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.

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.

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.

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.

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.

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...

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.

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

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.

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.

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.

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.

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.

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

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)…

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.

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.

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.

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.

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.

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

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

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...

Understanding the mechanisms of solid-water reactions through analysis of surface topography.

PubMed

Bandstra, Joel Z; Brantley, Susan L

2015-12-01

The topography of a reactive surface contains information about the reactions that form or modify the surface and, therefore, it should be possible to characterize reactivity using topography parameters such as surface area, roughness, or fractal dimension. As a test of this idea, we consider a two-dimensional (2D) lattice model for crystal dissolution and examine a suite of topography parameters to determine which may be useful for predicting rates and mechanisms of dissolution. The model is based on the assumption that the reactivity of a surface site decreases with the number of nearest neighbors. We show that the steady-state surface topography in our model system is a function of, at most, two variables: the ratio of the rate of loss of sites with two neighbors versus three neighbors (d(2)/d(3)) and the ratio of the rate of loss of sites with one neighbor versus three neighbors (d(1)/d(3)). This means that relative rates can be determined from two parameters characterizing the topography of a surface provided that the two parameters are independent of one another. It also means that absolute rates cannot be determined from measurements of surface topography alone. To identify independent sets of topography parameters, we simulated surfaces from a broad range of d(1)/d(3) and d(2)/d(3) and computed a suite of common topography parameters for each surface. Our results indicate that the fractal dimension D and the average spacing between steps, E[s], can serve to uniquely determine d(1)/d(3) and d(2)/d(3) provided that sufficiently strong correlations exist between the steps. Sufficiently strong correlations exist in our model system when D>1.5 (which corresponds to D>2.5 for real 3D reactive surfaces). When steps are uncorrelated, surface topography becomes independent of step retreat rate and D is equal to 1.5. Under these conditions, measures of surface topography are not independent and any single topography parameter contains all of the available mechanistic information about the surface. Our results also indicate that root-mean-square roughness cannot be used to reliably characterize the surface topography of fractal surfaces because it is an inherently noisy parameter for such surfaces with the scale of the noise being independent of length scale.

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.

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.

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.

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

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.

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

Chemical reactions at aqueous interfaces

NASA Astrophysics Data System (ADS)

Vecitis, Chad David

2009-12-01

Interfaces or phase boundaries are a unique chemical environment relative to individual gas, liquid, or solid phases. Interfacial reaction mechanisms and kinetics are often at variance with homogeneous chemistry due to mass transfer, molecular orientation, and catalytic effects. Aqueous interfaces are a common subject of environmental science and engineering research, and three environmentally relevant aqueous interfaces are investigated in this thesis: 1) fluorochemical sonochemistry (bubble-water), 2) aqueous aerosol ozonation (gas-water droplet), and 3) electrolytic hydrogen production and simultaneous organic oxidation (water-metal/semiconductor). Direct interfacial analysis under environmentally relevant conditions is difficult, since most surface-specific techniques require relatively `extreme' conditions. Thus, the experimental investigations here focus on the development of chemical reactors and analytical techniques for the completion of time/concentration-dependent measurements of reactants and their products. Kinetic modeling, estimations, and/or correlations were used to extract information on interfacially relevant processes. We found that interfacial chemistry was determined to be the rate-limiting step to a subsequent series of relatively fast homogeneous reactions, for example: 1) Pyrolytic cleavage of the ionic headgroup of perfluorooctanesulfonate (PFOS) and perfluorooctanoate (PFOA) adsorbed to cavitating bubble-water interfaces during sonolysis was the rate-determining step in transformation to their inorganic constituents carbon monoxide, carbon dioxide, and fluoride; 2) ozone oxidation of aqueous iodide to hypoiodous acid at the aerosol-gas interface is the rate-determining step in the oxidation of bromide and chloride to dihalogens; 3) Electrolytic oxidation of anodic titanol surface groups is rate-limiting for the overall oxidation of organics by the dichloride radical. We also found chemistry unique to the interface, for example: 1) Adsorption of dilute PFOS(aq) and PFOA(aq) to acoustically cavitating bubble interfaces was greater than equilibrium expectations due to high-velocity bubble radial oscillations; 2) Relative ozone oxidation kinetics of aqueous iodide, sulfite, and thiosulfate were at variance with previously reported bulk aqueous kinetics; 3) Organics that directly chelated with the anode surface were oxidized by direct electron transfer, resulting in immediate carbon dioxide production but slower overall oxidation kinetics. Chemical reactions at aqueous interfaces can be the rate-limiting step of a reaction network and often display novel mechanisms and kinetics as compared to homogeneous chemistry.

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.

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.

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.

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.

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.

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.

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.

Increasing preferred step rate during running reduces plantar pressures.

PubMed

Gerrard, James M; Bonanno, Daniel R

2018-01-01

Increasing preferred step rate during running is a commonly used strategy in the management of running-related injuries. This study investigated the effect of different step rates on plantar pressures during running. Thirty-two healthy runners ran at a comfortable speed on a treadmill at five step rates (preferred, ±5%, and ±10%). For each step rate, plantar pressure data were collected using the pedar-X in-shoe system. Compared to running with a preferred step rate, a 10% increase in step rate significantly reduced peak pressure (144.5±46.5 vs 129.3±51 kPa; P=.033) and maximum force (382.3±157.6 vs 334.0±159.8 N; P=.021) at the rearfoot, and reduced maximum force (426.4±130.4 vs 400.0±116.6 N; P=.001) at the midfoot. In contrast, a 10% decrease in step rate significantly increased peak pressure (144.5±46.5 vs 161.5±49.3 kPa; P=.011) and maximum force (382.3±157.6 vs 425.4±155.3 N; P=.032) at the rearfoot. Changing step rate by 5% provided no effect on plantar pressures, and no differences in plantar pressures were observed at the medial forefoot, lateral forefoot or hallux between the step rates. This study's findings indicate that increasing preferred step rate by 10% during running will reduce plantar pressures at the rearfoot and midfoot, while decreasing step rate by 10% will increase plantar pressures at the rearfoot. However, changing preferred step rate by 5% will provide no effect on plantar pressures, and forefoot pressures are unaffected by changes in step rate. © 2017 John Wiley & Sons A/S. Published by John Wiley & Sons Ltd.

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.

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.

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.

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.

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

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.

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...

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.

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.

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.

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

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.

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

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.

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.

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

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.

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

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.

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.

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

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.

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.

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,...

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

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…

Effects of step rate manipulation on joint mechanics during running.

PubMed

Heiderscheit, Bryan C; Chumanov, Elizabeth S; Michalski, Max P; Wille, Christa M; Ryan, Michael B

2011-02-01

the objective of this study was to characterize the biomechanical effects of step rate modification during running on the hip, knee, and ankle joints so as to evaluate a potential strategy to reduce lower extremity loading and risk for injury. three-dimensional kinematics and kinetics were recorded from 45 healthy recreational runners during treadmill running at constant speed under various step rate conditions (preferred, ± 5%, and ± 10%). We tested our primary hypothesis that a reduction in energy absorption by the lower extremity joints during the loading response would occur, primarily at the knee, when step rate was increased. less mechanical energy was absorbed at the knee (P < 0.01) during the +5% and +10% step rate conditions, whereas the hip (P < 0.01) absorbed less energy during the +10% condition only. All joints displayed substantially (P < 0.01) more energy absorption when preferred step rate was reduced by 10%. Step length (P < 0.01), center of mass vertical excursion (P < 0.01), braking impulse (P < 0.01), and peak knee flexion angle (P < 0.01) were observed to decrease with increasing step rate. When step rate was increased 10% above preferred, peak hip adduction angle (P < 0.01) and peak hip adduction (P < 0.01) and internal rotation (P < 0.01) moments were found to decrease. we conclude that subtle increases in step rate can substantially reduce the loading to the hip and knee joints during running and may prove beneficial in the prevention and treatment of common running-related injuries.

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

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

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

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

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

DOE PAGES

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

2016-03-19

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

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.

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

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.

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

Effects of Step Rate Manipulation on Joint Mechanics during Running

PubMed Central

Heiderscheit, Bryan C.; Chumanov, Elizabeth S.; Michalski, Max P.; Wille, Christa M.; Ryan, Michael B.

2010-01-01

Purpose The objective of this study was to characterize the biomechanical effects of step rate modification during running on the hip, knee and ankle joints, so as to evaluate a potential strategy to reduce lower extremity loading and risk for injury. Methods Three-dimensional kinematics and kinetics were recorded from 45 healthy recreational runners during treadmill running at constant speed under various step rate conditions (preferred, ± 5% and ± 10%). We tested our primary hypothesis that a reduction in energy absorption by the lower extremity joints during the loading response would occur, primarily at the knee, when step rate was increased. Results Less mechanical energy was absorbed at the knee (p<0.01) during the +5% and +10% step rate conditions, while the hip (p<0.01) absorbed less energy during the +10% condition only. All joints displayed substantially (p<0.01) more energy absorption when preferred step rate was reduced by 10. Step length (p<0.01), center of mass vertical excursion (p<0.01), breaking impulse (p<0.01) and peak knee flexion angle (p<0.01) were observed to decrease with increasing step rate. When step rate was increased 10% above preferred, peak hip adduction angle (p<0.01), as well as peak hip adduction (p<0.01) and internal rotation (p<0.01) moments, were found to decrease. Conclusion We conclude that subtle increases in step rate can substantially reduce the loading to the hip and knee joints during running and may prove beneficial in the prevention and treatment of common running-related injuries. PMID:20581720

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.

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.

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.

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.

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

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.

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.

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.

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.

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.

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.

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.

Identifying Medical Students Likely to Exhibit Poor Professionalism and Knowledge During Internship

PubMed Central

Durning, Steven J.; Cohen, Daniel L.; Cruess, David; Jackson, Jeffrey L.

2007-01-01

CONTEXT Identifying medical students who will perform poorly during residency is difficult. OBJECTIVE Determine whether commonly available data predicts low performance ratings during internship by residency program directors. DESIGN Prospective cohort involving medical school data from graduates of the Uniformed Services University (USU), surveys about experiences at USU, and ratings of their performance during internship by their program directors. SETTING Uniformed Services University. PARTICIPANTS One thousand sixty-nine graduates between 1993 and 2002. MAIN OUTCOME MEASURE(S) Residency program directors completed an 18-item survey assessing intern performance. Factor analysis of these items collapsed to 2 domains: knowledge and professionalism. These domains were scored and performance dichotomized at the 10th percentile. RESULTS Many variables showed a univariate relationship with ratings in the bottom 10% of both domains. Multivariable logistic regression modeling revealed that grades earned during the third year predicted low ratings in both knowledge (odds ratio [OR] = 4.9; 95%CI = 2.7–9.2) and professionalism (OR = 7.3; 95%CI = 4.1–13.0). USMLE step 1 scores (OR = 1.03; 95%CI = 1.01–1.05) predicted knowledge but not professionalism. The remaining variables were not independently predictive of performance ratings. The predictive ability for the knowledge and professionalism models was modest (respective area under ROC curves = 0.735 and 0.725). CONCLUSIONS A strong association exists between the third year GPA and internship ratings by program directors in professionalism and knowledge. In combination with third year grades, either the USMLE step 1 or step 2 scores predict poor knowledge ratings. Despite a wealth of available markers and a large data set, predicting poor performance during internship remains difficult. PMID:17952512

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

[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.

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

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

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...

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...

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.

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.

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.

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.

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

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.

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.

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.

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

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.

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.

A Method for Harmonic Sources Detection based on Harmonic Distortion Power Rate

NASA Astrophysics Data System (ADS)

Lin, Ruixing; Xu, Lin; Zheng, Xian

2018-03-01

Harmonic sources detection at the point of common coupling is an essential step for harmonic contribution determination and harmonic mitigation. The harmonic distortion power rate index is proposed for harmonic source location based on IEEE Std 1459-2010 in the paper. The method only based on harmonic distortion power is not suitable when the background harmonic is large. To solve this problem, a threshold is determined by the prior information, when the harmonic distortion power is larger than the threshold, the customer side is considered as the main harmonic source, otherwise, the utility side is. A simple model of public power system was built in MATLAB/Simulink and field test results of typical harmonic loads verified the effectiveness of proposed method.

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.

Prism adaptation and generalization during visually guided locomotor tasks.

PubMed

Alexander, M Scott; Flodin, Brent W G; Marigold, Daniel S

2011-08-01

The ability of individuals to adapt locomotion to constraints associated with the complex environments normally encountered in everyday life is paramount for survival. Here, we tested the ability of 24 healthy young adults to adapt to a rightward prism shift (∼11.3°) while either walking and stepping to targets (i.e., precision stepping task) or stepping over an obstacle (i.e., obstacle avoidance task). We subsequently tested for generalization to the other locomotor task. In the precision stepping task, we determined the lateral end-point error of foot placement from the targets. In the obstacle avoidance task, we determined toe clearance and lateral foot placement distance from the obstacle before and after stepping over the obstacle. We found large, rightward deviations in foot placement on initial exposure to prisms in both tasks. The majority of measures demonstrated adaptation over repeated trials, and adaptation rates were dependent mainly on the task. On removal of the prisms, we observed negative aftereffects for measures of both tasks. Additionally, we found a unilateral symmetric generalization pattern in that the left, but not the right, lower limb indicated generalization across the 2 locomotor tasks. These results indicate that the nervous system is capable of rapidly adapting to a visuomotor mismatch during visually demanding locomotor tasks and that the prism-induced adaptation can, at least partially, generalize across these tasks. The results also support the notion that the nervous system utilizes an internal model for the control of visually guided locomotion.

Structure of a low-population intermediate state in the release of an enzyme product.

PubMed

De Simone, Alfonso; Aprile, Francesco A; Dhulesia, Anne; Dobson, Christopher M; Vendruscolo, Michele

2015-01-09

Enzymes can increase the rate of biomolecular reactions by several orders of magnitude. Although the steps of substrate capture and product release are essential in the enzymatic process, complete atomic-level descriptions of these steps are difficult to obtain because of the transient nature of the intermediate conformations, which makes them largely inaccessible to standard structure determination methods. We describe here the determination of the structure of a low-population intermediate in the product release process by human lysozyme through a combination of NMR spectroscopy and molecular dynamics simulations. We validate this structure by rationally designing two mutations, the first engineered to destabilise the intermediate and the second to stabilise it, thus slowing down or speeding up, respectively, product release. These results illustrate how product release by an enzyme can be facilitated by the presence of a metastable intermediate with transient weak interactions between the enzyme and product.

UV-induced photocatalytic degradation of aqueous acetaminophen: the role of adsorption and reaction kinetics.

PubMed

Basha, Shaik; Keane, David; Nolan, Kieran; Oelgemöller, Michael; Lawler, Jenny; Tobin, John M; Morrissey, Anne

2015-02-01

Nanostructured titania supported on activated carbon (AC), termed as integrated photocatalytic adsorbents (IPCAs), were prepared by ultrasonication and investigated for the photocatalytic degradation of acetaminophen (AMP), a common analgesic and antipyretic drug. The IPCAs showed high affinity towards AMP (in dark adsorption studies), with the amount adsorbed proportional to the TiO2 content; the highest adsorption was at 10 wt% TiO2. Equilibrium isotherm studies showed that the adsorption followed the Langmuir model, indicating the dependence of the reaction on an initial adsorption step, with maximum adsorption capacity of 28.4 mg/g for 10 % TiO2 IPCA. The effects of initial pH, catalyst amount and initial AMP concentration on the photocatalytic degradation rates were studied. Generally, the AMP photodegradation activity of the IPCAs was better than that of bare TiO2. Kinetic studies on the photocatalytic degradation of AMP under UV suggest that the degradation followed Langmuir-Hinshelwood (L-H) kinetics, with an adsorption rate constant (K) that was considerably higher than the photocatalytic rate constant (k r), indicating that the photocatalysis of AMP is the rate-determining step during the adsorption/photocatalysis process.

Stepped care in the treatment of trichotillomania.

PubMed

Rogers, Kate; Banis, Maria; Falkenstein, Martha J; Malloy, Elizabeth J; McDonough, Lauren; Nelson, Samuel O; Rusch, Natalie; Haaga, David A F

2014-04-01

There are effective treatments of trichotillomania (TTM), but access to expert providers is limited. This study tested a stepped care model aimed at improving access. Participants were 60 (95% women, 75% Caucasian, 2% Hispanic) adults (M = 33.18 years) with TTM. They were randomly assigned to immediate versus waitlist (WL) conditions for Step 1 (10 weeks of web-based self-help via StopPulling.com). After Step 1, participants chose whether to engage in Step 2 (8 sessions of in-person habit reversal training [HRT]). In Step 1, the immediate condition had a small (d = .21) but significant advantage, relative to WL, in reducing TTM symptom ratings by interviewers (masked to experimental condition but not to assessment point); there were no differences in self-reported TTM symptoms, alopecia, functional impairment, or quality of life. Step 1 was more effective for those who used the site more often. Stepped care was highly acceptable: Motivation did not decrease during Step 1; treatment satisfaction was high, and 76% enrolled in Step 2. More symptomatic patients self-selected into HRT, and on average they improved significantly. Over one third (36%) made clinically significant improvement in self-reported TTM symptoms. Considering the entire stepped care program, participants significantly reduced symptoms, alopecia, and impairment, and increased quality of life. For quality of life and symptom severity, there was some relapse by 3-month follow-up. Stepped care is acceptable, and HRT was associated with improvement. Further work is needed to determine which patients with TTM can benefit from self-help and how to reduce relapse.

A tailored intervention to promote uptake of retinal screening among young adults with type 2 diabetes - an intervention mapping approach.

PubMed

Lake, Amelia J; Browne, Jessica L; Abraham, Charles; Tumino, Dee; Hines, Carolyn; Rees, Gwyneth; Speight, Jane

2018-05-31

Young adults (18-39 years) with type 2 diabetes are at risk of early development and rapid progression of diabetic retinopathy, a leading cause of vision loss and blindness in working-age adults. Retinal screening is key to the early detection of diabetic retinopathy, with risk of vision loss significantly reduced by timely treatment thereafter. Despite this, retinal screening rates are low among this at-risk group. The objective of this study was to develop a theoretically-grounded, evidence-based retinal screening promotion leaflet, tailored to young adults with type 2 diabetes. Utilising the six steps of Intervention Mapping, our multidisciplinary planning team conducted a mixed-methods needs assessment (Step 1); identified modifiable behavioural determinants of screening behaviour and constructed a matrix of change objectives (Step 2); designed, reviewed and debriefed leaflet content with stakeholders (Steps 3 and 4); and developed program implementation and evaluation plans (Steps 5 and 6). Step 1 included in-depth qualitative interviews (N = 10) and an online survey that recruited a nationally-representative sample (N = 227), both informed by literature review. The needs assessment highlighted the crucial roles of knowledge (about diabetic retinopathy and screening), perception of personal risk, awareness of the approval of significant others and engagement with healthcare team, on retinal screening intentions and uptake. In Step 2, we selected five modifiable behavioural determinants to be targeted: knowledge, attitudes, normative beliefs, intention, and behavioural skills. In Steps 3 and 4, the "Who is looking after your eyes?" leaflet was developed, containing persuasive messages targeting each determinant and utilising engaging, cohort-appropriate imagery. In Steps 5 and 6, we planned Statewide implementation and designed a randomised controlled trial to evaluate the leaflet. This research provides an example of a systematic, evidence-based approach to the development of a simple health intervention designed to promote uptake of screening in accordance with national guidelines. The methods and findings illustrate how Intervention Mapping can be employed to develop tailored retinal screening promotion materials for specific priority populations. This paper has implications for future program planners and is intended to assist those wishing to use Intervention Mapping to create similar theoretically-driven, tailored resources.

Theoretical evidence of the observed kinetic order dependence on temperature during the N(2)O decomposition over Fe-ZSM-5.

PubMed

Guesmi, Hazar; Berthomieu, Dorothee; Bromley, Bryan; Coq, Bernard; Kiwi-Minsker, Lioubov

2010-03-28

The characterization of Fe/ZSM5 zeolite materials, the nature of Fe-sites active in N(2)O direct decomposition, as well as the rate limiting step are still a matter of debate. The mechanism of N(2)O decomposition on the binuclear oxo-hydroxo bridged extraframework iron core site [Fe(II)(mu-O)(mu-OH)Fe(II)](+) inside the ZSM-5 zeolite has been studied by combining theoretical and experimental approaches. The overall calculated path of N(2)O decomposition involves the oxidation of binuclear Fe(II) core sites by N(2)O (atomic alpha-oxygen formation) and the recombination of two surface alpha-oxygen atoms leading to the formation of molecular oxygen. Rate parameters computed using standard statistical mechanics and transition state theory reveal that elementary catalytic steps involved into N(2)O decomposition are strongly dependent on the temperature. This theoretical result was compared to the experimentally observed steady state kinetics of the N(2)O decomposition and temperature-programmed desorption (TPD) experiments. A switch of the reaction order with respect to N(2)O pressure from zero to one occurs at around 800 K suggesting a change of the rate determining step from the alpha-oxygen recombination to alpha-oxygen formation. The TPD results on the molecular oxygen desorption confirmed the mechanism proposed.

A Multi-stage Carcinogenesis Model to Investigate Caloric Restriction as a Potential Tool for Post-irradiation Mitigation of Cancer Risk

PubMed Central

Tani, Shusuke; Blyth, Benjamin John; Shang, Yi; Morioka, Takamitsu; Kakinuma, Shizuko; Shimada, Yoshiya

2016-01-01

The risk of radiation-induced cancer adds to anxiety in low-dose exposed populations. Safe and effective lifestyle changes which can help mitigate excess cancer risk might provide exposed individuals the opportunity to pro-actively reduce their cancer risk, and improve mental health and well-being. Here, we applied a mathematical multi-stage carcinogenesis model to the mouse lifespan data using adult-onset caloric restriction following irradiation in early life. We re-evaluated autopsy records with a veterinary pathologist to determine which tumors were the probable causes of death in order to calculate age-specific mortality. The model revealed that in both irradiated and unirradiated mice, caloric restriction reduced the age-specific mortality of all solid tumors and hepatocellular carcinomas across most of the lifespan, with the mortality rate dependent more on age owing to an increase in the number of predicted rate-limiting steps. Conversely, irradiation did not significantly alter the number of steps, but did increase the overall transition rate between the steps. We show that the extent of the protective effect of caloric restriction is independent of the induction of cancer from radiation exposure, and discuss future avenues of research to explore the utility of caloric restriction as an example of a potential post-irradiation mitigation strategy. PMID:27390741

On the mechanism of the palladium catalyzed intramolecular Pauson-Khand-type reaction.

