be effective in reducing psychiatric problems. The initial step is to assess outcome of psychological treatments as they are conducted. This is followed by statistical analyses aimed at identifying patient groups who are not improving at acceptable rates. Therapists will then be trained in a 'best practice' approach, and controlled trials are used in a final step, testing new interventions specifically targeted at patient groups with sub-optimal outcomes.

Assay Methods for ACS Activity and ACS Phosphorylation by MAP Kinases In Vitro and In Vivo.

PubMed

Han, Xiaomin; Li, Guojing; Zhang, Shuqun

2017-01-01

Ethylene, a gaseous phytohormone, has profound effects on plant growth, development, and adaptation to the environment. Ethylene-regulated processes begin with the induction of ethylene biosynthesis. There are two key steps in ethylene biosynthesis. The first is the biosynthesis of 1-aminocyclopropane-1-carboxylic acid (ACC) from S-Adenosyl-Methionine (SAM), a common precursor in many metabolic pathways, which is catalyzed by ACC synthase (ACS). The second is the oxidative cleavage of ACC to form ethylene under the action of ACC oxidase (ACO). ACC biosynthesis is the committing and generally the rate-limiting step in ethylene biosynthesis. As a result, characterizing the cellular ACS activity and understanding its regulation are important. In this chapter, we detail the methods used to measure, (1) the enzymatic activity of both recombinant and native ACS proteins, and (2) the phosphorylation of ACS protein by mitogen-activated protein kinases (MAPKs) in vivo and in vitro.