PubMed

Lan, Yu; Deng, Lujiang; Liu, Jing; Wang, Can; Wiest, Olaf; Yang, Zhen; Wu, Yun-Dong

2009-07-17

Density functional theory calculations and experimental studies have been carried out on the intramolecular Pauson-Khand-Type reaction mediated by a PdCl(2)-thiourea catalyst, which proceeds under mild reaction conditions and provides a useful alternative to traditional Pauson-Khand reactions. The classical mechanism of the Pauson-Khand reaction involving the alkyne/alkene C-C bond formation as the key step has been found to be energetically unfavorable and is not in line with the experimental observations. A novel reaction mechanism has been proposed for the reaction. The first step involves the cis-halometalation of the alkyne, followed by sequential alkene and carbonyl insertion. The rate-determining fourth step is an intramolecular C-Cl oxidative addition, leading to a Pd(IV) intermediate. A C-C bond formation by reductive elimination completes the reaction. The mechanism is in agreement with the key experimental observations including (1) the need of a chloride for catalytic activity and the absence of catalysis with Pd(OAc)(2) alone; (2) the rate acceleration by the addition of LiCl; both with PdCl(2) and Pd(OAc)(2) catalysts; and (3) the preferred formation of the trans diastereomer in substituted cases. The cis halometalation and the formation and stability of the Pd(IV) intermediate is studied in detail and provides general insights into these novel steps.

Corrrelation of the Specific Rates of Solvolysis of Ethyl Fluoroformate Using the Extended Grunwald-Winstein Equation

PubMed Central

Seong, Mi Hye; Kyong, Jin Burm; Lee, Young Hoon; Kevill, Dennis N.

2009-01-01

The specific rates of solvolysis of ethyl fluoroformate have been measured at 24.2 °C in 21 pure and binary solvents. These give a satisfactory correlation over the full range of solvents when the extended Grunwald-Winstein equation is applied. The sensitivities to changes in the NT solvent nucleophilicity scale and the YCl solvent ionizing power scale, and the kF/kCl values are very similar to those for solvolyses of n-octyl fluoroformate, consistent with the addition step of an addition-elimination pathway being rate-determining. For methanolysis, a solvent deuterium isotope effect of 3.10 is compatible with the incorporation of general-base catalysis into the substitution process. For five representative solvents, studies were made at several temperatures and activation parameters determined. The results are also compared with those reported earlier for ethyl chloroformate and mechanistic conclusions are drawn. PMID:19399229

Combustion performance and scale effect from N2O/HTPB hybrid rocket motor simulations

NASA Astrophysics Data System (ADS)

Shan, Fanli; Hou, Lingyun; Piao, Ying

2013-04-01

HRM code for the simulation of N2O/HTPB hybrid rocket motor operation and scale effect analysis has been developed. This code can be used to calculate motor thrust and distributions of physical properties inside the combustion chamber and nozzle during the operational phase by solving the unsteady Navier-Stokes equations using a corrected compressible difference scheme and a two-step, five species combustion model. A dynamic fuel surface regression technique and a two-step calculation method together with the gas-solid coupling are applied in the calculation of fuel regression and the determination of combustion chamber wall profile as fuel regresses. Both the calculated motor thrust from start-up to shut-down mode and the combustion chamber wall profile after motor operation are in good agreements with experimental data. The fuel regression rate equation and the relation between fuel regression rate and axial distance have been derived. Analysis of results suggests improvements in combustion performance to the current hybrid rocket motor design and explains scale effects in the variation of fuel regression rate with combustion chamber diameter.

Artificial Aging Effects on Cryogenic Fracture Toughness of the Main Structural Alloy for the Super Lightweight Tank

NASA Technical Reports Server (NTRS)

Chen, P. S.; Stanton, W. P.

2002-01-01

In 1996, Marshall Space Flight Center developed a multistep heating rate-controlled (MSRC) aging technique that significantly enhanced cryogenic fracture toughness (CFT) and reduced the statistical spread of fracture toughness values in alloy 2195 by controlling the location and size of strengthening precipitate T1. However, it could not be readily applied to flight-related hardware production, primarily because large-scale production furnaces are unable to maintain a heating rate of 0.6 C (1 F)/hr. In August 1996, a new program was initiated to determine whether the MSRC aging treatment could be further modified to facilitate its implementation to flight hardware production. It was successfully redesigned into a simplified two-step aging treatment consisting of 132 C (270 F)/20 hr + 138 C (280 F)/40 hr. Results indicated that two-step aging can achieve the same yield strength levels as those produced by conventional aging while providing greatly improved ductility. Two-step aging proved to be very effective at enhancing CFT, enabling previously rejected materials to meet simulated service requirements. Cryogenic properties are improved by controlling T1 nucleation and growth so that they are promoted in the matrix and suppressed in the subgrain boundaries.

Visual Recognition of the Elderly Concerning Risks of Falling or Stumbling Indoors in the Home

PubMed Central

Katsura, Toshiki; Miura, Norio; Hoshino, Akiko; Usui, Kanae; Takahashi, Yasuro; Hisamoto, Seiichi

2011-01-01

Objective: The objective of this study was to verify the recognition of dangers and obstacles within a house in the elderly when walking based on analyses of gaze point fixation. Materials and Methods: The rate of recognizing indoor dangers was compared among 30 elderly, 14 middle-aged and 11 young individuals using the Eye Mark Recorder. Results: 1) All of the elderly, middle-aged and young individuals showed a high recognition rate of 100% or near 100% when ascending outdoor steps but a low rate of recognizing obstacles placed on the steps. They showed a recognition rate of about 60% when descending steps from residential premises to the street. The rate of recognizing middle steps in the elderly was significantly lower than that in younger and middle-aged individuals. Regarding recognition indoors, when ascending stairs, all of the elderly, middle-aged and young individuals showed a high recognition rate of nearly 100%. When descending stairs, they showed a recognition rate of 70-90%. However, although the recognition rate in the elderly was lower than in younger and middle-aged individuals, no significant difference was observed. 2) When moving indoors, all of the elderly, middle-aged and young individuals showed a recognition rate of 70%-80%. The recognition rate was high regarding obstacles such as floors, televisions and chests of drawers but low for obstacles in the bathroom and steps on the path. The rate of recognizing steps of doorsills forming the division between a Japanese-style room and corridor as well as obstacles in a Japanese-style room was low, and the rate in the elderly was low, being 40% or less. Conclusion: The rate of recognizing steps of doorsills as well as obstacles in a Japanese-style room was lower in the elderly in comparison with middle-aged or young individuals. PMID:25648876

Two-Step Oxidation of Refractory Gold Concentrates with Different Microbial Communities.

PubMed

Wang, Guo-Hua; Xie, Jian-Ping; Li, Shou-Peng; Guo, Yu-Jie; Pan, Ying; Wu, Haiyan; Liu, Xin-Xing

2016-11-28

Bio-oxidation is an effective technology for treatment of refractory gold concentrates. However, the unsatisfactory oxidation rate and long residence time, which cause a lower cyanide leaching rate and gold recovery, are key factors that restrict the application of traditional bio-oxidation technology. In this study, the oxidation rate of refractory gold concentrates and the adaption of microorganisms were analyzed to evaluate a newly developed two-step pretreatment process, which includes a high temperature chemical oxidation step and a subsequent bio-oxidation step. The oxidation rate and recovery rate of gold were improved significantly after the two-step process. The results showed that the highest oxidation rate of sulfide sulfur could reach to 99.01 % with an extreme thermophile microbial community when the pulp density was 5%. Accordingly, the recovery rate of gold was elevated to 92.51%. Meanwhile, the results revealed that moderate thermophiles performed better than acidophilic mesophiles and extreme thermophiles, whose oxidation rates declined drastically when the pulp density was increased to 10% and 15%. The oxidation rates of sulfide sulfur with moderate thermophiles were 93.94% and 65.73% when the pulp density was increased to 10% and 15%, respectively. All these results indicated that the two-step pretreatment increased the oxidation rate of refractory gold concentrates and is a potential technology to pretreat the refractory sample. Meanwhile, owing to the sensitivity of the microbial community under different pulp density levels, the optimization of microbial community in bio-oxidation is necessary in industry.

77 FR 56895 - Self-Regulatory Organizations; New York Stock Exchange LLC; Notice of Filing and Immediate...

Federal Register 2010, 2011, 2012, 2013, 2014

2012-09-14

... Transaction Fees To Eliminate the Step-Up Rate for Non-Floor Broker Transactions September 10, 2012. Pursuant... its Price List to eliminate the step-up rate for non-Floor broker transactions. The text of the... its Price List to eliminate the step-up rate for non-Floor broker transactions. The Exchange proposes...

Multiperspective smFRET reveals rate-determining late intermediates of ribosomal translocation.

PubMed

Wasserman, Michael R; Alejo, Jose L; Altman, Roger B; Blanchard, Scott C

2016-04-01

Directional translocation of the ribosome through the mRNA open reading frame is a critical determinant of translational fidelity. This process entails a complex interplay of large-scale conformational changes within the actively translating particle, which together coordinate the movement of tRNA and mRNA substrates with respect to the large and small ribosomal subunits. Using pre-steady state, single-molecule fluorescence resonance energy transfer imaging, we tracked the nature and timing of these conformational events within the Escherichia coli ribosome from five structural perspectives. Our investigations revealed direct evidence of structurally and kinetically distinct late intermediates during substrate movement, whose resolution determines the rate of translocation. These steps involve intramolecular events within the EF-G-GDP-bound ribosome, including exaggerated, reversible fluctuations of the small-subunit head domain, which ultimately facilitate peptidyl-tRNA's movement into its final post-translocation position.

Multi-perspective smFRET reveals rate-determining late intermediates of ribosomal translocation

PubMed Central

Wasserman, Michael R.; Alejo, Jose L.; Altman, Roger B.; Blanchard, Scott C.

2016-01-01

Directional translocation of the ribosome through the messenger RNA open reading frame is a critical determinant of translational fidelity. This process entails a complex interplay of large-scale conformational changes within the actively translating particle, which together coordinate the movement of transfer and messenger RNA substrates with respect to the large and small ribosomal subunits. Using pre-steady state, single-molecule fluorescence resonance energy transfer imaging, we have tracked the nature and timing of these conformational events within the Escherichia coli ribosome from five structural perspectives. Our investigations reveal direct evidence of structurally and kinetically distinct, late intermediates during substrate movement, whose resolution is rate-determining to the translocation mechanism. These steps involve intra-molecular events within the EFG(GDP)-bound ribosome, including exaggerated, reversible fluctuations of the small subunit head domain, which ultimately facilitate peptidyl-tRNA’s movement into its final post-translocation position. PMID:26926435

Low-Cycle Fatigue Behavior of Die-Cast Mg Alloy AZ91

NASA Astrophysics Data System (ADS)

Rettberg, Luke; Anderson, Warwick; Jones, J. Wayne

An investigation has been conducted on the influence of microstructure and artificial aging response (T6) on the low-cycle fatigue behavior of super vacuum die-cast (SVDC) AZ91. Fatigue lifetimes were determined from total strain-controlled fatigue tests for strain amplitudes of 0.2%, 0.4% and 0.6%, under fully reversed loading at a frequency of 5 Hz. Cyclic stress-strain behavior was determined using incremental step test (IST) methods. Two locations in a prototype casting with different thicknesses and, therefore, solidification rates, microstructure and porosity, were examined. In general., at all total strain amplitudes fatigue life was unaffected by microstructure refinement and was attributed to significant levels of porosity. Cyclic softening and a subsequent increased cyclic hardening rate, compared to monotonic tests, were observed, independent of microstructure. These results, fractography and damage accumulation processes, determined from metallographic sectioning, are discussed.

Role of boundary layer diffusion in vapor deposition growth of chalcogenide nanosheets: the case of GeS.

PubMed

Li, Chun; Huang, Liang; Snigdha, Gayatri Pongur; Yu, Yifei; Cao, Linyou

2012-10-23

We report a synthesis of single-crystalline two-dimensional GeS nanosheets using vapor deposition processes and show that the growth behavior of the nanosheet is substantially different from those of other nanomaterials and thin films grown by vapor depositions. The nanosheet growth is subject to strong influences of the diffusion of source materials through the boundary layer of gas flows. This boundary layer diffusion is found to be the rate-determining step of the growth under typical experimental conditions, evidenced by a substantial dependence of the nanosheet's size on diffusion fluxes. We also find that high-quality GeS nanosheets can grow only in the diffusion-limited regime, as the crystalline quality substantially deteriorates when the rate-determining step is changed away from the boundary layer diffusion. We establish a simple model to analyze the diffusion dynamics in experiments. Our analysis uncovers an intuitive correlation of diffusion flux with the partial pressure of source materials, the flow rate of carrier gas, and the total pressure in the synthetic setup. The observed significant role of boundary layer diffusions in the growth is unique for nanosheets. It may be correlated with the high growth rate of GeS nanosheets, ~3-5 μm/min, which is 1 order of magnitude higher than other nanomaterials (such as nanowires) and thin films. This fundamental understanding of the effect of boundary layer diffusions may generally apply to other chalcogenide nanosheets that can grow rapidly. It can provide useful guidance for the development of general paradigms to control the synthesis of nanosheets.

3-cyanoindole-based inhibitors of inosine monophosphate dehydrogenase: synthesis and initial structure-activity relationships.

PubMed

Dhar, T G Murali; Shen, Zhongqi; Gu, Henry H; Chen, Ping; Norris, Derek; Watterson, Scott H; Ballentine, Shelley K; Fleener, Catherine A; Rouleau, Katherine A; Barrish, Joel C; Townsend, Robert; Hollenbaugh, Diane L; Iwanowicz, Edwin J

2003-10-20

A series of novel small molecule inhibitors of inosine monophosphate dehydrogenase (IMPDH), based upon a 3-cyanoindole core, were 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 (SAR), derived from in vitro studies, for this new series of inhibitors is given.

On the kinetics of infection by pathogenic prion protein molecules

NASA Astrophysics Data System (ADS)

Durup, Jean

1997-03-01

Literature data on the transmission of spongiform encephalopathies between mammal species point to the importance of methionine residuies in species barriers. This in turn favours the assumption of an oligomerization of identical metastable pathogenic prion protein molecules as the rate-determining step in those diseases. Published experimental data on the analogous case of yeast prion proteins closely agree with the proposed scheme.

Patrol force allocation for law enforcement: An introductory planning guide

NASA Technical Reports Server (NTRS)

Sohn, R. L.; Kennedy, R. D.

1976-01-01

Previous and current methods for analyzing police patrol forces are reviewed and discussed. The steps in developing an allocation analysis procedure are defined, including the prediction of the rate of calls for service, determination of the number of patrol units needed, designing sectors, and analyzing dispatch strategies. Existing computer programs used for this purpose are briefly described, and some results of their application are given.

Design, synthesis and in vitro kinetic study of tranexamic acid prodrugs for the treatment of bleeding conditions

NASA Astrophysics Data System (ADS)

Karaman, Rafik; Ghareeb, Hiba; Dajani, Khuloud Kamal; Scrano, Laura; Hallak, Hussein; Abu-Lafi, Saleh; Mecca, Gennaro; Bufo, Sabino A.

2013-07-01

Based on density functional theory (DFT) calculations for the acid-catalyzed hydrolysis of several maleamic acid amide derivatives four tranexamic acid prodrugs were designed. The DFT results on the acid catalyzed hydrolysis revealed that the reaction rate-limiting step is determined on the nature of the amine leaving group. When the amine leaving group was a primary amine or tranexamic acid moiety, the tetrahedral intermediate collapse was the rate-limiting step, whereas in the cases by which the amine leaving group was aciclovir or cefuroxime the rate-limiting step was the tetrahedral intermediate formation. The linear correlation between the calculated DFT and experimental rates for N-methylmaleamic acids 1- 7 provided a credible basis for designing tranexamic acid prodrugs that have the potential to release the parent drug in a sustained release fashion. For example, based on the calculated B3LYP/6-31G(d,p) rates the predicted t1/2 (a time needed for 50 % of the prodrug to be converted into drug) values for tranexamic acid prodrugs ProD 1- ProD 4 at pH 2 were 556 h [50.5 h as calculated by B3LYP/311+G(d,p)] and 6.2 h as calculated by GGA: MPW1K), 253 h, 70 s and 1.7 h, respectively. Kinetic study on the interconversion of the newly synthesized tranexamic acid prodrug ProD 1 revealed that the t1/2 for its conversion to the parent drug was largely affected by the pH of the medium. The experimental t1/2 values in 1 N HCl, buffer pH 2 and buffer pH 5 were 54 min, 23.9 and 270 h, respectively.

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

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

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

2004-11-15

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

Kinetic mechanism and structural requirements of the amine-catalyzed decarboxylation of oxaloacetic acid.

PubMed

Thalji, Nabil K; Crowe, William E; Waldrop, Grover L

2009-01-02

The kinetic and chemical mechanism of amine-catalyzed decarboxylation of oxaloacetic acid at pH 8.0 has been reevaluated using a new and versatile assay. Amine-catalyzed decarboxylation of oxaloacetic acid proceeds via the formation of an imine intermediate, followed by decarboxylation of the intermediate and hydrolysis to yield pyruvate. The decrease in oxaloacetic acid was coupled to NADH formation by malate dehydrogenase, which allowed the rates of both initial carbinolamine formation (as part of the imination step) and decarboxylation to be determined. By comparing the rates observed for a variety of amines and, in particular, diamines, the structural and electronic requirements for diamine-catalyzed decarboxylation at pH 8.0 were identified. At pH 8.0, monoamines were found to be very poor catalysts, whereas some diamines, most notably ethylenediamine, were excellent catalysts. The results indicate that the second amino group of diamines enhances the rate of imine formation by acting as a proton shuttle during the carbinolamine formation step, which enables diamines to overcome high levels of solvation that would otherwise inhibit carbinolamine, and thus imine, formation. The presence of the second amino group may also enhance the rate of the carbinolamine dehydration step. In contrast to the findings of previous reports, the second amino group participates in the reaction by enhancing the rate of decarboxylation via hydrogen-bonding to the imine nitrogen to either stabilize the negative charge that develops on the imine during decarboxylation or preferentially stabilize the reactive imine over the unreactive enamine tautomer. These results provide insight into the precise catalytic mechanism of several enzymes whose reactions are known to proceed via an imine intermediate.

Simultaneous pharmacodynamic analysis of the lag and bactericidal phases exhibited by beta-lactams against Escherichia coli.

PubMed Central

Li, R C

1996-01-01

Antibiotic-bacterium interactions are complex in nature. In many cases, bacterial killing does not commence immediately after the addition of an antibiotic, and a lag period is observed. Antibiotic permeation and/or the intermediate steps that exist between antibiotic-receptor binding and expression of cell death are two major possible causes for such lag period. This study was primarily designed to determine the relationship, if any, between antibiotic concentrations and the lag periods by a modeling approach. Short-term time-kill studies were conducted for amoxicillin, ampicillin, penicillin-G, oxacillin, and dicloxacillin against Escherichia coli. In conjunction with the use of a saturable rate model to describe the concentration-dependent killing process, a first-order induction (initiation) rate constant was used to characterize the delay in bacterial killing during the lag period. For all of the beta-lactams tested, parameters describing the bactericidal effect suggest that amoxicillin and ampicillin were much more potent than oxacillin and dicloxacillin. The induction rate constant estimates for both ampicillin and amoxicillin were found to relate linearly to concentrations. Nevertheless, these induction rate constant estimates were lower for penicillin-G, oxacillin, and dicloxacillin and increased nonlinearly with concentrations until an apparent plateau was observed. These findings support the hypothesis that the permeation process is potentially a rate-limiting step for the rapid bactericidal beta-lactams such as ampicillin and amoxicillin. However, as suggested by previous observations of the various morphological changes induced by beta-lactams, the contribution of the steps following antibiotic-receptor complex formation to the lag period might be significant for the less bactericidal antibiotics such as oxacillin and dicloxacillin. Findings from the present modeling approach can potentially be used to guide future bench experimentation. PMID:8891135

Modeling metabolic networks in C. glutamicum: a comparison of rate laws in combination with various parameter optimization strategies

PubMed Central

Dräger, Andreas; Kronfeld, Marcel; Ziller, Michael J; Supper, Jochen; Planatscher, Hannes; Magnus, Jørgen B; Oldiges, Marco; Kohlbacher, Oliver; Zell, Andreas

2009-01-01

Background To understand the dynamic behavior of cellular systems, mathematical modeling is often necessary and comprises three steps: (1) experimental measurement of participating molecules, (2) assignment of rate laws to each reaction, and (3) parameter calibration with respect to the measurements. In each of these steps the modeler is confronted with a plethora of alternative approaches, e. g., the selection of approximative rate laws in step two as specific equations are often unknown, or the choice of an estimation procedure with its specific settings in step three. This overall process with its numerous choices and the mutual influence between them makes it hard to single out the best modeling approach for a given problem. Results We investigate the modeling process using multiple kinetic equations together with various parameter optimization methods for a well-characterized example network, the biosynthesis of valine and leucine in C. glutamicum. For this purpose, we derive seven dynamic models based on generalized mass action, Michaelis-Menten and convenience kinetics as well as the stochastic Langevin equation. In addition, we introduce two modeling approaches for feedback inhibition to the mass action kinetics. The parameters of each model are estimated using eight optimization strategies. To determine the most promising modeling approaches together with the best optimization algorithms, we carry out a two-step benchmark: (1) coarse-grained comparison of the algorithms on all models and (2) fine-grained tuning of the best optimization algorithms and models. To analyze the space of the best parameters found for each model, we apply clustering, variance, and correlation analysis. Conclusion A mixed model based on the convenience rate law and the Michaelis-Menten equation, in which all reactions are assumed to be reversible, is the most suitable deterministic modeling approach followed by a reversible generalized mass action kinetics model. A Langevin model is advisable to take stochastic effects into account. To estimate the model parameters, three algorithms are particularly useful: For first attempts the settings-free Tribes algorithm yields valuable results. Particle swarm optimization and differential evolution provide significantly better results with appropriate settings. PMID:19144170

The Association Between Visual Assessment of Quality of Movement and Three-Dimensional Analysis of Pelvis, Hip, and Knee Kinematics During a Lateral Step Down Test.

PubMed

Rabin, Alon; Portnoy, Sigal; Kozol, Zvi

2016-11-01

Rabin, A, Portnoy, S, and Kozol, Z. The association between visual assessment of quality of movement and three-dimensional analysis of pelvis, hip, and knee kinematics during a lateral step down test. J Strength Cond Res 30(11): 3204-3211, 2016-Altered movement patterns including contralateral pelvic drop, increased hip adduction, knee abduction, and external rotation have been previously implicated in several lower extremity pathologies. Although various methods exist for assessing movement patterns, real-time visual observation is the most readily available method. The purpose of this study was to determine whether differing visual ratings of trunk, pelvis, and knee alignment, as well as overall quality of movement, are associated with differences in 3-dimensional trunk, pelvis, hip, or knee kinematics during a lateral step down test. Trunk, pelvis, and knee alignment of 30 healthy participants performing the lateral step down were visually rated as "good" or "faulty" based on previously established criteria. An additional categorization of overall quality of movement as either good or moderate was performed based on the aggregate score of each individual rating criterion. Three-dimensional motion analysis of trunk, pelvis, hip, and knee kinematics was simultaneously performed. A faulty pelvis alignment displayed a greater peak contralateral pelvic drop (effect size [ES], 1.65; p < 0.01) and a greater peak hip adduction (ES: 1.04, p = 0.01) compared with participants with a good pelvis alignment. Participants with a faulty knee alignment displayed greater peak knee external rotation compared with participants with a good knee alignment (ES, 0.78; p = 0.02). Participants with an overall moderate quality of movement displayed increased peak contralateral pelvic drop (ES, 1.07; p = 0.01) and peak knee external rotation (ES, 0.72; p = 0.04) compared with those with an overall good quality of movement. Visual rating of quality of movement during a lateral step down test, as performed by an experienced physical therapist, is associated with differences in several kinematics previously implicated in various pathologies.

Analysis of Water Recovery Rate from the Heat Melt Compactor

NASA Technical Reports Server (NTRS)

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

2013-01-01

Human space missions generate trash with a substantial amount of plastic (20% or greater by mass). The trash also contains water trapped in food residue and paper products and other trash items. The Heat Melt Compactor (HMC) under development by NASA Ames Research Center (ARC) compresses the waste, dries it to recover water and melts the plastic to encapsulate the compressed trash. The resulting waste disk or puck represents an approximately ten-fold reduction in the volume of the initial trash loaded into the HMC. In the current design concept being pursued, the trash is compressed by a piston after it is loaded into the trash chamber. The piston face, the side walls of the waste processing chamber and the end surface in contact with the waste can be heated to evaporate the water and to melt the plastic. Water is recovered by the HMC in two phases. The first is a pre-process compaction without heat or with the heaters initially turned on but before the waste heats up. Tests have shown that during this step some liquid water may be expelled from the chamber. This water is believed to be free water (i.e., not bound with or absorbed in other waste constituents) that is present in the trash. This phase is herein termed Phase A of the water recovery process. During HMC operations, it is desired that liquid water recovery in Phase A be eliminated or minimized so that water-vapor processing equipment (e.g., condensers) downstream of the HMC are not fouled by liquid water and its constituents (i.e., suspended or dissolved matter) exiting the HMC. The primary water recovery process takes place next where the trash is further compacted while the heated surfaces reach their set temperatures for this step. This step will be referred to herein as Phase B of the water recovery process. During this step the waste chamber may be exposed to different selected pressures such as ambient, low pressure (e.g., 0.2 atm), or vacuum. The objective for this step is to remove both bound and any remaining free water in the trash by evaporation. The temperature settings of the heated surfaces are usually kept above the saturation temperature of water but below the melting temperature of the plastic in the waste during this step to avoid any encapsulation of wet trash which would reduce the amount of recovered water by blocking the vapor escape. In this paper, we analyze the water recovery rate during Phase B where the trash is heated and water leaves the waste chamber as vapor, for operation of the HMC in reduced gravity. We pursue a quasi-one-dimensional model with and without sidewall heating to determine the water recovery rate and the trash drying time. The influences of the trash thermal properties, the amount of water loading, and the distribution of the water in the trash on the water recovery rates are determined.

In vitro fertilization with cryopreserved spermatozoa in small pieces of gonad of the scallop Argopecten purpuratus (Lamarck, 1819).

PubMed

Dupré, Enrique; Covarrubias, Alejandra; Goldstein, Merari; Guerrero, Alicia; Rojas, Herman

2016-10-01

The aim of this work was to evaluate the fertilization rates through the first cleavage, obtained with fresh oocytes inseminated with sperm cryopreserved at different freezing rates (-8.8,-10 and -12 °C/min) and at two thawing rates, using cryoprotectant solution (Me2SO, at 1 M, 2 M, 3 M, 4 M and 5 M with or without egg yolk and sucrose). Sperm contained in small pieces of male gonad were frozen at the three freezing rates, stored in liquid nitrogen and later the samples were thawed at two rates by immersing the samples in water at 50 °C (rapid) or 30 °C. Control fertilization rates ranged from 69.2 ± 2.8%-45.5% ± 1.6%. To determine the best concentration of the cryoprotectant (between 1 M and 5 M), in a first step, a freezing of -15 °C/min and a rapid thawing was used. Fertilization rates ranged between 9.6 ± 2.5% and 34.6± 12.2% and the highest percentages of fertilized oocytes (34.6%) was obtained with 3 M concentration with cryoaditive. The second step, using 3 M Me2SO with cryoadditive, determined that the freezing rate -8.8 °C/min produces the best result 29 ± 2.9% of fertilized oocytes corresponding to 59.2 ± 9.1% compared to controls. Although there were no significant differences among the different freezing rates, the fertilization rate tended to be higher with a lower freezing rate. Comparing the results of the present study, which used a cryoprotective solution composed of Me2SO and a cryoadditive, to those of other studies that used Me2SO without cryoadditives, suggests that the addition of a cryoadditive to the cryoprotectant Me2SO improves the fertilizing capacity of the sperm of Argopecten purpuratus after being cryopreserved. Copyright © 2016 Elsevier Inc. All rights reserved.

Direct decarbonylation of furfural to furan: A density functional theory study on Pt-graphene

NASA Astrophysics Data System (ADS)

Fellah, Mehmet Ferdi

2017-05-01

The catalytic mechanism of direct decarbonylation of furfural to furan on Pt graphene surface has been investigated by means of density functional theory (DFT) calculations. The main catalytic mechanism proposed in this study has six steps such as furfural adsorption, dissociation of H from adsorbed furfural, dissociation of carbon monoxide (molecularly) from adsorbed complex, furan formation and desorption of products. It has been concluded that the rate determining step for direct decarbonylation of furfural to furan is furan formation step and global activation barrier for this catalytic system is 82 kJ/mol consisting of zero point energy and thermal energy corrections. Pt-graphene structure has an important role on the catalytic decarbonylation of furfural to furan without any other reactants. This accordingly points out that Pt doped graphene structure might be an encouraging catalyst for direct decarbonylation of furfural to furan molecule as a valuable chemical material.

How Conformational Dynamics of DNA Polymerase Select Correct Substrates: Experiments and Simulations

PubMed Central

Kirmizialtin, Serdal; Nguyen, Virginia; Johnson, Kenneth A.; Elber, Ron

2012-01-01

Summary Nearly every enzyme undergoes a significant change in structure after binding it’s substrate. New experimental and theoretical analyses of the role of changes in HIV reverse transcriptase structure in selecting a correct substrate are presented. Atomically detailed simulations using the Milestoning method predict a rate and free energy profile of the conformational change commensurate with experimental data. A large conformational change occurring on a ms timescale locks the correct nucleotide at the active site, but promotes release of a mismatched nucleotide. The positions along the reaction coordinate that decide the yield of the reaction are not determined by the chemical step. Rather, the initial steps of weak substrate binding and protein conformational transition significantly enrich the yield of a reaction with a correct substrate, while the same steps diminish the reaction probability of an incorrect substrate. PMID:22483109

Fundamental Reaction Pathway for Peptide Metabolism by Proteasome: Insights from First-principles Quantum Mechanical/Molecular Mechanical Free Energy Calculations

PubMed Central

Wei, Donghui; Fang, Lei; Tang, Mingsheng; Zhan, Chang-Guo

2013-01-01

Proteasome is the major component of the crucial nonlysosomal protein degradation pathway in the cells, but the detailed reaction pathway is unclear. In this study, first-principles quantum mechanical/molecular mechanical free energy calculations have been performed to explore, for the first time, possible reaction pathways for proteasomal proteolysis/hydrolysis of a representative peptide, succinyl-leucyl-leucyl-valyl-tyrosyl-7-amino-4-methylcoumarin (Suc-LLVY-AMC). The computational results reveal that the most favorable reaction pathway consists of six steps. The first is a water-assisted proton transfer within proteasome, activating Thr1-Oγ. The second is a nucleophilic attack on the carbonyl carbon of a Tyr residue of substrate by the negatively charged Thr1-Oγ, followed by the dissociation of the amine AMC (third step). The fourth step is a nucleophilic attack on the carbonyl carbon of the Tyr residue of substrate by a water molecule, accompanied by a proton transfer from the water molecule to Thr1-Nz. Then, Suc-LLVY is dissociated (fifth step), and Thr1 is regenerated via a direct proton transfer from Thr1-Nz to Thr1-Oγ. According to the calculated energetic results, the overall reaction energy barrier of the proteasomal hydrolysis is associated with the transition state (TS3b) for the third step involving a water-assisted proton transfer. The determined most favorable reaction pathway and the rate-determining step have provided a reasonable interpretation of the reported experimental observations concerning the substituent and isotopic effects on the kinetics. The calculated overall free energy barrier of 18.2 kcal/mol is close to the experimentally-derived activation free energy of ~18.3–19.4 kcal/mol, suggesting that the computational results are reasonable. PMID:24111489

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.

5 CFR 531.405 - Waiting periods for within-grade increase.

Code of Federal Regulations, 2010 CFR

2010-01-01

... step 4-52 calendar weeks of creditable service; (ii) Rate of basic pay equal to or greater than the... creditable service; and (iii) Rate of basic pay equal to or greater than the rate of basic pay at step 7-156... step 4-260 days of creditable service in a pay status over a period of not less than 52 calendar weeks...

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

Nganga, John K.; Samanamu, Christian R.; Tanski, Joseph M.

In a series of rhenium tricarbonyl complexes coordinated by asymmetric diimine ligands containing a pyridine moiety bound to an oxazoline ring were synthesized, structurally and electrochemically characterized, and screened for CO 2 reduction ability. We reported complexes are of the type Re(N-N)(CO) 3Cl, with N-N = 2-(pyridin-2-yl)-4,5-dihydrooxazole (1), 5-methyl-2-(pyridin-2-yl)-4,5-dihydrooxazole (2), and 5-phenyl-2-(pyridin-2-yl)-4,5-dihydrooxazole (3). The electrocatalytic reduction of CO 2 by these complexes was observed in a variety of solvents and proceeds more quickly in acetonitrile than in dimethylformamide (DMF) and dimethyl sulfoxide (DMSO). The analysis of the catalytic cycle for electrochemical CO 2 reduction by 1 in acetonitrile using densitymore » functional theory (DFT) supports the C–O bond cleavage step being the rate-determining step (RDS) (ΔG ‡ = 27.2 kcal mol –1). Furthermore, the dependency of the turnover frequencies (TOFs) on the donor number (DN) of the solvent also supports that C–O bond cleavage is the rate-determining step. Moreover, the calculations using explicit solvent molecules indicate that the solvent dependence likely arises from a protonation-first mechanism. Unlike other complexes derived from fac-Re(bpy)(CO) 3Cl (I; bpy = 2,2'-bipyridine), in which one of the pyridyl moieties in the bpy ligand is replaced by another imine, no catalytic enhancement occurs during the first reduction potential. Remarkably, catalysts 1 and 2 display relative turnover frequencies, (i cat/i p) 2, up to 7 times larger than that of I.« less

A facilitated diffusion model constrained by the probability isotherm: a pedagogical exercise in intuitive non-equilibrium thermodynamics.

PubMed

Chapman, Brian

2017-06-01

This paper seeks to develop a more thermodynamically sound pedagogy for students of biological transport than is currently available from either of the competing schools of linear non-equilibrium thermodynamics (LNET) or Michaelis-Menten kinetics (MMK). To this end, a minimal model of facilitated diffusion was constructed comprising four reversible steps: cis- substrate binding, cis → trans bound enzyme shuttling, trans -substrate dissociation and trans → cis free enzyme shuttling. All model parameters were subject to the second law constraint of the probability isotherm, which determined the unidirectional and net rates for each step and for the overall reaction through the law of mass action. Rapid equilibration scenarios require sensitive 'tuning' of the thermodynamic binding parameters to the equilibrium substrate concentration. All non-equilibrium scenarios show sigmoidal force-flux relations, with only a minority of cases having their quasi -linear portions close to equilibrium. Few cases fulfil the expectations of MMK relating reaction rates to enzyme saturation. This new approach illuminates and extends the concept of rate-limiting steps by focusing on the free energy dissipation associated with each reaction step and thereby deducing its respective relative chemical impedance. The crucial importance of an enzyme's being thermodynamically 'tuned' to its particular task, dependent on the cis- and trans- substrate concentrations with which it deals, is consistent with the occurrence of numerous isoforms for enzymes that transport a given substrate in physiologically different circumstances. This approach to kinetic modelling, being aligned with neither MMK nor LNET, is best described as intuitive non-equilibrium thermodynamics, and is recommended as a useful adjunct to the design and interpretation of experiments in biotransport.

A facilitated diffusion model constrained by the probability isotherm: a pedagogical exercise in intuitive non-equilibrium thermodynamics

PubMed Central

2017-01-01

This paper seeks to develop a more thermodynamically sound pedagogy for students of biological transport than is currently available from either of the competing schools of linear non-equilibrium thermodynamics (LNET) or Michaelis–Menten kinetics (MMK). To this end, a minimal model of facilitated diffusion was constructed comprising four reversible steps: cis-substrate binding, cis→trans bound enzyme shuttling, trans-substrate dissociation and trans→cis free enzyme shuttling. All model parameters were subject to the second law constraint of the probability isotherm, which determined the unidirectional and net rates for each step and for the overall reaction through the law of mass action. Rapid equilibration scenarios require sensitive ‘tuning’ of the thermodynamic binding parameters to the equilibrium substrate concentration. All non-equilibrium scenarios show sigmoidal force–flux relations, with only a minority of cases having their quasi-linear portions close to equilibrium. Few cases fulfil the expectations of MMK relating reaction rates to enzyme saturation. This new approach illuminates and extends the concept of rate-limiting steps by focusing on the free energy dissipation associated with each reaction step and thereby deducing its respective relative chemical impedance. The crucial importance of an enzyme's being thermodynamically ‘tuned’ to its particular task, dependent on the cis- and trans-substrate concentrations with which it deals, is consistent with the occurrence of numerous isoforms for enzymes that transport a given substrate in physiologically different circumstances. This approach to kinetic modelling, being aligned with neither MMK nor LNET, is best described as intuitive non-equilibrium thermodynamics, and is recommended as a useful adjunct to the design and interpretation of experiments in biotransport. PMID:28680687

A theoretical model to determine the capacity performance of shape-specific electrodes

NASA Astrophysics Data System (ADS)

Yue, Yuan; Liang, Hong

2018-06-01

A theory is proposed to explain and predict the electrochemical process during reaction between lithium ions and electrode materials. In the model, the process of reaction is proceeded into two steps, surface adsorption and diffusion of lithium ions. The surface adsorption is an instantaneous process for lithium ions to adsorb onto the surface sites of active materials. The diffusion of lithium ions into particles is determined by the charge-discharge condition. A formula to determine the maximum specific capacity of active materials at different charging rates (C-rates) is derived. The maximum specific capacity is correlated to characteristic parameters of materials and cycling - such as size, aspect ratio, surface area, and C-rate. Analysis indicates that larger particle size or greater aspect ratio of active materials and faster C-rates can reduce maximum specific capacity. This suggests that reducing particle size of active materials and slowing the charge-discharge speed can provide enhanced electrochemical performance of a battery cell. Furthermore, the model is validated by published experimental results. This model brings new understanding in quantification of electrochemical kinetics and capacity performance. It enables development of design strategies for novel electrodes and future generation of energy storage devices.

Determination of the mass transfer limiting step of dye adsorption onto commercial adsorbent by using mathematical models.

PubMed

Marin, Pricila; Borba, Carlos Eduardo; Módenes, Aparecido Nivaldo; Espinoza-Quiñones, Fernando R; de Oliveira, Silvia Priscila Dias; Kroumov, Alexander Dimitrov

2014-01-01

Reactive blue 5G dye removal in a fixed-bed column packed with Dowex Optipore SD-2 adsorbent was modelled. Three mathematical models were tested in order to determine the limiting step of the mass transfer of the dye adsorption process onto the adsorbent. The mass transfer resistance was considered to be a criterion for the determination of the difference between models. The models contained information about the external, internal, or surface adsorption limiting step. In the model development procedure, two hypotheses were applied to describe the internal mass transfer resistance. First, the mass transfer coefficient constant was considered. Second, the mass transfer coefficient was considered as a function of the dye concentration in the adsorbent. The experimental breakthrough curves were obtained for different particle diameters of the adsorbent, flow rates, and feed dye concentrations in order to evaluate the predictive power of the models. The values of the mass transfer parameters of the mathematical models were estimated by using the downhill simplex optimization method. The results showed that the model that considered internal resistance with a variable mass transfer coefficient was more flexible than the other ones and this model described the dynamics of the adsorption process of the dye in the fixed-bed column better. Hence, this model can be used for optimization and column design purposes for the investigated systems and similar ones.

Bulk-modified modified screen-printing carbon electrodes with both lactate oxidase (LOD) and horseradish peroxide (HRP) for the determination of L-lactate in flow injection analysis mode.

PubMed

Ghamouss, Fouad; Ledru, Sophie; Ruillé, Nadine; Lantier, Françoise; Boujtita, Mohammed

2006-06-16

A screen-printed carbon electrode modified with both HRP and LOD (SPCE-HRP/LOD) has been developed for the determination of L-lactate concentration in real samples. The resulting SPCE-HRP/LOD was prepared in a one-step procedure, and was then optimised as an amperometric biosensor operating at [0, -100]mV versus Ag/AgCl for L-lactate determination in flow injection mode. A significant improvement in the reproducibility (coefficient variation of about 10%) of the preparation of the biosensors was obtained when graphite powder was modified with LOD in the presence of HRP previously oxidised by periodate ion (IO4-). Optimisation studies were performed by examining the effects of LOD loading, periodation step and rate of the binder on analytical performances of SPCE-HRP/LOD. The sensitivity of the optimised SPCE-HRP/LOD to L-lactate was 0.84 nAL micromol(-1) in a detection range between 10 and 180 microMol. The possibility of using the developed biosensor to determine L-lactate concentrations in various dairy products was also evaluated.

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

NASA Astrophysics Data System (ADS)

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

2017-11-01

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

Structure sensitivity in the kinetics and the dynamics of CO oxidation over stepped Pd(335) studied by the molecular beam infrared chemiluminescence technique: Determination of working sites during the steady-state reaction

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

Uetsuka, H.; Watanabe, K.; Kimpara, H.

Kinetics and dynamics of CO oxidation have been studied on a stepped Pd(335) surface at a steady-state condition and compared with those on flat Pd(111). The infrared (IR) chemiluminescence technique was applied to determine where the active catalytic sites are on the Pd(335) surface. Since the vibrational energy state of the product CO{sub 2} is sensitive to the structures of the reaction sites on Pd surfaces, information about the working reaction sites during the steady-state CO oxidation can be obtained from the IR emission spectra of the product CO{sub 2}. The production rate of CO{sub 2} was higher on Pd(335)more » than on Pd(111), indicating that the steps on the surface enhance the catalytic activity for Co oxidation under the steady-state condition. However, the rate data do not necessarily show the real active sites for the CO + O recombination reaction. At a surface temperature of 850 K, the vibrational Boltzmann temperature (T{sub v}) of the product CO{sub 2} on Pd(335) was quite different from (much lower than) that on Pd(111), although the Pd(335) surface has four-atom wide (111) terraces. The lower T{sub v} value on Pd(335) was similar to that on Pd(110)(1 x 1), indicating that a relatively linear activated CO{sub 2} complex was formed. Therefore, during the steady-state CO oxidation on Pd(335), the reaction does not take place on the (111) terrace sites, but mostly on the step sites at 850 K. On the contrary, as the CO coverage increased at a lower surface temperature and at a high CO/O{sub 2} ratio, the T{sub v} values on Pd(335) tend to approach those on Pd(111), indicating that the contribution of the active sites on the steps is decreased and the working reaction sites shift to the (111) terrace sites.« less

Effect of rhythm on the recovery from intense exercise.

PubMed

Eliakim, Michal; Bodner, Ehud; Meckel, Yoav; Nemet, Dan; Eliakim, Alon

2013-04-01

Motivational music (music that stimulates physical activity) was previously shown to enhance the recovery from intense exercise. The aim of the present study was to isolate the effect of rhythm (presumed to be the most effective factor of motivational music) on the recovery from intense exercise. Ten young adult active men (age: 26.1 ± 1.7 years) performed 6-minute run at peak oxygen consumption speed, at 3 separate visits (random order). At 1 visit, no music was played during the recovery after exercise. In the other visits, participants listened to motivational music that was previously shown to enhance recovery (a Western CD collection of greatest hits of all times converted to dance style, 140 b·min, strong bit, played by portable MP3 device using headphones at a volume of 70 dB) or only to the rhythm beats derived from the same songs. Mean heart rate (HR), rating of perceived exertion (RPE), number of steps (measured by step counter) and blood lactate concentrations were determined at 3, 6, 9, 12, and 15 minutes of the recovery. There was no difference in HR changes during the recovery at all conditions. Compared with the recovery without music, listening to motivational music during recovery was associated with significant greater number of steps, lower absolute lactate levels, and greater mean decrease of RPE. Listening only to rhythm beats, derived from the same music, during the recovery was associated with significant greater number of steps and lower absolute lactate levels compared to recovery without music. Music was significantly more effective than rhythm only in the absolute mean number of steps. The beneficial effect of both music and rhythm was greater toward the end of the recovery period. Results suggest that listening to music during nonstructured recovery can be used by professional athletes to enhance recovery from intense exercise. Rhythm plays a very important role in the effect of music on recovery and can be used to enhance nonstructured recovery when music is unavailable or when cultural barriers and individual music preferences may apply. The optimal music and rhythm selection is yet to be determined.

A new approach for bioassays based on frequency- and time-domain measurements of magnetic nanoparticles.

PubMed

Oisjöen, Fredrik; Schneiderman, Justin F; Astalan, Andrea Prieto; Kalabukhov, Alexey; Johansson, Christer; Winkler, Dag

2010-01-15

We demonstrate a one-step wash-free bioassay measurement system capable of tracking biochemical binding events. Our approach combines the high resolution of frequency- and high speed of time-domain measurements in a single device in combination with a fast one-step bioassay. The one-step nature of our magnetic nanoparticle (MNP) based assay reduces the time between sample extraction and quantitative results while mitigating the risks of contamination related to washing steps. Our method also enables tracking of binding events, providing the possibility of, for example, investigation of how chemical/biological environments affect the rate of a binding process or study of the action of certain drugs. We detect specific biological binding events occurring on the surfaces of fluid-suspended MNPs that modify their magnetic relaxation behavior. Herein, we extrapolate a modest sensitivity to analyte of 100 ng/ml with the present setup using our rapid one-step bioassay. More importantly, we determine the size-distributions of the MNP systems with theoretical fits to our data obtained from the two complementary measurement modalities and demonstrate quantitative agreement between them. Copyright 2009 Elsevier B.V. All rights reserved.

Optimization of operating parameters of hybrid vertical down-flow constructed wetland systems for domestic sewerage treatment.

PubMed

Huang, Zhujian; Zhang, Xianning; Cui, Lihua; Yu, Guangwei

2016-09-15

In this work, three hybrid vertical down-flow constructed wetland (HVDF-CW) systems with different compound substrates were fed with domestic sewage and their pollutants removal performance under different hydraulic loading and step-feeding ratio was investigated. The results showed that the hydraulic loading and step-feeding ratio were two crucial factors determining the removal efficiency of most pollutants, while substrate types only significantly affected the removal of COD and NH4(+)-N. Generally, the lower the hydraulic loading, the better removal efficiency of all contaminants, except for TN. By contrast, the increase of step-feeding ratio would slightly reduce the removal rate of ammonium and TP but obviously promoted the TN removal. Therefore, the optimal operation of this CWs could be achieved with low hydraulic loading combined with 50% of step-feeding ratio when TN removal is the priority, whereas medium or low hydraulic loading without step-feeding would be suitable when TN removal is not taken into consideration. The obtained results in this study can provide us with a guideline for design and optimization of hybrid vertical flow constructed wetland systems to improve the pollutants removal from domestic sewage. Copyright © 2016 Elsevier Ltd. All rights reserved.

Pulse radiolysis studies of the reactions of bromine atoms and dimethyl sulfoxide bromine atom complexes with alcohols

NASA Astrophysics Data System (ADS)

Sumiyoshi, Takashi; Fujiyoshi, Ryoko; Katagiri, Miho; Sawamura, Sadashi

2007-05-01

Dimethylsulfoxide (DMSO)-Br complexes were generated by pulse radiolysis of DMSO/bromomethane mixtures and the formation mechanism and spectral characteristics of the formed complexes were investigated in detail. The rate constant for the reaction of bromine atoms with DMSO and the extinction coefficient of the complex were obtained to be 4.6×10 9 M -1 s -1 and 6300 M -1 cm -1 at the absorption maximum of 430 nm. Rate constants for the reaction of bromine atoms with a series of alcohols were determined in CBrCl 3 solutions applying a competitive kinetic method using the DMSO-Br complex as the reference system. The obtained rate constants were ˜10 8 M -1 s -1, one or two orders larger than those reported for highly polar solvents. Rate constants of DMSO-Br complexes with alcohols were determined to be ˜ 10 7 M -1 s -1. A comparison of the reactivities of Br atoms and DMSO-Br complexes with those of chlorine atoms and chlorine atom complexes which are ascribed to hydrogen abstracting reactants strongly indicates that hydrogen abstraction from alcohols is not the rate determining step in the case of Br atoms and DMSO-Br complexes.

Chlorination of 2-phenoxypropanoic acid with NCP in aqueous acetic acid: using a novel ortho-para relationship and the para/meta ratio of substituent effects for mechanism elucidation.

PubMed

Segurado, Manuel A P; Reis, João Carlos R; de Oliveira, Jaime D Gomes; Kabilan, Senthamaraikannan; Shanthi, Manohar

2007-07-06

Rate constants were measured for the oxidative chlorodehydrogenation of (R,S)-2-phenoxypropanoic acid and nine ortho-, ten para- and five meta-substituted derivatives using (R,S)-1-chloro-3-methyl-2,6-diphenylpiperidin-4-one (NCP) as chlorinating agent. The kinetics was run in 50% (v/v) aqueous acetic acid acidified with perchloric acid under pseudo-first-order conditions with respect to NCP at temperature intervals of 5 K between 298 and 318 K, except at the highest temperature for the meta derivatives. The dependence of rate constants on temperature was analyzed in terms of the isokinetic relationship (IKR). For the 20 reactions studied at five different temperatures, the isokinetic temperature was estimated to be 382 K, which suggests the preferential involvement of water molecules in the rate-determining step. The dependence of rate constants on meta and para substitution was analyzed using the tetralinear extension of the Hammett equation. The parameter lambda for the para/meta ratio of polar substituent effects was estimated to be 0.926, and its electrostatic modeling suggests the formation of an activated complex bearing an electric charge near the oxygen atom belonging to the phenoxy group. A new approach is introduced for examining the effect of ortho substituents on reaction rates. Using IKR-determined values of activation enthalpies for a set of nine pairs of substrates with a given substituent, a linear correlation is found between activation enthalpies of ortho and para derivatives. The correlation is interpreted in terms of the selectivity of the reactant toward para- or ortho-monosubstituted substrates, the slope of which being related to the ortho effect. This slope is thought to be approximated by the ratio of polar substituent effects from ortho and para positions in benzene derivatives. Using the electrostatic theory of through-space interactions and a dipole length of 0.153 nm, this ratio was calculated at various positions of a charged reaction center along the benzene C1-C4 axis, being about 2.5 near the ring and decreasing steeply with increasing distance until reaching a minimum value of -0.565 at 1.3 nm beyond the aromatic ring. Activation enthalpies and entropies were estimated for substrates bearing the isoselective substituent in either ortho and para positions, being demonstrated that they are much different from the values for the parent substrate. The electrophilic attack on the phenolic oxygen atom by the protonated chlorinating agent is proposed as the rate-determining step, this step being followed by the fast rearrangement of the intermediate thus formed, leading to products containing chlorine in the aromatic ring.

Referral for competency committee review for poor performance on the internal medicine clerkship is associated with poor performance in internship.

PubMed

Hemann, Brian A; Durning, Steven J; Kelly, William F; Dong, Ting; Pangaro, Louis N; Hemmer, Paul A

2015-04-01

To determine how students who are referred to a competency committee for concern over performance, and ultimately judged not to require remediation, perform during internship. Uniformed Services University of the Health Sciences' students who graduated between 2007 and 2011 were included in this study. We compared the performance during internship of three groups: students who were referred to the internal medicine competency committee for review who met passing criterion, students who were reviewed by the internal medicine competency committee who were determined not to have passed the clerkship and were prescribed remediation, and students who were never reviewed by this competency committee. Program Director survey results and United States Medical Licensing Examination (USMLE) Step 3 examination results were used as the outcomes of interest. The overall survey response rate for this 5-year cohort was 81% (689/853). 102 students were referred to this competency committee for review. 63/102 students were reviewed by this competency committee, given passing grades in the internal medicine clerkship, and were not required to do additional remediation. 39/102 students were given less than passing grades by this competency committee and required to perform additional clinical work in the department of medicine to remediate their performance. 751 students were never presented to this competency committee. Compared to students who were never presented for review, the group of reviewed students who did not require remediation was 5.6 times more likely to receive low internship survey ratings in the realm of professionalism, 8.6 times more likely to receive low ratings in the domain of medical expertise, and had a higher rate of USMLE Step 3 failure (9.4% vs. 2.8%). When comparing the reviewed group to students who were reviewed and also required remediation, the only significant difference between groups regarding professionalism ratings with 50% of the group requiring remediation garnering low ratings compared to 18% of the reviewed group. Students who are referred to a committee for review following completion of their internal medicine clerkship are more likely to receive poor ratings in internship and fail USMLE Step 3 compared to students whose performance in the medicine clerkship does not trigger a committee review. These findings provide validity evidence for our competency committee review in that the students identified as requiring further clinical work had significantly higher rates of poor ratings in professionalism than students who were reviewed by the competency committee but not required to remediate. Additionally, students reviewed but not required to remediate were nonetheless at risk of low internship ratings, suggesting that these students might need some intervention prior to graduation. Reprint & Copyright © 2015 Association of Military Surgeons of the U.S.

Correlation of the Rates of Solvolysis of i-Butyl Fluoroformate and a Consideration of Leaving-Group Effects

PubMed Central

Lee, Yelin; Park, Kyoung-Ho; Seong, Mi Hye; Kyong, Jin Burm; Kevill, Dennis N.

2011-01-01

The specific rates of solvolysis of isobutyl fluoroformate (1) have been measured at 40.0 °C in 22 pure and binary solvents. These results correlated well with the extended Grunwald-Winstein (G-W) equation, which incorporated the NT solvent nucleophilicity scale and the YCl solvent ionizing power scale. The sensitivities (l and m-values) to changes in solvent nucleophilicity and solvent ionizing power, and the kF/kCl values are very similar to those observed previously for solvolyses of n-octyl fluoroformate, consistent with the additional step of an addition-elimination pathway being rate-determining. The solvent deuterium isotope effect value (kMeOH/kMeOD) for methanolysis of 1 was determined, and for solvolyses in ethanol, methanol, 80% ethanol, and 70% TFE, the values of the enthalpy and the entropy of activation for the solvolysis of 1 were also determined. The results are compared with those reported earlier for isobutyl chloroformate (2) and other alkyl haloformate esters and mechanistic conclusions are drawn. PMID:22174633

Study on Kinetic Mechanism of Bastnaesite Concentrates Decomposition Using Calcium Hydroxide

NASA Astrophysics Data System (ADS)

Cen, Peng; Wu, Wenyuan; Bian, Xue

2018-06-01

The thermal decomposition of bastnaesite concentrates using calcium hydroxide was studied. Calcium hydroxide can effectively inhibit the emission of fluorine during roasting by transforming it to calcium fluoride. The decomposition rate increased with increasing reaction temperature and amount of calcium hydroxide. The decomposition kinetics were investigated. The decomposition reaction was determined to be a heterogeneous gas-solid reaction, and it followed an unreacted shrinking core model. By means of the integrated rate equation method, the reaction was proven to be kinetically first order. Different reaction models were fit to the experimental data to determine the reaction control process. The chemical reaction at the phase interface controlled the reaction rate in the temperatures ranging from 673 K to 773 K (400 °C to 500 °C) with an apparent activation energy of 82.044 kJ·mol-1. From 773 K to 973 K (500 °C to 700 °C), diffusion through the solid product's layer became the determining step, with a lower activation energy of 15.841 kJ·mol-1.

Excision of Sleeping Beauty transposons: parameters and applications to gene therapy

PubMed Central

Liu, Geyi; Aronovich, Elena L.; Cui, Zongbin; Whitley, Chester B.; Hackett, Perry B.

2007-01-01

A major problem in gene therapy is the determination of the rates at which gene transfer has occurred. Our work has focused on applications of the Sleeping Beauty (SB) transposon system as a non-viral vector for gene therapy. Excision of a transposon from a donor molecule and its integration into a cellular chromosome are catalyzed by SB transposase. In this study, we used a plasmid-based excision assay to study the excision step of transposition. We used the excision assay to evaluate the importance of various sequences that border the sites of excision inside and outside the transposon in order to determine the most active sequences for transposition from a donor plasmid. These findings together with our previous results in transposase binding to the terminal repeats suggest that the sequences in the transposon-junction of SB are involved in steps subsequent to DNA binding but before excision, and that they may have a role in transposase–transposon interaction. We found that SB transposons leave characteristically different footprints at excision sites in different cell types, suggesting that alternative repair machineries operate in concert with transposition. Most importantly, we found that the rates of excision correlate with the rates of transposition. We used this finding to assess transposition in livers of mice that were injected with the SB transposon and transposase. The excision assay appears to be a relatively quick and easy method to optimize protocols for delivery of genes in SB transposons to mammalian chromosomes in living animals. PMID:15133768

Mechanism of SO2 removal by carbon

USGS Publications Warehouse

Lizzio, Anthony A.; DeBarr, Joseph A.

1997-01-01

The reaction of SO2 with carbon (C) in the presence of O2 and H2O involves a series of reactions that leads to the formation of sulfuric acid as the final product. The rate-determining step in the overall process is the oxidation of SO2 to SO3. Three SO2 oxidation reactions are possible. Adsorbed SO2 (C−SO2) can react either with gas phase O2 or with adsorbed oxygen (C−O complex) to form sulfur trioxide (SO3), or gas phase SO2 can react directly with the C−O complex. In optimizing the SO2 removal capabilities of carbon, most studies only assume a given mechanism for SO2 adsorption and conversion to H2SO4 to be operable. The appropriate SO2 oxidation step and role of the C−O complex in this mechanism remain to be determined. The ultimate goal of this study was to prepare activated char from Illinois coal with optimal properties for low-temperature (80−150°C) removal of sulfur dioxide from coal combustion flue gas. The SO2 adsorption capacity of activated char was found to be inversely proportional to the amount of oxygen adsorbed on its surface. A temperature-programmed desorption technique was developed to titrate those sites responsible for adsorption of SO2 and conversion to H2SO4. On the basis of these results, a mechanism for SO2 removal by carbon was proposed. The derived rate expression showed SO2 adsorption to be dependent only on the fundamental rate constant and concentration of carbon atoms designated as free sites. Recent studies indicate a similar relationship exists between the rate of carbon gasification (in CO2 or H2O) and the number of reactive sites as determined by transient kinetics experiments. Utilizing the concept of active or free sites, it was possible to produce a char from Illinois coal having an SO2 adsorption capacity surpassing that of a commercial catalytic activated carbon.

Oxygen cost and physiological responses of recreational badminton match play.

PubMed

Deka, Pallav; Berg, Kris; Harder, Jeanette; Batelaan, Herman; McGRATH, Melanie

2017-06-01

Badminton, as an Olympic sport, is popular worldwide. However, the benefits of recreational badminton match play are not well known. The purpose of the study was to determine the oxygen cost of recreational badminton match play. Heart rate (HR), blood lactate (BL), rating of perceived exertion (RPE), step count and energy expenditure were also assessed. Fourteen male recreational badminton players aged 35.9±6.62 years participated in test sessions to assess oxygen uptake (VO2) and the related physiological responses of match play. During the match play sessions, participants played singles badminton matches for 30 min while wearing a portable metabolic system. VO2 and HR were continuously recorded while blood lactate and RPE were determined following warm-up, at 15 minutes and 30 minutes of match play. Step count was recorded at 15 minutes and 30 minutes of play. VO2 over 30 minutes was 34.4±5.8 mL/kg/min which was 76.1% of maximal oxygen uptake. Across three 10-minute periods of play, VO2 was not significantly different while HR was higher in the third 10-minute period than the first and second 10-minute periods (P=0.001). Mean HR over 30 minutes was 167.9±9.4 bpm. BL was significantly higher at 15 and 30 minutes than following warm-up while RPE of 17.57±1.91 after 30 minutes was significantly higher (P=0.009) than RPE of 15.79±1.63 at 15 minutes. Step count did not vary between the two 15-minute periods of play with a total of 2404±360 steps while energy expenditure over 30 minutes of play was 391.7±66 kcal. Recreational badminton match play can be categorized as vigorous intensity suggesting that it can be a viable means of achieving recommended physical activity and improving aerobic fitness.

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.

Centralized Outpatient Education Center for Patients with Diabetes at Walter Reed Army Medical Center

DTIC Science & Technology

1984-05-16

rated into the study where appropriate. Interviews with education coordinators from nonmilitary diabetes treatment facilities were evaluated and...personnel were evaluated to determine the acceptance of the concept of an outpatient education center for diabetic patients. 12 The data from the...step was to evaluate the data from 100 outpatients to ascertain the degree of acceptance of an outpatient education center for diabetic patients. The

Deconvolution of complex differential scanning calorimetry profiles for protein transitions under kinetic control.

PubMed

Toledo-Núñez, Citlali; Vera-Robles, L Iraís; Arroyo-Maya, Izlia J; Hernández-Arana, Andrés

2016-09-15

A frequent outcome in differential scanning calorimetry (DSC) experiments carried out with large proteins is the irreversibility of the observed endothermic effects. In these cases, DSC profiles are analyzed according to methods developed for temperature-induced denaturation transitions occurring under kinetic control. In the one-step irreversible model (native → denatured) the characteristics of the observed single-peaked endotherm depend on the denaturation enthalpy and the temperature dependence of the reaction rate constant, k. Several procedures have been devised to obtain the parameters that determine the variation of k with temperature. Here, we have elaborated on one of these procedures in order to analyze more complex DSC profiles. Synthetic data for a heat capacity curve were generated according to a model with two sequential reactions; the temperature dependence of each of the two rate constants involved was determined, according to the Eyring's equation, by two fixed parameters. It was then shown that our deconvolution procedure, by making use of heat capacity data alone, permits to extract the parameter values that were initially used. Finally, experimental DSC traces showing two and three maxima were analyzed and reproduced with relative success according to two- and four-step sequential models. Copyright © 2016 Elsevier Inc. All rights reserved.

Characterization of pure Ni ultrafine/nanoparticles synthesized by electromagnetic levitational gas condensation method

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

Khodaei, Azin, E-mail: Azin.Khodaei@gmail.com; Hasannasab, Malihe; Amousoltani, Narges

2016-02-15

Highlights: • Ni ultrafine/nanoparticles were produced using the single-step ELGC method. • Ar and He–20%Ar gas mixtures were used as the condensing gas under 1 atm. • Effects of gas type and flow rate on particle size distribution were investigated. • The nanoparticles showed both high saturation magnetization and low coercivity. - Abstract: In this work, Ni ultrafine/nanoparticles were directly produced using the one-step, relatively large-scale electromagnetic levitational gas condensation method. In this process, Ni vapors ascending from the levitated droplet were condensed by Ar and He–20%Ar gas mixtures under atmospheric pressure. Effects of type and flow rate of themore » condensing gas on the size, size distribution and crystallinity of Ni particles were investigated. The particles were characterized by scanning electron microscopy, X-ray diffraction and vibrating sample magnetometer (VSM). The process parameters for the synthesis of the crystalline Ni ultrafine/nanoparticles were determined.« less

Multiresponse kinetic modelling of Maillard reaction and caramelisation in a heated glucose/wheat flour system.

PubMed

Kocadağlı, Tolgahan; Gökmen, Vural

2016-11-15

The study describes the kinetics of the formation and degradation of α-dicarbonyl compounds in glucose/wheat flour system heated under low moisture conditions. Changes in the concentrations of glucose, fructose, individual free amino acids, lysine and arginine residues, glucosone, 1-deoxyglucosone, 3-deoxyglucosone, 3,4-dideoxyglucosone, 5-hydroxymethyl-2-furfural, glyoxal, methylglyoxal and diacetyl concentrations were determined to form a multiresponse kinetic model for isomerisation and degradation reactions of glucose. Degradation of Amadori product mainly produced 1-deoxyglucosone. Formation of 3-deoxyglucosone proceeded directly from glucose and also Amadori product degradation. Glyoxal formation was predominant from glucosone while methylglyoxal and diacetyl originated from 1-deoxyglucosone. Formation of 5-hydroxymethyl-2-furfural from fructose was found to be a key step. Multi-response kinetic modelling of Maillard reaction and caramelisation simultaneously indicated quantitatively predominant parallel and consecutive pathways and rate limiting steps by estimating the reaction rate constants. Copyright © 2016 Elsevier Ltd. All rights reserved.

Platinum and rhenium extraction from a spent refinery catalyst using Bacillus megaterium as a cyanogenic bacterium: statistical modeling and process optimization.

PubMed

Motaghed, M; Mousavi, S M; Rastegar, S O; Shojaosadati, S A

2014-11-01

The present study evaluated the potential of Bacillus megaterium as a cyanogenic bacterium to produce cyanide for solubilization of platinum and rhenium from a spent refinery catalyst. Response surface methodology was applied to study the effects and interaction between two main effective parameters including initial glycine concentration and pulp density. Maximum Pt and Re recovery was obtained 15.7% and 98%, respectively, under optimum conditions of 12.8 g/l initial glycine concentration and 4% (w/v) pulp density after 7 days. Increasing the free cyanide concentration to 3.6 mg/l, varying the pH from 6.7 to 9, and increasing the dissolved oxygen from 2 to 5mg/l demonstrated the growth characteristics of B. megaterium during bioleaching process. The modified shrinking core model was used to determine the rate limiting step of the process. It was found that diffusion through the product layer is the rate controlling step. Copyright © 2014 Elsevier Ltd. All rights reserved.

Breastfeeding Practices and Barriers to Implementing the Ten Steps to Successful Breastfeeding in Mississippi Hospitals.

PubMed

Alakaam, Amir; Lemacks, Jennifer; Yadrick, Kathleen; Connell, Carol; Choi, Hwanseok Winston; Newman, Ray G

2018-05-01

Mississippi has the lowest rates of breastfeeding in the United States at 6 and 12 months. There is growing evidence that the rates and duration of infant breastfeeding improve after hospitals implement the Ten Steps to Successful Breastfeeding; moreover, the Ten Steps approach is considered the standard model for evaluation of breastfeeding practices in birthplaces. Research aim: This study aimed to examine the implementation level of the Ten Steps and identify barriers to implementing the Ten Steps in Mississippi hospitals. A cross-sectional self-report survey was used to answer the research aim. Nurse managers of the birthing and maternity units of all 43 Mississippi hospitals that provided birthing and maternity care were recruited. A response rate of 72% ( N = 31) was obtained. Implementation of the Ten Steps in these hospitals was categorized as low, partial, moderate, or high. The researcher classified implementation in 29% of hospitals as moderate and in 71% as partial. The hospital level of implementation was significantly positively associated with the hospital delivery rate along with the hospital cesarean section rate per year. The main barriers for the implementation process of the Ten Steps reported were resistance to new policies, limited financial and human resources, and lack of support from national and state governments. Breastfeeding practices in Mississippi hospitals need to be improved. New policies need to be established in Mississippi to encourage hospitals to adopt the Ten Steps policies and practice in the maternity and birthing units.

Theoretical investigations on the mechanism of benzoin condensation catalyzed by pyrido[1,2-a]-2-ethyl[1,2,4]triazol-3-ylidene.

PubMed

He, Yunqing; Xue, Ying

2011-03-03

A new annulated N-heterocyclic carbene (NHC), pyrido[1,2-a]-2-ethyl[1,2,4]triazol-3-ylidene, has been synthesized and its good catalytic activity for benzoin condensation has been experimentally determined by You and co-workers recently [ Ma , Y. J. , Wei , S. P. , Lan , J. B. , Wang , J. Z. , Xie , R. G. , and You , J. S. J. Org. Chem. 2008 , 73 , 8256 ]. In this work, the mechanism of the title reaction has been intensively studied computationally by employing the density functional theory (B3LYP) method in conjunction with 6-31+G(d) and 6-311+G(2d,p) basis sets. Our results indicate that path A (in which a sequence of intermolecular proton transfers between two carbene/benzaldehyde coupling intermediates affords enamine) and path B (in which a t-BuOH assisted hydrogen transfer generates enamine) proposed on the basis of the Breslow mechanism are competitive for their similar barriers. In path A, the first intermolecular proton transfer between two N-heterocyclic carbene/benzaldehyde coupled intermediates to form tertiary alcohol and enolate anion is theoretically the rate-determining step with corresponding barrier (30.93 kcal/mol), while the t-BuOH assisted hydrogen transfer generating Breslow enamine is the rate-determining step with corresponding barrier (28.84 kcal/mol) in path B. The coupling of carbene and benzaldehyde, and the coupling of enamine and another benzaldehyde to form a C-C bond are partially rate-determining for their relatively significant barriers (24.06 and 26.95 kcal/mol, respectively), being the same in both paths A and B. Our results are in nice agreement with the experimental result in a kinetic investigation of thiazolium ion-catalyzed benzoin condensation performed by White and Leeper in 2001.

Fast and calibration free determination of first order reaction kinetics in API synthesis using in-situ ATR-FTIR.

PubMed

Rehbein, Moritz C; Husmann, Sascha; Lechner, Christian; Kunick, Conrad; Scholl, Stephan

2018-05-01

In early stages of drug development only sparse amounts of the key substances are available, which is problematic for the determination of important process data like reaction kinetics. Therefore, it is important to perform experiments as economically as possible, especially in regards to limiting compounds. Here we demonstrate the use of a temperature step experiment enabling the determination of complete reaction kinetics in a single non-isothermal experiment. In contrast to the traditionally used HPLC, the method takes advantage of the high measuring rate and the low amount of labor involved in using in-situ ATR-FTIR to determine time-dependent concentration-equivalent data. Copyright © 2017 Elsevier B.V. All rights reserved.

Inhibiting renin angiotensin system in rate limiting step by aliskiren as a new approach for preventing indomethacin induced gastric ulcers.

PubMed

Halici, Zekai; Polat, Beyzagul; Cadirci, Elif; Topcu, Atilla; Karakus, Emre; Kose, Duygu; Albayrak, Abdulmecit; Bayir, Yasin

2016-10-25

Previously blocking the renin angiotensin system (RAAS) has been effective in the prevention of gastric damage. Therefore, the aim of this study was to investigate the effects of aliskiren, and thus, direct renin blockage, in indomethacin-induced gastric damage model. Effects of aliskiren were evaluated in indomethacin-induced gastric damage model on Albino Wistar rats. Effects of famotidine has been investigated as standard antiulcer agent. Stereological analyses for ulcer area determination, biochemical analyses for oxidative status determination and molecular analyses for tissue cytokine and cyclooxygenase determination were performed on stomach tissues. In addition, to clarify antiulcer effect mechanism of aliskiren pylorus ligation-induced gastric acid secretion model was applied on rats. Aliskiren was able to inhibit indomethacin-induced ulcer formation. It also inhibited renin, and thus, decreased over-produced Angiotensin-II during ulcer formation. Aliskiren improved the oxidative status and cytokine profile of the stomach, which was most probably impaired by increased Angiotensin II concentration. Aliskiren also increased gastroprotective prostaglandin E2 concentration. Finally, aliskiren did not change the gastric acidity in pylorus ligation model. Aliskiren exerted its protective effects on stomach tissue by decreasing inflammatory cytokines and oxidative stress as a result of inhibiting the RAAS, at a rate-limiting step, as well as its end product, angiotensin II. Aliskiren also significantly increased protective factors such as PGE2, but not affect aggressive factors such as gastric acidity. Copyright © 2016 Elsevier Ireland Ltd. All rights reserved.

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.

Detailed reaction mechanism of macrophomate synthase. Extraordinary enzyme catalyzing five-step transformation from 2-pyrones to benzoates.

PubMed

Watanabe, K; Mie, T; Ichihara, A; Oikawa, H; Honma, M

2000-12-08

Macrophomate synthase from the fungus Macrophoma commelinae IFO 9570 is a Mg(II)-dependent dimeric enzyme that catalyzes an extraordinary, complex five-step chemical transformation from 2-pyrone and oxalacetate to benzoate involving decarboxylation, C-C bond formation, and dehydration. The catalytic mechanism of the whole pathway was investigated in three separate chemical steps. In the first decarboxylation step, the enzyme loses oxalacetate decarboxylation activity upon incubation with EDTA. Activity is fully restored by addition of Mg(II) and is not restored with other divalent metal cations. The dissociation constant of 0.93 x 10(-)(7) for Mg(II) and atomic absorption analysis established a 1:1 stoichiometric complex. Inhibition of pyruvate formation with 2-pyrone revealed that the actual product in the first step is a pyruvate enolate, which undergoes C-C bond formation in the presence of 2-pyrone. Incubation of substrate analogs provided aberrant adducts that were produced via C-C bond formation and rearrangement. This strongly indicates that the second step is two C-C bond formations, affording a bicyclic intermediate. Based on the stereospecificity, involvement of a Diels-Alder reaction at the second step is proposed. Incubation of the stereospecifically deuterium-labeled malate with 2-pyrones in the presence of malate dehydrogenase provided information for the stereochemical course of the reaction catalyzed by macrophomate synthase, indicating that the first decarboxylation provides pyruvate (Z)-[3-(2)H]enolate and that dehydration at the final step occurs with anti-elimination accompanied by concomitant decarboxylation. Examination of kinetic parameters in the individual steps suggests that the third step is the rate-determining step of the overall transformation.

Is pain assessment feasible as a performance indicator for Dutch nursing homes? A cross-sectional approach.

PubMed

Boerlage, Anneke A; Masman, Anniek D; Hagoort, Jacobus; Tibboel, Dick; Baar, Frans P M; van Dijk, Monique

2013-03-01

Quality of care gains transparency with the help of performance indicators. For Dutch nursing homes, the current set of performance indicators does not include pain. To determine the feasibility of pain assessment as performance indicator, information about pain prevalence and analgesic prescription in one nursing home was collected. Within the time span of 3 days, pain intensity was measured in 91% of the residents (201 out of 221), either with a numeric rating scale, a verbal rating scale, or the Rotterdam Elderly Pain Observation Scale (REPOS). Numerical rating was used for 72%, verbal rating for 3%, and REPOS observation for 25% of the residents. Pain was substantial in 65 residents (32%), who received the following analgesic prescription: World Health Organization (WHO) step 1, 45%; WHO step 3, 12%; and neuroactive agents, 5%. Thirty-eight percent of these residents were in pain and received no analgesics. Residents with substantial pain significantly more often received analgesics (p = .007). Results suggest that pain assessment is feasible in a nursing home and would stimulate staff attention to pain. Further investigation is necessary to find out if a pain algorithm is feasible and will lead to improved pain treatment. Copyright © 2013 American Society for Pain Management Nursing. Published by Elsevier Inc. All rights reserved.

How to harvest solar energy with the photosynthetic reaction center

NASA Astrophysics Data System (ADS)

Balaeff, Alexander; Reyes, Justin

Photosynthetic reaction center (PRC) is a protein complex that performs a key step in photosynthesis: the electron-hole separation driven by photon absorbtion. The PRC has a great promise for applications in solar energy harvesting and photosensing. Such applications, however, are hampered by the difficulty in extracting the photogenerated electric charge from the PRC. To that end, it was proposed to attach the PRC to a molecular wire through which the charge could be collected. In order to find the attachment point for the wire that would maximize the rate of charge outflow from the PRC, we performed a computational study of the PRC from the R. virdis bacterium. An ensemble of PRC structures generated by a molecular dynamics simulation was used to calculate the rate of charge transport from the site of initial charge separation to several trial sites on the protein surface. The Pathways model was used to calculate the charge transfer rate in each step of the network of heme co-factors through which the charge transport was presumed to proceed. A simple kinetic model was then used to determine the overall rate of the multistep charge transport. The calculations revealed several candidate sites for the molecular wire attachment, recommended for experimental verification.

Decoding nitric oxide release rates of amine-based diazeniumdiolates.

PubMed

Wang, Yan-Ni; Collins, Jack; Holland, Ryan J; Keefer, Larry K; Ivanic, Joseph

2013-08-01

Amine-based diazeniumdiolates (NONOates) have garnered widespread use as nitric oxide (NO) donors, and their potential for nitroxyl (HNO) release has more recently been realized. While NO release rates can vary significantly with the type of amine, half-lives of seconds to days under physiological conditions, there is as yet no way to determine a priori the NO or HNO production rates of a given species, and no discernible trends have manifested other than that secondary amines produce only NO (i.e., no HNO). As a step to understanding these complex systems, here we describe a procedure for modeling amine-based NONOates in water solvent that provides an excellent correlation (R(2) = 0.94) between experimentally measured dissociation rates of seven secondary amine species and their computed NO release activation energies. The significant difference in behavior of NONOates in the gas and solvent phases is also rigorously demonstrated via explicit additions of quantum mechanical water molecules. The presented results suggest that the as-yet unsynthesized simplest amine-based NONOate, the diazeniumdiolated ammonia anion [H2N-N(O)═NO(-)], could serve as an unperturbed HNO donor. These results provide a step forward toward the accurate modeling of general NO and/or HNO donors as well as for the identification of tailored prodrug candidates.

Tennis for physical health: acute age- and gender-based physiological responses to cardio tennis.

PubMed

Murphy, Alistair P; Duffield, Rob; Reid, Machar

2014-11-01

This study described physiological and perceptual responses to Cardio tennis for "younger" and "older" adult populations of both sexes for health-related outcomes. Thirty-one active participants, each with prior recreational tennis experience (∼2 years) (8 younger and 8 older males, and 7 younger and 8 older females) performed preliminary testing and a 50-minute instructor-led Cardio tennis session. Cardio tennis is a conditioning-based tennis program comprised of warm-up movements, drill-based exercises (set movement and hitting games), and competitive play scenarios. Participants performed the 20-m shuttle run test to determine maximal heart rate (HR) during preliminary testing. Before, after, and 30-minute post Cardio tennis session, HR, blood pressure (BP), rate pressure product (RPP), and capillary blood lactate and glucose were determined. Furthermore, HR and pedometer-derived step counts were measured throughout, while the session was filmed and coded for technical skill. After the session, ratings of perceived exertion, enjoyment, and challenge were obtained. Heart rate, systolic BP, and RPP were significantly increased by Cardio tennis (p ≤ 0.05), though returned to pre-exercise levels after 30 minutes (p > 0.05). Heart rate and BP did not differ between groups pre- or 30-minute postexercise (p > 0.05); however, these were lower in younger males during and higher in younger females postsession (p ≤ 0.05). Lactate and glucose concentrations were increased in all groups (p ≤ 0.05), with lactate being highest in male groups (p ≤ 0.05), without differences in glucose between groups (p > 0.05). Stroke and step counts were not different between groups (p > 0.05). Ratings of perceived exertion and perceived challenge were lowest in the younger male group compared with all other groups (p ≤ 0.05). Cardio tennis presents as an effective stimulus to invoke sufficient cardiovascular and metabolic load to benefit health and fitness, though age- and sex-based responses should be considered in prescription.

Control in the Rate-Determining Step Provides a Promising Strategy To Develop New Catalysts for CO2 Hydrogenation: A Local Pair Natural Orbital Coupled Cluster Theory Study.

PubMed

Mondal, Bhaskar; Neese, Frank; Ye, Shengfa

2015-08-03

The development of efficient catalysts with base metals for CO2 hydrogenation has always been a major thrust of interest. A series of experimental and theoretical work has revealed that the catalytic cycle typically involves two key steps, namely, base-promoted heterolytic H2 splitting and hydride transfer to CO2, either of which can be the rate-determining step (RDS) of the entire reaction. To explore the determining factor for the nature of RDS, we present herein a comparative mechanistic investigation on CO2 hydrogenation mediated by [M(H)(η(2)-H2)(PP3(Ph))](n+) (M = Fe(II), Ru(II), and Co(III); PP3(Ph) = tris(2-(diphenylphosphino)phenyl)phosphine) type complexes. In order to construct reliable free energy profiles, we used highly correlated wave function based ab initio methods of the coupled cluster type alongside the standard density functional theory. Our calculations demonstrate that the hydricity of the metal-hydride intermediate generated by H2 splitting dictates the nature of the RDS for the Fe(II) and Co(III) systems, while the RDS for the Ru(II) catalyst appears to be ambiguous. CO2 hydrogenation catalyzed by the Fe(II) complex that possesses moderate hydricity traverses an H2-splitting RDS, whereas the RDS for the high-hydricity Co(III) species is found to be the hydride transfer. Thus, our findings suggest that hydricity can be used as a practical guide in future catalyst design. Enhancing the electron-accepting ability of low-hydricity catalysts is likely to improve their catalytic performance, while increasing the electron-donating ability of high-hydricity complexes may speed up CO2 conversion. Moreover, we also established the active roles of base NEt3 in directing the heterolytic H2 splitting and assisting product release through the formation of an acid-base complex.

Associations Between Rate of Force Development Metrics and Throwing Velocity in Elite Team Handball Players: a Short Research Report

PubMed Central

Marques, Mário C.; Saavedra, Francisco J.; Abrantes, Catarina; Aidar, Felipe J.

2011-01-01

Performance assessment has become an invaluable component of monitoring participant’s development in distinct sports, yet limited and contradictory data are available in trained subjects. The purpose of this study was to examine the relationship between ball throwing velocity during a 3-step running throw in elite team handball players and selected measures of rate of force development like force, power, velocity, and bar displacement during a concentric only bench press exercise in elite male handball players. Fitteen elite senior male team handball players volunteered to participate. Each volunteer had power and bar velocity measured during a concentric only bench press test with 25, 35, and 45 kg as well as having one-repetition maximum strength determined. Ball throwing velocity was evaluated with a standard 3-step running throw using a radar gun. The results of this study indicated significant associations between ball velocity and time at maximum rate of force development (0, 66; p<0.05) and rate of force development at peak force (0,56; p<0.05) only with 25kg load. The current research indicated that ball velocity was only median associated with maximum rate of force development with light loads. A training regimen designed to improve ball-throwing velocity in elite male team handball players should emphasize bench press movement using light loads. PMID:23487363

Associations between rate of force development metrics and throwing velocity in elite team handball players: a short research report.

PubMed

Marques, Mário C; Saavedra, Francisco J; Abrantes, Catarina; Aidar, Felipe J

2011-09-01

Performance assessment has become an invaluable component of monitoring participant's development in distinct sports, yet limited and contradictory data are available in trained subjects. The purpose of this study was to examine the relationship between ball throwing velocity during a 3-step running throw in elite team handball players and selected measures of rate of force development like force, power, velocity, and bar displacement during a concentric only bench press exercise in elite male handball players. Fitteen elite senior male team handball players volunteered to participate. Each volunteer had power and bar velocity measured during a concentric only bench press test with 25, 35, and 45 kg as well as having one-repetition maximum strength determined. Ball throwing velocity was evaluated with a standard 3-step running throw using a radar gun. The results of this study indicated significant associations between ball velocity and time at maximum rate of force development (0, 66; p<0.05) and rate of force development at peak force (0,56; p<0.05) only with 25kg load. The current research indicated that ball velocity was only median associated with maximum rate of force development with light loads. A training regimen designed to improve ball-throwing velocity in elite male team handball players should emphasize bench press movement using light loads.

The Kinetics of Myosin Light Chain Kinase Activation of Smooth Muscle Myosin in an In Vitro Model System

PubMed Central

Hong, Feng; Facemyer, Kevin C.; Carter, Michael S.; Jackson, Del R.; Haldeman, Brian D.; Ruana, Nick; Sutherland, Cindy; Walsh, Michael P.; Cremo, Christine R.; Baker, Josh E.

2013-01-01

During activation of smooth muscle contraction, one myosin light chain kinase (MLCK) molecule rapidly phosphorylates many smooth muscle myosin (SMM) molecules, suggesting that muscle activation rates are influenced by the kinetics of MLCK-SMM interactions. To determine the rate-limiting step underlying activation of SMM by MLCK, we measured the kinetics of calcium-calmodulin (Ca2+-CaM)-MLCK-mediated SMM phosphorylation and the corresponding initiation of SMM-based F-actin motility in an in vitro system with SMM attached to a coverslip surface. Fitting the time course of SMM phosphorylation to a kinetic model gave an initial phosphorylation rate, kpo, of ~1.17 heads s−1·MLCK−1. Also we measured the dwell time of single QD-labeled MLCK molecules interacting with surface-attached SMM and phosphorylated SMM using total internal reflection fluorescence microscopy. From these data, the dissociation rate constant from phosphorylated SMM was 0.80 s−1, which was similar to kpo mentioned above and with rates measured in solution. This dissociation rate was essentially independent of the phosphorylation state of SMM. From calculations using our measured dissociation rates and Kds, and estimates of [SMM] and [MLCK] in muscle, we predict that the dissociation of MLCK from phosphorylated SMM is rate-limiting and that the rate of the phosphorylation step is faster than this dissociation rate. Also, association to SMM (11-46 s−1) would be much faster than to pSMM (<0.1-0.2 s−1). This suggests that the probability of MLCK interacting with unphosphorylated versus pSMM is 55-460 times greater. This would avoid sequestering MLCK to unproductive interactions with previously phosphorylated SMM, potentially leading to faster rates of phosphorylation in muscle. PMID:24144337

Preparation for Compensatory Forward Stepping in Parkinson’s Disease

PubMed Central

King, Laurie A.; St George, Rebecca J.; Carlson-Kuhta, Patricia; Nutt, John G.; Horak, Fay B.

2010-01-01

Objective To characterize preparation for compensatory stepping in people with Parkinson’s disease (PD) compared with healthy control subjects, and to determine whether levodopa medication improves preparation or the execution phases of the step. Design Observational study. Setting Outpatient neuroscience laboratory. Participants Nineteen participants with idiopathic PD tested both in the on and off levodopa states and 17 healthy subjects. Intervention Moveable platform with posterior translations of 24cm at 56cm/s. Main Outcome Measures Compensatory steps forward, in response to a backward surface translation (24cm amplitude at 56cm/s), were categorized according to the presence of an anticipatory postural adjustment (APA) before stepping: no APA, single APA, or multiple APAs. The following step parameters were calculated: step latency, step length, center of mass (CoM) average velocity, and CoM displacement at the step initiation. Results Lateral APAs were evident in 57% and 42% of trials for people with PD in the off and on medication states, respectively, compared with only 10% of trials for control subjects. Compared with subjects with PD who did not have APAs, those subjects with PD who did make an APA prior to stepping had significantly later (mean ± SEM, 356 ± 16ms vs 305 ± 8ms) and shorter (mean ± SEM, 251 ± 27mm vs 300 ± 16mm) steps, their CoM was significantly farther forward (185 ± 7mm vs 171 ± 5mm) at foot-off, and they took significantly more steps to regain equilibrium. Levodopa did not affect the preparation or execution phase of compensatory stepping. Poor axial scores and reports of freezing in the United Parkinson’s Disease Rating Scale were associated with use of 1 or more APAs before compensatory stepping. Conclusions Lateral postural preparation prior to compensatory stepping in subjects with PD was associated with inefficient balance recovery from external perturbations. PMID:20801249

Kinetics and mechanisms of iron sulfide reductions in hydrogen and in carbon monoxide

USGS Publications Warehouse

Wiltowski, T.; Hinckley, C.C.; Smith, Gerard V.; Nishizawa, T.; Saporoschenko, Mykola; Shiley, R.H.; Webster, J.R.

1987-01-01

The reduction of iron sulfides by hydrogen and by carbon monoxide has been studied using plug flow and thermogravimetric methods. The reactions were studied in the 523-723??K temperature range and were found to be first-order processes. Plug flow studies were used to correlate reaction rates between pyrite and the gases as a function of the surface area of the pyrite. The rate of H2S formation increases with the surface area of the pyrite sample. The results of thermogravimetric experiments indicate that the reactions consist of several steps. Rate constants for the pyrite reduction by H2 and by CO were obtained. The activation energies increased with degree of reduction. Values of Ea were 113.2 (step I) and 122.5 kJ/mole (step II) for pyrite reduction with CO and 99.4 (step I), 122.4 (step II), 125.2 (step III), and 142.6 kJ/mole (step IV) for pyrite reduction with hydrogen. ?? 1987.

Modeling of the oxygen reduction reaction for dense LSM thin films

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

Yang, Tao; Liu, Jian; Yu, Yang

In this study, the oxygen reduction reaction mechanism is investigated using numerical methods on a dense thin (La 1-xSr x) yMnO 3±δ film deposited on a YSZ substrate. This 1-D continuum model consists of defect chemistry and elementary oxygen reduction reaction steps coupled via reaction rates. The defect chemistry model contains eight species including cation vacancies on the A- and B-sites. The oxygen vacancy is calculated by solving species transportation equations in multiphysics simulations. Due to the simple geometry of a dense thin film, the oxygen reduction reaction was reduced to three elementary steps: surface adsorption and dissociation, incorporation onmore » the surface, and charge transfer across the LSM/YSZ interface. The numerical simulations allow for calculation of the temperature- and oxygen partial pressure-dependent properties of LSM. The parameters of the model are calibrated with experimental impedance data for various oxygen partial pressures at different temperatures. The results indicate that surface adsorption and dissociation is the rate-determining step in the ORR of LSM thin films. With the fine-tuned parameters, further quantitative analysis is performed. The activation energy of the oxygen exchange reaction and the dependence of oxygen non-stoichiometry on oxygen partial pressure are also calculated and verified using the literature results.« less

Modeling of the oxygen reduction reaction for dense LSM thin films

DOE PAGES

Yang, Tao; Liu, Jian; Yu, Yang; ...

2017-10-17

In this study, the oxygen reduction reaction mechanism is investigated using numerical methods on a dense thin (La 1-xSr x) yMnO 3±δ film deposited on a YSZ substrate. This 1-D continuum model consists of defect chemistry and elementary oxygen reduction reaction steps coupled via reaction rates. The defect chemistry model contains eight species including cation vacancies on the A- and B-sites. The oxygen vacancy is calculated by solving species transportation equations in multiphysics simulations. Due to the simple geometry of a dense thin film, the oxygen reduction reaction was reduced to three elementary steps: surface adsorption and dissociation, incorporation onmore » the surface, and charge transfer across the LSM/YSZ interface. The numerical simulations allow for calculation of the temperature- and oxygen partial pressure-dependent properties of LSM. The parameters of the model are calibrated with experimental impedance data for various oxygen partial pressures at different temperatures. The results indicate that surface adsorption and dissociation is the rate-determining step in the ORR of LSM thin films. With the fine-tuned parameters, further quantitative analysis is performed. The activation energy of the oxygen exchange reaction and the dependence of oxygen non-stoichiometry on oxygen partial pressure are also calculated and verified using the literature results.« less

Graphene oxide electrocatalyst on MnO2 air cathode as an efficient electron pump for enhanced oxygen reduction in alkaline solution

NASA Astrophysics Data System (ADS)

Basirun, Wan Jeffrey; Sookhakian, Mehran; Baradaran, Saeid; Endut, Zulkarnain; Mahmoudian, Mohammad Reza; Ebadi, Mehdi; Yousefi, Ramin; Ghadimi, Hanieh; Ahmed, Sohail

2015-03-01

Graphene oxide (GO) was deposited on the surface of a MnO2 air cathode by thermal evaporation at 50°C from a GO colloidal suspension. Fourier transformed infrared spectroscopy and field emission scanning electron microscopy confirmed the presence of GO on the MnO2 air cathode (GO-MnO2). Voltammetry and chrono-amperometry showed increased currents for the oxygen reduction reaction (ORR) in 6 M KOH solution for GO-MnO2 compared to the MnO2 cathode. The GO-MnO2 was used as an air cathode in an alkaline tin-air cell and produced a maximum power density of 13 mW cm-2, in contrast to MnO2, which produced a maximum power density of 9.2 mW cm-2. The electrochemical impedance spectroscopy results suggest that the chemical step for the ORR is the rate determining step, as proposed earlier by different researchers. It is suggested that the presence of GO and electrochemically reduced graphene oxide (ERGO) on the MnO2 surface are responsible for the increased rate of this step, whereby GO and ERGO accelerate the process of electron donation to the MnO2 and to adsorbed oxygen atoms.

Lunar gravity derived from long-period satellite motion, a proposed method

NASA Technical Reports Server (NTRS)

Ferrari, A. J.

1971-01-01

A method was devised to determine the spherical harmonic coefficients of the lunar gravity field. The method consists of a two-step data reduction and estimation process. Pseudo-Doppler data were generated simulating two different lunar orbits. The analysis included the perturbing effects of the L1 lunar gravity field, the earth, the sun, and solar radiation pressure. Orbit determinations were performed on these data and long-period orbital elements were obtained. The Kepler element rates from these solutions were used to recover L1 lunar gravity coefficients. Overall results of the experiment show that lunar gravity coefficients can be accurately determined and that the method is dynamically consistent with long-period perturbation theory.

Interconversion of CO2 and formic acid by bio-inspired Ir complexes with pendent bases.

PubMed

Fujita, Etsuko; Muckerman, James T; Himeda, Yuichiro

2013-01-01

Recent investigations of the interconversion of CO2 and formic acid using Ru, Ir and Fe complexes are summarized in this review. During the past several years, both the reaction rates and catalyst stabilities have been significantly improved. Remarkably, the interconversion (i.e., reversibility) has also been achieved under mild conditions in environmentally benign water solvent by slightly changing the pH of the aqueous solution. Only a few catalysts seem to reflect a bio-inspired design such as the use of proton responsive ligands, ligands with pendent bases or acids for a second-coordination-sphere interaction, electroresponsive ligands, and/or ligands having a hydrogen bonding function with a solvent molecule or an added reagent. The most successful of these is an iridium dinuclear complex catalyst that at least has the first three of these characteristics associated with its bridging ligand. By utilizing an acid/base equilibrium for proton removal, the ligand becomes a strong electron donor, resulting in Ir(I) character with a vacant coordination site at each metal center in slightly basic solution. Complemented by DFT calculations, kinetic studies of the rates of formate production using a related family of Ir complexes with and without such functions on the ligand reveal that the rate-determining step for the CO2 hydrogenation is likely to be H2 addition through heterolytic cleavage involving a "proton relay" through the pendent base. The dehydrogenation of formic acid, owing to the proton responsive ligands changing character under slightly acidic pH conditions, is likely to occur by a mechanism with a different rate-determining step. This article is part of a Special Issue entitled: Metals in Bioenergetics and Biomimetics Systems. Copyright © 2012 Elsevier B.V. All rights reserved.

Inhibition of the hammerhead ribozyme by neomycin.

PubMed Central

Stage, T K; Hertel, K J; Uhlenbeck, O C

1995-01-01

A series of antibiotics was tested for stimulation or inhibition of the hammerhead ribozyme cleavage reaction. Neomycin was found to be a potent inhibitor of the reaction with a Kl of 13.5 microM. Two hammerheads with well-characterized kinetics were used to determine which steps in the reaction mechanism were inhibited by neomycin. The data suggest that neomycin interacts preferentially with the enzyme-substrate complex and that this interaction leads to a reduction in the cleavage rate by stabilizing the ground state of the complex and destabilizing the transition state of the cleavage step. A comparison of neomycin with other aminoglycosides and inhibitors of hammerhead cleavage implies that the ammonium ions of neomycin are important for the antibiotic-hammerhead interaction. PMID:7489494

Approximated affine projection algorithm for feedback cancellation in hearing aids.

PubMed

Lee, Sangmin; Kim, In-Young; Park, Young-Cheol

2007-09-01

We propose an approximated affine projection (AP) algorithm for feedback cancellation in hearing aids. It is based on the conventional approach using the Gauss-Seidel (GS) iteration, but provides more stable convergence behaviour even with small step sizes. In the proposed algorithm, a residue of the weighted error vector, instead of the current error sample, is used to provide stable convergence. A new learning rate control scheme is also applied to the proposed algorithm to prevent signal cancellation and system instability. The new scheme determines step size in proportion to the prediction factor of the input, so that adaptation is inhibited whenever tone-like signals are present in the input. Simulation results verified the efficiency of the proposed algorithm.

Solution of the 2-D steady-state radiative transfer equation in participating media with specular reflections using SUPG and DG finite elements

NASA Astrophysics Data System (ADS)

Le Hardy, D.; Favennec, Y.; Rousseau, B.

2016-08-01

The 2D radiative transfer equation coupled with specular reflection boundary conditions is solved using finite element schemes. Both Discontinuous Galerkin and Streamline-Upwind Petrov-Galerkin variational formulations are fully developed. These two schemes are validated step-by-step for all involved operators (transport, scattering, reflection) using analytical formulations. Numerical comparisons of the two schemes, in terms of convergence rate, reveal that the quadratic SUPG scheme proves efficient for solving such problems. This comparison constitutes the main issue of the paper. Moreover, the solution process is accelerated using block SOR-type iterative methods, for which the determination of the optimal parameter is found in a very cheap way.

Dynamic investigation of DNA bending and wrapping by type II topoisomerases

NASA Astrophysics Data System (ADS)

Shao, Qing; Finzi, Laura; Dunlap, David

2009-11-01

Type II topoisomerases catalyze DNA decatenation and unwinding which is crucial for cell division, and therefore type II topoisomerases are some of the main targets of anti-cancer drugs. A recent crystal structure shows that, during the catalytic cycle, a yeast type II topoimerase can bend a 10 base pair DNA segment by up to 150 degrees. Bacterial gyrase, another type II topoisomerase, can wrap DNA into a tight 180 degree turn. Bending a stiff polymer like DNA requires considerable energy and could represent the rate limiting step in the catalytic (topological) cycle. Using modified deoxyribonucleotides in PCR reactions, stiffer DNA fragments have been produced and used as substrates for topoisomerase II-mediated relaxation of plectonemes introduced in single molecules using magnetic tweezers. The wrapping ability of gyrase decreases for diamino-purine-substituted DNA in which every base pair has three hydrogen-bonds. The overall rate of relaxation of plectonemes by recombinant human topoisomerase II alpha also decreases. These results reveal the dynamic properties of DNA bending and wrapping by type II topisomerases and suggest that A:T base pair melting is a rate determining step for bending and wrapping.

The Energy Landscape, Folding Pathways and the Kinetics of a Knotted Protein

PubMed Central

Prentiss, Michael C.; Wales, David J.; Wolynes, Peter G.

2010-01-01

The folding pathway and rate coefficients of the folding of a knotted protein are calculated for a potential energy function with minimal energetic frustration. A kinetic transition network is constructed using the discrete path sampling approach, and the resulting potential energy surface is visualized by constructing disconnectivity graphs. Owing to topological constraints, the low-lying portion of the landscape consists of three distinct regions, corresponding to the native knotted state and to configurations where either the N or C terminus is not yet folded into the knot. The fastest folding pathways from denatured states exhibit early formation of the N terminus portion of the knot and a rate-determining step where the C terminus is incorporated. The low-lying minima with the N terminus knotted and the C terminus free therefore constitute an off-pathway intermediate for this model. The insertion of both the N and C termini into the knot occurs late in the folding process, creating large energy barriers that are the rate limiting steps in the folding process. When compared to other protein folding proteins of a similar length, this system folds over six orders of magnitude more slowly. PMID:20617197

In Situ Observation of Calcium Aluminate Inclusions Dissolution into Steelmaking Slag

NASA Astrophysics Data System (ADS)

Miao, Keyan; Haas, Alyssa; Sharma, Mukesh; Mu, Wangzhong; Dogan, Neslihan

2018-06-01

The dissolution rate of calcium aluminate inclusions in CaO-SiO2-Al2O3 slags has been studied using confocal scanning laser microscopy (CSLM) at elevated temperatures: 1773 K, 1823 K, and 1873 K (1500 °C, 1550 °C, and 1600 °C). The inclusion particles used in this experimental work were produced in our laboratory and their production technique is explained in detail. Even though the particles had irregular shapes, there was no rotation observed. Further, the total dissolution time decreased with increasing temperature and decreasing SiO2 content in the slag. The rate limiting steps are discussed in terms of shrinking core models and diffusion into a stagnant fluid model. It is shown that the rate limiting step for dissolution is mass transfer in the slag at 1823 K and 1873 K (1550 °C and 1600 °C). Further investigations are required to determine the dissolution mechanism at 1773 K (1500 °C). The calculated diffusion coefficients were inversely proportional to the slag viscosity and the obtained values for the systems studied ranged between 5.64 × 10-12 and 5.8 × 10-10 m2/s.

In Situ Graphene Growth Dynamics on Polycrystalline Catalyst Foils

PubMed Central

2016-01-01

The dynamics of graphene growth on polycrystalline Pt foils during chemical vapor deposition (CVD) are investigated using in situ scanning electron microscopy and complementary structural characterization of the catalyst with electron backscatter diffraction. A general growth model is outlined that considers precursor dissociation, mass transport, and attachment to the edge of a growing domain. We thereby analyze graphene growth dynamics at different length scales and reveal that the rate-limiting step varies throughout the process and across different regions of the catalyst surface, including different facets of an individual graphene domain. The facets that define the domain shapes lie normal to slow growth directions, which are determined by the interfacial mobility when attachment to domain edges is rate-limiting, as well as anisotropy in surface diffusion as diffusion becomes rate-limiting. Our observations and analysis thus reveal that the structure of CVD graphene films is intimately linked to that of the underlying polycrystalline catalyst, with both interfacial mobility and diffusional anisotropy depending on the presence of step edges and grain boundaries. The growth model developed serves as a general framework for understanding and optimizing the growth of 2D materials on polycrystalline catalysts. PMID:27576749

Sequential control of step-bunching during graphene growth on SiC (0001)

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

Bao, Jianfeng; Kusunoki, Michiko; Yasui, Osamu

2016-08-22

We have investigated the relation between the step-bunching and graphene growth phenomena on an SiC substrate. We found that only a minimum amount of step-bunching occurred during the graphene growth process with a high heating rate. On the other hand, a large amount of step-bunching occurred using a slow heating process. These results indicated that we can control the degree of step-bunching during graphene growth by controlling the heating rate. We also found that graphene coverage suppressed step bunching, which is an effective methodology not only in the graphene technology but also in the SiC-based power electronics.

Evaluating Validity Evidence for USMLE Step 2 Clinical Skills Data Gathering and Data Interpretation Scores: Does Performance Predict History-Taking and Physical Examination Ratings for First-Year Internal Medicine Residents?

PubMed

Cuddy, Monica M; Winward, Marcia L; Johnston, Mary M; Lipner, Rebecca S; Clauser, Brian E

2016-01-01

To add to the small body of validity research addressing whether scores from performance assessments of clinical skills are related to performance in supervised patient settings, the authors examined relationships between United States Medical Licensing Examination (USMLE) Step 2 Clinical Skills (CS) data gathering and data interpretation scores and subsequent performance in history taking and physical examination in internal medicine residency training. The sample included 6,306 examinees from 238 internal medicine residency programs who completed Step 2 CS for the first time in 2005 and whose performance ratings from their first year of residency training were available. Hierarchical linear modeling techniques were used to examine the relationships among Step 2 CS data gathering and data interpretation scores and history-taking and physical examination ratings. Step 2 CS data interpretation scores were positively related to both history-taking and physical examination ratings. Step 2 CS data gathering scores were not related to either history-taking or physical examination ratings after other USMLE scores were taken into account. Step 2 CS data interpretation scores provide useful information for predicting subsequent performance in history taking and physical examination in supervised practice and thus provide validity evidence for their intended use as an indication of readiness to enter supervised practice. The results show that there is less evidence to support the usefulness of Step 2 CS data gathering scores. This study provides important information for practitioners interested in Step 2 CS specifically or in performance assessments of medical students' clinical skills more generally.

Parameter dependence of the MCNP electron transport in determining dose distributions.

PubMed

Reynaert, N; Palmans, H; Thierens, H; Jeraj, R

2002-10-01

In this paper, a detailed study of the electron transport in MCNP is performed, separating the effects of the energy binning technique on the energy loss rate, the scattering angles, and the sub-step length as a function of energy. As this problem is already well known, in this paper we focus on the explanation as to why the default mode of MCNP can lead to large deviations. The resolution dependence was investigated as well. An error in the MCNP code in the energy binning technique in the default mode (DBCN 18 card = 0) was revealed, more specific in the updating of cross sections when a sub-step is performed corresponding to a high-energy loss. This updating error is not present in the ITS mode (DBCN 18 card = 1) and leads to a systematically lower dose deposition rate in the default mode. The effect is present for all energies studied (0.5-10 MeV) and depends on the geometrical resolution of the scoring regions and the energy grid resolution. The effect of the energy binning technique is of the same order of that of the updating error for energies below 2 MeV, and becomes less important for higher energies. For a 1 MeV point source surrounded by homogeneous water, the deviation of the default MCNP results at short distances attains 9% and remains approximately the same for all energies. This effect could be corrected by removing the completion of an energy step each time an electron changes from an energy bin during a sub-step. Another solution consists of performing all calculations in the ITS mode. Another problem is the resolution dependence, even in the ITS mode. The higher the resolution is chosen (the smaller the scoring regions) the faster the energy is deposited along the electron track. It is proven that this is caused by starting a new energy step when crossing a surface. The resolution effect should be investigated for every specific case when calculating dose distributions around beta sources. The resolution should not be higher than 0.85*(1-EFAC)*CSDA, where EFAC is the energy loss per energy step and CSDA a continuous slowing down approximation range. This effect could as well be removed by determining the cross sections for energy loss and multiple scattering at the average energy of an energy step and by sampling the cross sections for each sub-step. Overall, we conclude that MCNP cannot be used without a caution due to possible errors in the electron transport. When care is taken, it is possible to obtain correct results that are in agreement with other Monte Carlo codes.

Reactivity of chemisorbed oxygen atoms and their catalytic consequences during CH4-O2 catalysis on supported Pt clusters.

PubMed

Chin, Ya-Huei Cathy; Buda, Corneliu; Neurock, Matthew; Iglesia, Enrique

2011-10-12

Kinetic and isotopic data and density functional theory treatments provide evidence for the elementary steps and the active site requirements involved in the four distinct kinetic regimes observed during CH(4) oxidation reactions using O(2), H(2)O, or CO(2) as oxidants on Pt clusters. These four regimes exhibit distinct rate equations because of the involvement of different kinetically relevant steps, predominant adsorbed species, and rate and equilibrium constants for different elementary steps. Transitions among regimes occur as chemisorbed oxygen (O*) coverages change on Pt clusters. O* coverages are given, in turn, by a virtual O(2) pressure, which represents the pressure that would give the prevalent steady-state O* coverages if their adsorption-desorption equilibrium was maintained. The virtual O(2) pressure acts as a surrogate for oxygen chemical potentials at catalytic surfaces and reflects the kinetic coupling between C-H and O═O activation steps. O* coverages and virtual pressures depend on O(2) pressure when O(2) activation is equilibrated and on O(2)/CH(4) ratios when this step becomes irreversible as a result of fast scavenging of O* by CH(4)-derived intermediates. In three of these kinetic regimes, C-H bond activation is the sole kinetically relevant step, but occurs on different active sites, which evolve from oxygen-oxygen (O*-O*), to oxygen-oxygen vacancy (O*-*), and to vacancy-vacancy (*-*) site pairs as O* coverages decrease. On O*-saturated cluster surfaces, O*-O* site pairs activate C-H bonds in CH(4) via homolytic hydrogen abstraction steps that form CH(3) groups with significant radical character and weak interactions with the surface at the transition state. In this regime, rates depend linearly on CH(4) pressure but are independent of O(2) pressure. The observed normal CH(4)/CD(4) kinetic isotope effects are consistent with the kinetic-relevance of C-H bond activation; identical (16)O(2)-(18)O(2) isotopic exchange rates in the presence or absence of CH(4) show that O(2) activation steps are quasi-equilibrated during catalysis. Measured and DFT-derived C-H bond activation barriers are large, because of the weak stabilization of the CH(3) fragments at transition states, but are compensated by the high entropy of these radical-like species. Turnover rates in this regime decrease with increasing Pt dispersion, because low-coordination exposed Pt atoms on small clusters bind O* more strongly than those that reside at low-index facets on large clusters, thus making O* less effective in H-abstraction. As vacancies (*, also exposed Pt atoms) become available on O*-covered surfaces, O*-* site pairs activate C-H bonds via concerted oxidative addition and H-abstraction in transition states effectively stabilized by CH(3) interactions with the vacancies, which lead to much higher turnover rates than on O*-O* pairs. In this regime, O(2) activation becomes irreversible, because fast C-H bond activation steps scavenge O* as it forms. Thus, O* coverages are set by the prevalent O(2)/CH(4) ratios instead of the O(2) pressures. CH(4)/CD(4) kinetic isotope effects are much larger for turnovers mediated by O*-* than by O*-O* site pairs, because C-H (and C-D) activation steps are required to form the * sites involved in C-H bond activation. Turnover rates for CH(4)-O(2) reactions mediated by O*-* pairs decrease with increasing Pt dispersion, as in the case of O*-O* active structures, because stronger O* binding on small clusters leads not only to less reactive O* atoms, but also to lower vacancy concentrations at cluster surfaces. As O(2)/CH(4) ratios and O* coverages become smaller, O(2) activation on bare Pt clusters becomes the sole kinetically relevant step; turnover rates are proportional to O(2) pressures and independent of CH(4) pressure and no CH(4)/CD(4) kinetic isotope effects are observed. In this regime, turnover rates become nearly independent of Pt dispersion, because the O(2) activation step is essentially barrierless. In the absence of O(2), alternate weaker oxidants, such as H(2)O or CO(2), lead to a final kinetic regime in which C-H bond dissociation on *-* pairs at bare cluster surfaces limit CH(4) conversion rates. Rates become first-order in CH(4) and independent of coreactant and normal CH(4)/CD(4) kinetic isotope effects are observed. In this case, turnover rates increase with increasing dispersion, because low-coordination Pt atoms stabilize the C-H bond activation transition states more effectively via stronger binding to CH(3) and H fragments. These findings and their mechanistic interpretations are consistent with all rate and isotopic data and with theoretical estimates of activation barriers and of cluster size effects on transition states. They serve to demonstrate the essential role of the coverage and reactivity of chemisorbed oxygen in determining the type and effectiveness of surface structures in CH(4) oxidation reactions using O(2), H(2)O, or CO(2) as oxidants, as well as the diversity of rate dependencies, activation energies and entropies, and cluster size effects that prevail in these reactions. These results also show how theory and experiments can unravel complex surface chemistries on realistic catalysts under practical conditions and provide through the resulting mechanistic insights specific predictions for the effects of cluster size and surface coordination on turnover rates, the trends and magnitude of which depend sensitively on the nature of the predominant adsorbed intermediates and the kinetically relevant steps.

True cadence and step accumulation are not equivalent: the effect of intermittent claudication on free-living cadence.

PubMed

Stansfield, B; Clarke, C; Dall, P; Godwin, J; Holdsworth, R; Granat, M

2015-02-01

'True cadence' is the rate of stepping during the period of stepping. 'Step accumulation' is the steps within an epoch of time (e.g. 1min). These terms have been used interchangeably in the literature. These outcomes are compared within a population with intermittent claudication (IC). Multiday, 24h stepping activity of those with IC (30) and controls (30) was measured objectively using the activPAL physical activity monitor. 'True cadence' and 'step accumulation' outcomes were calculated. Those with IC took fewer steps/d 6531±2712 than controls 8692±2945 (P=0.003). However, these steps were taken within approximately the same number of minute epochs (IC 301±100min/d; controls 300±70min/d, P=0.894) with only slightly lower true cadence (IC 69 (IQ 66,72) steps/min; controls 72 (IQ 68,76) steps/min, P=0.026), giving substantially lower step accumulation (IC 22 (IQ 19,24) steps/min; controls 30 (IQ 23,34) steps/min) (P<0.001). However, the true cadence of stepping within the blocks of the 1, 5, 20, 30 and 60min with the maximum number of steps accumulated was lower for those with IC than controls (P<0.05). Those with IC took 1300 steps fewer per day above a true cadence of 90 steps/min. True cadence and step accumulation outcomes were radically different for the outcomes examined. 'True cadence' and 'step accumulation' were not equivalent in those with IC or controls. The measurement of true cadence in the population of people with IC provides information about their stepping rate during the time they are stepping. True cadence should be used to correctly describe the rate of stepping as performed. Copyright © 2014 Elsevier B.V. All rights reserved.

An item response theory evaluation of the young mania rating scale and the montgomery-asberg depression rating scale in the systematic treatment enhancement program for bipolar disorder (STEP-BD).

PubMed

Prisciandaro, James J; Tolliver, Bryan K

2016-11-15

The Young Mania Rating Scale (YMRS) and Montgomery-Asberg Depression Rating Scale (MADRS) are among the most widely used outcome measures for clinical trials of medications for Bipolar Disorder (BD). Nonetheless, very few studies have examined the measurement characteristics of the YMRS and MADRS in individuals with BD using modern psychometric methods. The present study evaluated the YMRS and MADRS in the Systematic Treatment Enhancement Program for BD (STEP-BD) study using Item Response Theory (IRT). Baseline data from 3716 STEP-BD participants were available for the present analysis. The Graded Response Model (GRM) was fit separately to YMRS and MADRS item responses. Differential item functioning (DIF) was examined by regressing a variety of clinically relevant covariates (e.g., sex, substance dependence) on all test items and on the latent symptom severity dimension, within each scale. Both scales: 1) contained several items that provided little or no psychometric information, 2) were inefficient, in that the majority of item response categories did not provide incremental psychometric information, 3) poorly measured participants outside of a narrow band of severity, 4) evidenced DIF for nearly all items, suggesting that item responses were, in part, determined by factors other than symptom severity. Limited to outpatients; DIF analysis only sensitive to certain forms of DIF. The present study provides evidence for significant measurement problems involving the YMRS and MADRS. More work is needed to refine these measures and/or develop suitable alternative measures of BD symptomatology for clinical trials research. Copyright © 2016 Elsevier B.V. All rights reserved.

The relationship between communication scores from the USMLE Step 2 Clinical Skills examination and communication ratings for first-year internal medicine residents.

PubMed

Winward, Marcia L; Lipner, Rebecca S; Johnston, Mary M; Cuddy, Monica M; Clauser, Brian E

2013-05-01

This study extends available evidence about the relationship between scores on the Step 2 Clinical Skills (CS) component of the United States Medical Licensing Examination and subsequent performance in residency. It focuses on the relationship between Step 2 CS communication and interpersonal skills scores and communication skills ratings that residency directors assign to residents in their first postgraduate year of internal medicine training. It represents the first large-scale evaluation of the extent to which Step 2 CS communication and interpersonal skills scores can be extrapolated to examinee performance in supervised practice. Hierarchical linear modeling techniques were used to examine the relationships among examinee characteristics, residency program characteristics, and residency-director-provided ratings. The sample comprised 6,306 examinees from 238 internal medicine residency programs who completed Step 2 CS for the first time in 2005 and received ratings during their first year of internal medicine residency training. Although the relationship is modest, Step 2 CS communication and interpersonal skills scores predict communication skills ratings for first-year internal medicine residents after accounting for other factors. The results of this study make a reasonable case that Step 2 CS communication and interpersonal skills scores provide useful information for predicting the level of communication skill that examinees will display in their first year of internal medicine residency training. This finding demonstrates some level of extrapolation from the testing context to behavior in supervised practice, thus providing validity-related evidence for using Step 2 CS communication and interpersonal skills scores in high-stakes decisions.

Microphytobenthos potential productivity estimated in three tidal embayments of the San Francisco Bay system

USGS Publications Warehouse

Guarini, Jean-Marc; Cloern, James E.; Edmunds, Jody L.; Gros, Philippe

2002-01-01

In this paper we describe a three-step procedure to infer the spatial heterogeneity in microphytobenthos primary productivity at the scale of tidal estuaries and embayments. The first step involves local measurement of the carbon assimilation rate of benthic microalgae to determine the parameters of the photosynthesis-irradiance (P-E) curves (using non-linear optimization methods). In the next step, a resampling technique is used to rebuild pseudo-sampling distributions of the local productivity estimates; these provide error estimates for determining the significance level of differences between sites. The third step combines the previous results with deterministic models of tidal elevation and solar irradiance to compute mean and variance of the daily areal primary productivity over an entire intertidal mudflat area within each embayment. This scheme was applied on three different intertidal mudflat regions of the San Francisco Bay estuary during autumn 1998. Microphytobenthos productivity exhibits strong (ca. 3-fold) significant differences among the major sub-basins of San Francisco Bay. This spatial heterogeneity is attributed to two main causes: significant differences in the photosynthetic competence (P-E parameters) of the microphytobenthos in the different sub-basins, and spatial differences in the phase shifts between the tidal and solar cycles controlling the exposure of intertidal areas to sunlight. The procedure is general and can be used in other estuaries to assess the magnitude and patterns of spatial variability of microphytobenthos productivity at the level of the ecosystems.

Microphytobenthic potential productivity estimated in three tidal embayments of the San Francisco Bay: A comparative study

USGS Publications Warehouse

Guarini, J.-M.; Cloern, James E.; Edmunds, J.

2002-01-01

In this paper we describe a three-step procedure to infer the spatial heterogeneity in microphytobenthos primary productivity at the scale of tidal estuaries and embayments. The first step involves local measurement of the carbon assimilation rate of benthic microalgae to determine the parameters of the photosynthesis-irradiance (P-E) curves (using non-linear optimization methods). In the next step, a resampling technique is used to rebuild pseudo-sampling distributions of the local productivity estimates; these provide error estimates for determining the significance level of differences between sites. The third step combines the previous results with deterministic models of tidal elevation and solar irradiance to compute mean and variance of the daily areal primary productivity over an entire intertidal mudflat area within each embayment. This scheme was applied on three different intertidal mudflat regions of the San Francisco Bay estuary during autumn 1998. Microphytobenthos productivity exhibits strong (ca. 3-fold) significant differences among the major sub-basins of San Francisco Bay. This spatial heterogeneity is attributed to two main causes: significant differences in the photosynthetic competence (P-E parameters) of the microphytobenthos in the different sub-basins, and spatial differences in the phase shifts between the tidal and solar cycles controlling the exposure of intertidal areas to sunlight. The procedure is general and can be used in other estuaries to assess the magnitude and patterns of spatial variability of microphytobenthos productivity at the level of the ecosystems.

Optimization of High-Throughput Sequencing Kinetics for determining enzymatic rate constants of thousands of RNA substrates

PubMed Central

Niland, Courtney N.; Jankowsky, Eckhard; Harris, Michael E.

2016-01-01

Quantification of the specificity of RNA binding proteins and RNA processing enzymes is essential to understanding their fundamental roles in biological processes. High Throughput Sequencing Kinetics (HTS-Kin) uses high throughput sequencing and internal competition kinetics to simultaneously monitor the processing rate constants of thousands of substrates by RNA processing enzymes. This technique has provided unprecedented insight into the substrate specificity of the tRNA processing endonuclease ribonuclease P. Here, we investigate the accuracy and robustness of measurements associated with each step of the HTS-Kin procedure. We examine the effect of substrate concentration on the observed rate constant, determine the optimal kinetic parameters, and provide guidelines for reducing error in amplification of the substrate population. Importantly, we find that high-throughput sequencing, and experimental reproducibility contribute their own sources of error, and these are the main sources of imprecision in the quantified results when otherwise optimized guidelines are followed. PMID:27296633

An Examination of the Counting Talk Test's Ability to Discern Individual Variability in Exercise-Induced Metabolic Stress

ERIC Educational Resources Information Center

Bonafiglia, Jacob T.; Sawula, Laura J.; Gurd, Brendon J.

2018-01-01

The purpose of this study was to determine if the counting talk test can be used to discern whether an individual is exercising above or at/below maximal lactate steady state. Twenty-two participants completed VO[subscript 2]peak and counting talk test incremental step tests followed by an endurance test at 65% of work rate at VO[subscript 2]peak…

Development of a Framework for Model-Based Analysis, Uncertainty Quantification, and Robust Control Design of Nonlinear Smart Composite Systems

DTIC Science & Technology

2015-06-04

control, vibration and noise control, health monitoring, and energy harvesting . However, these advantages come at the cost of rate-dependent hysteresis...configuration used for energy harvesting . Uncertainty Quantification Uncertainty quantification is pursued in two steps: (i) determination of densities...Crews and R.C. Smith, “Quantification of parameter and model uncertainty for shape mem- ory alloy bending actuators,” Journal of Intelligent material

Incremental value of Veterans Specific Activity Questionnaire and the YMCA-step test for the assessment of cardiorespiratory fitness in population-based studies.

PubMed

Teren, Andrej; Zachariae, Silke; Beutner, Frank; Ubrich, Romy; Sandri, Marcus; Engel, Christoph; Löffler, Markus; Gielen, Stephan

2016-07-01

Cardiorespiratory fitness is a well-established independent predictor of cardiovascular health. However, the relevance of alternative exercise and non-exercise tests for cardiorespiratory fitness assessment in large cohorts has not been studied in detail. We aimed to evaluate the YMCA-step test and the Veterans Specific Activity Questionnaire (VSAQ) for the estimation of cardiorespiratory fitness in the general population. One hundred and five subjects answered the VSAQ, performed the YMCA-step test and a maximal cardiopulmonary exercise test (CPX) and gave BORG ratings for both exercise tests (BORGSTEP, BORGCPX). Correlations of peak oxygen uptake on a treadmill (VO2_PEAK) with VSAQ, BORGSTEP, one-minute, post-exercise heartbeat count, and peak oxygen uptake during the step test (VO2_STEP) were determined. Moreover, the incremental values of the questionnaire and the step test in addition to other fitness-related parameters were evaluated using block-wise hierarchical regression analysis. Eighty-six subjects completed the step test according to the protocol. For completers, correlations of VO2_PEAK with the age- and gender-adjusted VSAQ, heartbeat count and VO2_STEP were 0.67, 0.63 and 0.49, respectively. However, using hierarchical regression analysis, age, gender and body mass index already explained 68.8% of the variance of VO2_PEAK, while the additional benefit of VSAQ was rather low (3.4%). The inclusion of BORGSTEP, heartbeat count and VO2_STEP increased R(2) by a further 2.2%, 3.3% and 5.6%, respectively, yielding a total R(2) of 83.3%. Neither VSAQ nor the YMCA-step test contributes sufficiently to the assessment of cardiorespiratory fitness in population-based studies. © The European Society of Cardiology 2015.

Electrochemical Reduction of CO 2 Catalyzed by Re(pyridine-oxazoline)(CO) 3 Cl Complexes

DOE PAGES

Nganga, John K.; Samanamu, Christian R.; Tanski, Joseph M.; ...

2017-03-09

In a series of rhenium tricarbonyl complexes coordinated by asymmetric diimine ligands containing a pyridine moiety bound to an oxazoline ring were synthesized, structurally and electrochemically characterized, and screened for CO 2 reduction ability. We reported complexes are of the type Re(N-N)(CO) 3Cl, with N-N = 2-(pyridin-2-yl)-4,5-dihydrooxazole (1), 5-methyl-2-(pyridin-2-yl)-4,5-dihydrooxazole (2), and 5-phenyl-2-(pyridin-2-yl)-4,5-dihydrooxazole (3). The electrocatalytic reduction of CO 2 by these complexes was observed in a variety of solvents and proceeds more quickly in acetonitrile than in dimethylformamide (DMF) and dimethyl sulfoxide (DMSO). The analysis of the catalytic cycle for electrochemical CO 2 reduction by 1 in acetonitrile using densitymore » functional theory (DFT) supports the C–O bond cleavage step being the rate-determining step (RDS) (ΔG ‡ = 27.2 kcal mol –1). Furthermore, the dependency of the turnover frequencies (TOFs) on the donor number (DN) of the solvent also supports that C–O bond cleavage is the rate-determining step. Moreover, the calculations using explicit solvent molecules indicate that the solvent dependence likely arises from a protonation-first mechanism. Unlike other complexes derived from fac-Re(bpy)(CO) 3Cl (I; bpy = 2,2'-bipyridine), in which one of the pyridyl moieties in the bpy ligand is replaced by another imine, no catalytic enhancement occurs during the first reduction potential. Remarkably, catalysts 1 and 2 display relative turnover frequencies, (i cat/i p) 2, up to 7 times larger than that of I.« less

Mechanistic Insights into Dye-Decolorizing Peroxidase Revealed by Solvent Isotope and Viscosity Effects

PubMed Central

Shrestha, Ruben; Huang, Gaochao; Meekins, David A.; Geisbrecht, Brian V.; Li, Ping

2017-01-01

Dye-decolorizing peroxidases (DyPs) are a family of H2O2-dependent heme peroxidases, which 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 uncovered for the B-class ElDyP from Enterobacter lignolyticus. Its structure revealed that a water molecule acts as the sixth axial ligand with two channels at diameters of ~3.0 and 8.0 Å leading 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-Pong mechanism. This step is also the rate-determining step in ABTS oxidation. The normal KIE of wild-type ElDyP with D2O2 at pH 3.5 suggested that cmpd 0 deprotonation by the distal aspartate is rate-limiting in the formation of cmpd 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 cmpd I instead of the free enzyme. The significant inverse sKIEs of kcat/KM and kERS* suggested that the aquo release in DyPs is mechanistically important and may explain the enzyme’s adoption of two-electron reduction for cmpd I. The distal aspartate is catalytically more important than the distal arginine and plays key roles in determining DyPs’ acidic pH optimum. 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. PMID:29308295

Magnesite Step Growth Rates as a Function of the Aqueous Magnesium:Carbonate Ratio

DOE PAGES

Bracco, Jacquelyn N.; Stack, Andrew G.; Higgins, Steven R.

2014-10-01

Step velocities of monolayer-height steps on the (101 ⁻4) magnesite surface have been measured as functions of the aqueous magnesium-to-carbonate ratio and saturation index (SI) using a hydrothermal atomic force microscope (HAFM). At SI ≤ 1.9 and 80-90 °C, step velocities were found to be invariant with changes in the magnesium-to-carbonate ratio, an observation in contrast with standard models for growth and dissolution of ionically-bonded, multi-component crystals. However, at high saturation indices (SI = 2.15), step velocities displayed a ratio dependence, maximized at magnesium-to-carbonate ratios slightly greater than 1:1. Traditional affinity-based models were unable to describe growth rates at themore » higher saturation index. Step velocities also could not be modeled solely through nucleation of kink sites, in contrast to other minerals whose bonding between constituent ions is also dominantly ionic in nature, such as calcite and barite. Instead, they could be described only by a model that incorporates both kink nucleation and propagation. Based on observed step morphological changes at these higher saturation indices, the step velocity maximum at SI = 2.15 is likely due to the rate of attachment to propagating kink sites overcoming the rate of detachment from kink sites as the latter becomes less significant under far from equilibrium conditions.« less

International PV QA Task Force's Proposed Comparative Rating System for PV Modules: Preprint

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

Wohlgemuth, J.; Kurtz, S.

The International PV Quality Assurance Task Force is developing a rating system that provides comparative information about the relative durability of PV modules. Development of accelerated stress tests that can provide such comparative information is seen as a major step toward being able to predict PV module service life. This paper will provide details of the ongoing effort to determine the format of such an overall module rating system. The latest proposal is based on using three distinct climate zones as defined in IEC 60721-2-1 for two different mounting systems. Specific stresses beyond those used in the qualification tests aremore » being developed for each of the selected climate zones.« less

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

PubMed

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

2016-10-04

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

Development and evaluation of a tool for retrospective exposure assessment of selected endocrine disrupting chemicals and EMF in the car manufacturing industry.

PubMed

Mester, Birte; Schmeisser, Nils; Lünzmann, Hauke; Pohlabeln, Hermann; Langner, Ingo; Behrens, Thomas; Ahrens, Wolfgang

2011-08-01

A system for retrospective occupational exposure assessment combining the efficiency of a job exposure matrix (JEM) and the precision of a subsequent individual expert exposure assessment (IEEA) was developed. All steps of the exposure assessment were performed by an interdisciplinary expert panel in the context of a case-control study on male germ cell cancer nested in the car manufacturing industries. An industry-specific JEM was developed and automatic exposure estimation was performed based on this JEM. A subsample of exposure ratings was done by IEEA to identify determinants of disagreement between the JEM and the individual review. Possible determinants were analyzed by calculating odds ratios (ORs) of disagreement between ratings with regard to different dimensions (e.g. high versus low intensity of exposure). Disagreement in ≥20% of the sampled exposure ratings with a statistically significant OR was chosen as a threshold for inclusion of the exposure ratings into a final IEEA. The most important determinants of disagreement between JEM and individual review were working outside of the production line (disagreement 80%), low probability of exposure (disagreement 25%), and exposure depending on specific activities like usage of specific lacquers (disagreement 32%) for jobs within the production line. These determinants were the selection criteria of exposure ratings for the subsequent final IEEA. Combining a JEM and a subsequent final IEEA for a selected subset of exposure ratings is a feasible and labor-saving approach for exposure assessment in large occupational epidemiological studies.

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

PubMed

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

2015-07-28

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

Characterization of pulsed flow attenuation on a regulated montane river

NASA Astrophysics Data System (ADS)

Fong, C. S.; Yarnell, S. M.; Fleenor, W. E.; Viers, J. H.

2013-12-01

A major benefit of hydropower is its ability to respond quickly to fluctuating electrical loads. However, the sharp changes in discharge caused by this practice have detrimental environmental effects downstream. This study investigated the effects of hydrograph shape on attenuation of regulated pulsed flow events by first categorizing, then modeling the downstream movement of representative pulses on the upper Tuolumne River below Holm Powerhouse in the Sierra Nevada mountains of California. This system was managed by a public utility and produced flow pulses primarily for hydroelectricity generation and/or whitewater recreation. Operations were highly influenced by a system-wide "Water First" policy, which prioritized drinking water supply and quality over other beneficial uses. Pulses were therefore associated with a spectrum of time scales, from predetermined schedules decided far in advance to hydropeaking operations responding to real-time demands. We extracted underlying hydrograph shape patterns using principal component analysis on individual pulsed flow events released from 1988-2012 (n=4439). From principal component loadings, six shape categories were determined: rectangular, front-step, back-step, goalpost, centered tower, and other. The rectangular and stepped shapes were the most frequent, composing 62% and 24% of total events, respectively. The rectangular shape was often produced by 'standard' hydropeaking or recreational releases, while the stepped shapes were often used for water conservation or were recreational flows bordered by periods of electricity generation. The stepped shape increased in occurrence after the "Water First" policy took effect in 1993 and dominated two drier years (2007 and 2009). After categorization by shape, magnitude and durational indices were used to fabricate representative pulsed flow events. Attenuation of these representative pulses was then modeled using a 1D hydraulic model of 42 river km prepared in HEC-RAS. As no operational measures or physical structures existed within the system to counter the adverse effects of pulsed flow events, natural attenuation was the only potential major mitigation agent. However, model results demonstrated a clear durational threshold for representative pulses (~ 3-5 hrs) over which the degree of attenuation of ramping rates and peak discharge approached a limit. These thresholds were unique to the study reach and were dependent upon river morphology, bed characteristics, and flow rates. Increasing baseflows did not necessarily increase attenuation of pulses, most likely due to minimal increases in bed friction forces in this fairly steep and confined channel. Simulations of front and back-step representative pulses showed trade-offs between attenuation of peak magnitudes and steepness of ramping rates. Finally, a range of rising ramping rates were shown to steepen downstream above initial rates due to the study reach's channel morphology. Reshaping pulses to be more ecologically benign at all points downstream was infeasible if the system was required to maintain current electricity production and recreational service levels.

Implementation of Time-Resolved Step-Scan Fourier Transform Infrared (FT-IR) Spectroscopy Using a kHz Repetition Rate Pump Laser

PubMed Central

MAGANA, DONNY; PARUL, DZMITRY; DYER, R. BRIAN; SHREVE, ANDREW P.

2011-01-01

Time-resolved step-scan Fourier transform infrared (FT-IR) spectroscopy has been shown to be invaluable for studying excited-state structures and dynamics in both biological and inorganic systems. Despite the established utility of this method, technical challenges continue to limit the data quality and more wide ranging applications. A critical problem has been the low laser repetition rate and interferometer stepping rate (both are typically 10 Hz) used for data acquisition. Here we demonstrate significant improvement in the quality of time-resolved spectra through the use of a kHz repetition rate laser to achieve kHz excitation and data collection rates while stepping the spectrometer at 200 Hz. We have studied the metal-to-ligand charge transfer excited state of Ru(bipyridine)3Cl2 in deuterated acetonitrile to test and optimize high repetition rate data collection. Comparison of different interferometer stepping rates reveals an optimum rate of 200 Hz due to minimization of long-term baseline drift. With the improved collection efficiency and signal-to-noise ratio, better assignments of the MLCT excited-state bands can be made. Using optimized parameters, carbonmonoxy myoglobin in deuterated buffer is also studied by observing the infrared signatures of carbon monoxide photolysis upon excitation of the heme. We conclude from these studies that a substantial increase in performance of ss-FT-IR instrumentation is achieved by coupling commercial infrared benches with kHz repetition rate lasers. PMID:21513597

Modelling uveal melanoma

PubMed Central

Foss, A.; Cree, I.; Dolin, P.; Hungerford, J.

1999-01-01

BACKGROUND/AIM—There has been no consistent pattern reported on how mortality for uveal melanoma varies with age. This information can be useful to model the complexity of the disease. The authors have examined ocular cancer trends, as an indirect measure for uveal melanoma mortality, to see how rates vary with age and to compare the results with their other studies on predicting metastatic disease.
METHODS—Age specific mortality was examined for England and Wales, the USA, and Canada. A log-log model was fitted to the data. The slopes of the log-log plots were used as measure of disease complexity and compared with the results of previous work on predicting metastatic disease.
RESULTS—The log-log model provided a good fit for the US and Canadian data, but the observed rates deviated for England and Wales among people over the age of 65 years. The log-log model for mortality data suggests that the underlying process depends upon four rate limiting steps, while a similar model for the incidence data suggests between three and four rate limiting steps. Further analysis of previous data on predicting metastatic disease on the basis of tumour size and blood vessel density would indicate a single rate limiting step between developing the primary tumour and developing metastatic disease.
CONCLUSIONS—There is significant underreporting or underdiagnosis of ocular melanoma for England and Wales in those over the age of 65 years. In those under the age of 65, a model is presented for ocular melanoma oncogenesis requiring three rate limiting steps to develop the primary tumour and a fourth rate limiting step to develop metastatic disease. The three steps in the generation of the primary tumour involve two key processes—namely, growth and angiogenesis within the primary tumour. The step from development of the primary to development of metastatic disease is likely to involve a single rate limiting process.

 PMID:10216060

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

Kim H. Y.; Henkelman, G.

To reveal the richer chemistry of CO oxidation by CeO2 supported Au Nanoclusters NCs)/Nanoparticles, we design a Au12 supported on a stepped-CeO2 model (Au/CeO2-step) and study various kinds of CO oxidation mechanisms at the interface of the Au/CeO2-step: oxygen spillover from the CeO2 to the Au NCs;2 CO oxidation by the O2 bound to the Au-Ce3+ interface;3 and CO oxidation by the Mars-van Krevelen (M-vK) mechanism.4 DFT+U calculations show that lattice oxygen at the CeO2 step edge oxidizes CO bound to Au NCs by the M-vK mechanism. CO2 desorption determines the rate of CO oxidation and the vacancy formation energymore » (Evac) is a reactivity descriptor for CO oxidation. The maximum Evac that insures spontaneous CO2 production is higher for the Au/CeO2-step than the Au/CeO2-surface suggesting that the CeO2-step is a better supporting material than the CeO2-surface for CO oxidation by the Au/CeO2. Our results also suggest that for CO oxidation by Au NCs supported on nano- or meso-structured CeO2, which is the case of industrial catalysts, the M-vK mechanism accounts for a large portion of the total activity.« less

Methodology for processing pressure traces used as inputs for combustion analyses in diesel engines

NASA Astrophysics Data System (ADS)

Rašić, Davor; Vihar, Rok; Žvar Baškovič, Urban; Katrašnik, Tomaž

2017-05-01

This study proposes a novel methodology for designing an optimum equiripple finite impulse response (FIR) filter for processing in-cylinder pressure traces of a diesel internal combustion engine, which serve as inputs for high-precision combustion analyses. The proposed automated workflow is based on an innovative approach of determining the transition band frequencies and optimum filter order. The methodology is based on discrete Fourier transform analysis, which is the first step to estimate the location of the pass-band and stop-band frequencies. The second step uses short-time Fourier transform analysis to refine the estimated aforementioned frequencies. These pass-band and stop-band frequencies are further used to determine the most appropriate FIR filter order. The most widely used existing methods for estimating the FIR filter order are not effective in suppressing the oscillations in the rate- of-heat-release (ROHR) trace, thus hindering the accuracy of combustion analyses. To address this problem, an innovative method for determining the order of an FIR filter is proposed in this study. This method is based on the minimization of the integral of normalized signal-to-noise differences between the stop-band frequency and the Nyquist frequency. Developed filters were validated using spectral analysis and calculation of the ROHR. The validation results showed that the filters designed using the proposed innovative method were superior compared with those using the existing methods for all analyzed cases. Highlights • Pressure traces of a diesel engine were processed by finite impulse response (FIR) filters with different orders • Transition band frequencies were determined with an innovative method based on discrete Fourier transform and short-time Fourier transform • Spectral analyses showed deficiencies of existing methods in determining the FIR filter order • A new method of determining the FIR filter order for processing pressure traces was proposed • The efficiency of the new method was demonstrated by spectral analyses and calculations of rate-of-heat-release traces

Responsiveness and Minimally Important Difference of the 6-Minute Stepper Test in Patients with Chronic Obstructive Pulmonary Disease.

PubMed

Pichon, Romain; Couturaud, Francis; Mialon, Philippe; Le Ber-Moy, Catherine; Péran, Loïc; Lochon, Chantal; Nowak, Emmanuel; Beaumont, Marc

2016-01-01

The validity and reproducibility of the 6-minute stepper test (6MST) have already been demonstrated in patients with chronic obstructive pulmonary disease (COPD). The aim of this study was to evaluate the responsiveness of the 6MST to pulmonary rehabilitation (PR) in patients with COPD, to determine a minimal important difference (MID) for the 6MST, and to compare the 6MST and the 6-minute walk test (6MWT). Sixty-two patients with COPD were included in a prospective experimental study. Participants underwent a 3-week inpatient PR program. The primary outcome was the change in the number of steps during the 6MST measured before and after PR. The secondary outcome included the change in the 6-minute walking distance (6MWD) pulse oximetry, heart rate, dyspnea, and leg discomfort during the tests measured before and after PR. MID was determined by anchor-based and distribution approaches. After PR, we observed a significant increase in the number of steps during the 6MST (22.5 steps; 95% CI 13.8-31.3; p < 0.0001) and in the 6MWD (26.6 m; 95% CI 17.6-35.5; p < 0.0001). The 6MST and 6MWT were improved by 10.1 and 6.5%, respectively. The number of steps during the 6MST was significantly correlated with the 6MWD before (r = 0.72; p < 0.0001) and after PR (r = 0.66; p < 0.0001). MID was estimated to be around 20 steps. The 6MST appears to be as responsive as the 6MWT in assessing functional improvement during PR in patients with COPD. The 6MST is a low-cost assessment and requires limited space. © 2016 S. Karger AG, Basel.

Daily step count predicts acute exacerbations in a US cohort with COPD.

PubMed

Moy, Marilyn L; Teylan, Merilee; Weston, Nicole A; Gagnon, David R; Garshick, Eric

2013-01-01

COPD is characterized by variability in exercise capacity and physical activity (PA), and acute exacerbations (AEs). Little is known about the relationship between daily step count, a direct measure of PA, and the risk of AEs, including hospitalizations. In an observational cohort study of 169 persons with COPD, we directly assessed PA with the StepWatch Activity Monitor, an ankle-worn accelerometer that measures daily step count. We also assessed exercise capacity with the 6-minute walk test (6MWT) and patient-reported PA with the St. George's Respiratory Questionnaire Activity Score (SGRQ-AS). AEs and COPD-related hospitalizations were assessed and validated prospectively over a median of 16 months. Mean daily step count was 5804±3141 steps. Over 209 person-years of observation, there were 263 AEs (incidence rate 1.3±1.6 per person-year) and 116 COPD-related hospitalizations (incidence rate 0.56±1.09 per person-year). Adjusting for FEV1 % predicted and prednisone use for AE in previous year, for each 1000 fewer steps per day walked at baseline, there was an increased rate of AEs (rate ratio 1.07; 95%CI = 1.003-1.15) and COPD-related hospitalizations (rate ratio 1.24; 95%CI = 1.08-1.42). There was a significant linear trend of decreasing daily step count by quartiles and increasing rate ratios for AEs (P = 0.008) and COPD-related hospitalizations (P = 0.003). Each 30-meter decrease in 6MWT distance was associated with an increased rate ratio of 1.07 (95%CI = 1.01-1.14) for AEs and 1.18 (95%CI = 1.07-1.30) for COPD-related hospitalizations. Worsening of SGRQ-AS by 4 points was associated with an increased rate ratio of 1.05 (95%CI = 1.01-1.09) for AEs and 1.10 (95%CI = 1.02-1.17) for COPD-related hospitalizations. Lower daily step count, lower 6MWT distance, and worse SGRQ-AS predict future AEs and COPD-related hospitalizations, independent of pulmonary function and previous AE history. These results support the importance of assessing PA in patients with COPD, and provide the rationale to promote PA as part of exacerbation-prevention strategies.

Evaluating the Validity of Current Mainstream Wearable Devices in Fitness Tracking Under Various Physical Activities: Comparative Study

PubMed Central

Xie, Junqing; Wen, Dong; Liang, Lizhong; Jia, Yuxi; Gao, Li

2018-01-01

Background Wearable devices have attracted much attention from the market in recent years for their fitness monitoring and other health-related metrics; however, the accuracy of fitness tracking results still plays a major role in health promotion. Objective The aim of this study was to evaluate the accuracy of a host of latest wearable devices in measuring fitness-related indicators under various seminatural activities. Methods A total of 44 healthy subjects were recruited, and each subject was asked to simultaneously wear 6 devices (Apple Watch 2, Samsung Gear S3, Jawbone Up3, Fitbit Surge, Huawei Talk Band B3, and Xiaomi Mi Band 2) and 2 smartphone apps (Dongdong and Ledongli) to measure five major health indicators (heart rate, number of steps, distance, energy consumption, and sleep duration) under various activity states (resting, walking, running, cycling, and sleeping), which were then compared with the gold standard (manual measurements of the heart rate, number of steps, distance, and sleep, and energy consumption through oxygen consumption) and calculated to determine their respective mean absolute percentage errors (MAPEs). Results Wearable devices had a rather high measurement accuracy with respect to heart rate, number of steps, distance, and sleep duration, with a MAPE of approximately 0.10, whereas poor measurement accuracy was observed for energy consumption (calories), indicated by a MAPE of up to 0.44. The measurements varied for the same indicator measured by different fitness trackers. The variation in measurement of the number of steps was the highest (Apple Watch 2: 0.42; Dongdong: 0.01), whereas it was the lowest for heart rate (Samsung Gear S3: 0.34; Xiaomi Mi Band 2: 0.12). Measurements differed insignificantly for the same indicator measured under different states of activity; the MAPE of distance and energy measurements were in the range of 0.08 to 0.17 and 0.41 to 0.48, respectively. Overall, the Samsung Gear S3 performed the best for the measurement of heart rate under the resting state (MAPE of 0.04), whereas Dongdong performed the best for the measurement of the number of steps under the walking state (MAPE of 0.01). Fitbit Surge performed the best for distance measurement under the cycling state (MAPE of 0.04), and Huawei Talk Band B3 performed the best for energy consumption measurement under the walking state (MAPE of 0.17). Conclusions At present, mainstream devices are able to reliably measure heart rate, number of steps, distance, and sleep duration, which can be used as effective health evaluation indicators, but the measurement accuracy of energy consumption is still inadequate. Fitness trackers of different brands vary with regard to measurement of indicators and are all affected by the activity state, which indicates that manufacturers of fitness trackers need to improve their algorithms for different activity states. PMID:29650506

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.

Association of MCAT scores obtained with standard vs extra administration time with medical school admission, medical student performance, and time to graduation.

PubMed

Searcy, Cynthia A; Dowd, Keith W; Hughes, Michael G; Baldwin, Sean; Pigg, Trey

2015-06-09

Individuals with documented disabilities may receive accommodations on the Medical College Admission Test (MCAT). Whether such accommodations are associated with MCAT scores, medical school admission, and medical school performance is unclear. To determine the comparability of MCAT scores obtained with standard vs extra administration time with respect to likelihood of acceptance to medical school and future medical student performance. Retrospective cohort study of applicants to US medical schools for the 2011-2013 entering classes who reported MCAT scores obtained with standard time (n = 133,962) vs extra time (n = 435), and of students who matriculated in US medical schools from 2000-2004 who reported MCAT scores obtained with standard time (n = 76,262) vs extra time (n = 449). Standard or extra administration time during MCAT. Primary outcome measures were acceptance rates at US medical schools and graduation rates within 4 or 5 years after matriculation. Secondary outcome measures were pass rates on the United States Medical Licensing Examination (USMLE) Step examinations and graduation rates within 6 to 8 years after matriculation. Acceptance rates were not significantly different for applicants who had MCAT scores obtained with standard vs extra time (44.5% [59,585/133,962] vs 43.9% [191/435]; difference, 0.6% [95% CI, -4.1 to 5.3]). Students who tested with extra time passed the Step examinations on first attempt at significantly lower rates (Step 1, 82.1% [344/419] vs 94.0% [70,188/74,668]; difference, 11.9% [95% CI, 9.6% to 14.2%]; Step 2 CK, 85.5% [349/408] vs 95.4% [70,476/73,866]; difference, 9.9% [95% CI, 7.8% to 11.9%]; Step 2 CS, 92.0% [288/313] vs 97.0% [60,039/61,882]; difference, 5.0% [95% CI, 3.1% to 6.9%]). They also graduated from medical school at significantly lower rates at different times (4 years, 67.2% [285/424] vs 86.1% [60,547/70,305]; difference, 18.9% [95% CI, 15.6% to 22.2%]; 5 years, 81.6% [346/424] vs 94.4% [66,369/70,305]; difference, 12.8% [95% CI, 10.6% to 15.0%]; 6 years, 85.4% [362/424] vs 95.8% [67,351/70,305]; difference, 10.4% [95% CI, 8.5% to 12.4%]; 7 years, 88.0% [373/424] vs 96.2% [67,639/70,305]; difference, 8.2% [95% CI, 6.4% to 10.1%]; 8 years, 88.4% [375/424] vs 96.5% [67,847/70,305]; difference, 8.1% [95% CI, 6.3% to 9.8%]). These differences remained after controlling for MCAT scores and undergraduate grade point averages. Among applicants to US medical schools, those with MCAT scores obtained with extra test administration time, compared with standard administration time, had no significant difference in rate of medical school admission but had lower rates of passing the USMLE Step examinations and of medical school graduation within 4 to 8 years after matriculation. These findings raise questions about the types of learning environments and support systems needed by students who test with extra time on the MCAT to enable them to succeed in medical school.

Quantitative UV spectroscopy of early O stars on the Magellanic Clouds: The determination of the stellar metallicities

NASA Technical Reports Server (NTRS)

Haser, Stefan M.; Pauldrach, Adalbert W. A.; Lennon, Danny J.; Kudritzki, Rolf-Peter; Lennon, Maguerite; Puls, Joachim; Voels, Stephen A.

1997-01-01

Ultraviolet spectra of four O stars in the Magellanic Clouds obtained with the faint object spectrograph of the Hubble Space Telescope are analyzed with respect to their metallicity. The metal abundances are derived from the stellar parameters and the mass loss rate with a two step procedure: hydrodynamic radiation-driven wind models with metallicity as a free parameter are constructed to fit the observed wind momentum rate and thus yield a dynamical metallicity, and synthetic spectra are computed for different metal abundances and compared to the observed spectra in order to obtain a spectroscopic metallicity.

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

NASA Astrophysics Data System (ADS)

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

2018-02-01

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

Tyrosine content, influx and accumulation rate, and catecholamine biosynthesis measured in vivo, in the central nervous system and in peripheral organs of the young rat. Influence of neonatal hypo- and hyperthyroidism.

PubMed

Diarra, A; Lefauconnier, J M; Valens, M; Georges, P; Gripois, D

1989-10-01

The influence of neonatal hypo- and hyperthyroidism on different aspects of tyrosine metabolism in the hypothalamus, striatum, brainstem, adrenal glands, heart and brown adipose tissue (BAT) were studied in 14-day old rats. The synthesis rate of catecholamines (CA) was also determined in vivo after the injection of labelled tyrosine. Hypothyroidism increases tyrosinaemia and endogenous tyrosine concentration in the hypothalamus and BAT. Hyperthyroidism decreases tyrosinaemia and endogenous tyrosine levels in the striatum, adrenals and heart. The accumulation rate of tyrosine determined 30 min after an intravenous injection of the labelled amino acid has been determined in the organs, together with the influx of the amino acid, determined within 20s. Hypothyroidism increases tyrosine accumulation rate in all the organs studied, and tyrosine clearance is decreased in the striatum and brainstem; together with an increased tyrosinaemia, this leads to a normal influx. The influx of tyrosine is increased in the hypothalamus. Hyperthyroidism decreases tyrosine accumulation rate in all the organs except the adrenals. These results indicate that the thyroid status of the young rat can influence tyrosine uptake mechanisms, without modifying an organ's tyrosine content. The fact that hypothyroidism increases tyrosine influx in the hypothalamus without modifying it in the brainstem and striatum reflects an heterogeneous reactivity to the lack of thyroid hormones in different brain structures. Neonatal hypothyroidism decreases the CA synthesis rate in the striatum, the heart and the interscapular brown adipose tissue, while synthesis was enhanced in the brainstem and the adrenals. It is likely that these variations in CA synthesis are due to thyroid hormone modulation of tyrosine hydroxylase activity, the enzyme which catalyses the rate limiting step in CA biosynthesis.

Heat and mass transfer during the cryopreservation of a bioartificial liver device: a computational model.

PubMed

Balasubramanian, Saravana K; Coger, Robin N

2005-01-01

Bioartificial liver devices (BALs) have proven to be an effective bridge to transplantation for cases of acute liver failure. Enabling the long-term storage of these devices using a method such as cryopreservation will ensure their easy off the shelf availability. To date, cryopreservation of liver cells has been attempted for both single cells and sandwich cultures. This study presents the potential of using computational modeling to help develop a cryopreservation protocol for storing the three dimensional BAL: Hepatassist. The focus is upon determining the thermal and concentration profiles as the BAL is cooled from 37 degrees C-100 degrees C, and is completed in two steps: a cryoprotectant loading step and a phase change step. The results indicate that, for the loading step, mass transfer controls the duration of the protocol, whereas for the phase change step, when mass transfer is assumed negligible, the latent heat released during freezing is the control factor. The cryoprotocol that is ultimately proposed considers time, cooling rate, and the temperature gradients that the cellular space is exposed to during cooling. To our knowledge, this study is the first reported effort toward designing an effective protocol for the cryopreservation of a three-dimensional BAL device.

An iterative procedure for obtaining maximum-likelihood estimates of the parameters for a mixture of normal distributions

NASA Technical Reports Server (NTRS)

Peters, B. C., Jr.; Walker, H. F.

1978-01-01

This paper addresses the problem of obtaining numerically maximum-likelihood estimates of the parameters for a mixture of normal distributions. In recent literature, a certain successive-approximations procedure, based on the likelihood equations, was shown empirically to be effective in numerically approximating such maximum-likelihood estimates; however, the reliability of this procedure was not established theoretically. Here, we introduce a general iterative procedure, of the generalized steepest-ascent (deflected-gradient) type, which is just the procedure known in the literature when the step-size is taken to be 1. We show that, with probability 1 as the sample size grows large, this procedure converges locally to the strongly consistent maximum-likelihood estimate whenever the step-size lies between 0 and 2. We also show that the step-size which yields optimal local convergence rates for large samples is determined in a sense by the 'separation' of the component normal densities and is bounded below by a number between 1 and 2.

An iterative procedure for obtaining maximum-likelihood estimates of the parameters for a mixture of normal distributions, 2

NASA Technical Reports Server (NTRS)

Peters, B. C., Jr.; Walker, H. F.

1976-01-01

The problem of obtaining numerically maximum likelihood estimates of the parameters for a mixture of normal distributions is addressed. In recent literature, a certain successive approximations procedure, based on the likelihood equations, is shown empirically to be effective in numerically approximating such maximum-likelihood estimates; however, the reliability of this procedure was not established theoretically. Here, a general iterative procedure is introduced, of the generalized steepest-ascent (deflected-gradient) type, which is just the procedure known in the literature when the step-size is taken to be 1. With probability 1 as the sample size grows large, it is shown that this procedure converges locally to the strongly consistent maximum-likelihood estimate whenever the step-size lies between 0 and 2. The step-size which yields optimal local convergence rates for large samples is determined in a sense by the separation of the component normal densities and is bounded below by a number between 1 and 2.

Highly efficient one-pot/one-step synthesis of multiblock copolymers from three-component polymerization of carbon dioxide, epoxide and lactone.

PubMed

Li, Yang; Hong, Jiali; Wei, Renjian; Zhang, Yingying; Tong, Zaizai; Zhang, Xinghong; Du, Binyang; Xu, Junting; Fan, Zhiqiang

2015-02-01

It is a long-standing challenge to combine mixed monomers into multiblock copolymer (MBC) in a one-pot/one-step polymerization manner. We report the first example of MBC with biodegradable polycarbonate and polyester blocks that were synthesized from highly efficient one-pot/one-step polymerization of cyclohexene oxide (CHO), CO 2 and ε-caprolactone (ε-CL) in the presence of zinc-cobalt double metal cyanide complex and stannous octoate. In this protocol, two cross-chain exchange reactions (CCER) occurred at dual catalysts respectively and connected two independent chain propagation procedures ( i.e. , polycarbonate formation and polyester formation) simultaneously in a block-by-block manner, affording MBC without tapering structure. The multiblock structure of MBC was determined by the rate ratio of CCER to the two chain propagations and could be simply tuned by various kinetic factors. This protocol is also of significance due to partial utilization of renewable CO 2 and improved mechanical properties of the resultant MBC.

Filler bar heating due to stepped tiles in the shuttle orbiter thermal protection system

NASA Technical Reports Server (NTRS)

Petley, D. H.; Smith, D. M.; Edwards, C. L. W.; Patten, A. B.; Hamilton, H. H., II

1983-01-01

An analytical study was performed to investigate the excessive heating in the tile to tile gaps of the Shuttle Orbiter Thermal Protection System due to stepped tiles. The excessive heating was evidence by visible discoloration and charring of the filler bar and strain isolation pad that is used in the attachment of tiles to the aluminum substrate. Two tile locations on the Shuttle orbiter were considered, one on the lower surface of the fuselage and one on the lower surface of the wing. The gap heating analysis involved the calculation of external and internal gas pressures and temperatures, internal mass flow rates, and the transient thermal response of the thermal protection system. The results of the analysis are presented for the fuselage and wing location for several step heights. The results of a study to determine the effectiveness of a half height ceramic fiber gap filler in preventing hot gas flow in the tile gaps are also presented.

Fluidic Automation of Nitrate and Nitrite Bioassays in Whole Blood by Dissolvable-Film Based Centrifugo-Pneumatic Actuation

PubMed Central

Nwankire, Charles E.; Chan, Di-Sien S.; Gaughran, Jennifer; Burger, Robert; Gorkin, Robert; Ducrée, Jens

2013-01-01

This paper demonstrates the full centrifugal microfluidic integration and automation of all liquid handling steps of a 7-step fluorescence-linked immunosorbent assay (FLISA) for quantifying nitrate and nitrite levels in whole blood within about 15 min. The assay protocol encompasses the extraction of metered plasma, the controlled release of sample and reagents (enzymes, co-factors and fluorescent labels), and incubation and detection steps. Flow control is implemented by a rotationally actuated dissolvable film (DF) valving scheme. In the valves, the burst pressure is primarily determined by the radial position, geometry and volume of the valve chamber and its inlet channel and can thus be individually tuned over an extraordinarily wide range of equivalent spin rates between 1,000 RPM and 5,500 RPM. Furthermore, the vapour barrier properties of the DF valves are investigated in this paper in order to further show the potential for commercially relevant on-board storage of liquid reagents during shelf-life of bioanalytical, ready-to-use discs. PMID:24064595

Fluidic automation of nitrate and nitrite bioassays in whole blood by dissolvable-film based centrifugo-pneumatic actuation.

PubMed

Nwankire, Charles E; Chan, Di-Sien S; Gaughran, Jennifer; Burger, Robert; Gorkin, Robert; Ducrée, Jens

2013-08-26

This paper demonstrates the full centrifugal microfluidic integration and automation of all liquid handling steps of a 7-step fluorescence-linked immunosorbent assay (FLISA) for quantifying nitrate and nitrite levels in whole blood within about 15 min. The assay protocol encompasses the extraction of metered plasma, the controlled release of sample and reagents (enzymes, co-factors and fluorescent labels), and incubation and detection steps. Flow control is implemented by a rotationally actuated dissolvable film (DF) valving scheme. In the valves, the burst pressure is primarily determined by the radial position, geometry and volume of the valve chamber and its inlet channel and can thus be individually tuned over an extraordinarily wide range of equivalent spin rates between 1,000 RPM and 5,500 RPM. Furthermore, the vapour barrier properties of the DF valves are investigated in this paper in order to further show the potential for commercially relevant on-board storage of liquid reagents during shelf-life of bioanalytical, ready-to-use discs.

The dissolution kinetics of industrial brine sludge wastes from a chlor-alkali industry as a sorbent for wet flue gas desulfurization (FGD).

PubMed

Masilela, E; Lerotholi, L; Seodigeng, T; Rutto, H

2018-02-01

The disposal of industrial brine sludge waste (IBSW) in chlor-alkali plants can be avoided by utilization of IBSW as a sorbent in wet flue gas desulfurization (FGD). The shrinking core model was used to determine the dissolution kinetics of IBSW, which is a vital step in wet FGD. The effects of solid-to-liquid ratio (m/v), temperature, pH, particle size, and stirring speed on the conversion and dissolution rate constant are determined. The conversion and dissolution rate constant decreases as the pH, particle size, and solid-to-liquid ratio are increased and increases as the temperature, concentration of acid, and stirring speed are increased. The sorbents before and after dissolution were characterized using x-ray fluorescence (XRF), x-ray diffraction (XRD), and scanning electron microscopy (SEM). An activation energy of 7.195 kJ/mol was obtained and the product layer diffusion model was found to be the rate-controlling step. The use of industrial brine sludge waste as an alternative sorbent in wet flue gas desulfurization can reduce the amounts of industrial wastes disposed of in landfills. This study has proved that the sorbent can contain up to 91% calcium carbonate and trace amounts of sulfate, magnesium, and so on. This can be used as new sorbent to reduce the amount of sulfur dioxide in the atmosphere and the by-product gypsum can be used in construction, as a plaster ingredient, as a fertilizer, and for soil conditioning. Therefore, the sorbent has both economic and environmental benefits.

A Finite-Rate-Catalytic Model For Hypersonic Flows Informed By Molecular Dynamics

NASA Astrophysics Data System (ADS)

Schwartzentruber, T. E.; Valentini, P.; Norman, P.; Sorensen, C.

2011-05-01

The implementation of a finite-rate catalytic (FRC) wall boundary condition within a general 3D unstructured CFD solver is described. A set of one-step gas-surface chemical equations and atomistic parameters that deter- mine the reaction rates must be prescribed as input to the model. The chemical rate equations are solved at each wall face in the CFD simulation and result in a net production of species at the wall. In order for a finite- rate gas-surface reaction model to be consistent at equilibrium, it is determined that not all forward and back- ward rates can be specified arbitrarily. Provided that the forward rates for each surface recombination are as- signed, the backward rates must be determined using equilibrium constants that are consistent with the gas- phase chemistry model and thermodynamics. Reactive molecular dynamics (MD) simulations are performed us- ing the ReaxFFSiO potential to investigate oxygen-silica interactions. β-quartz and amorphous SiO2 surfaces are accommodated to a high temperature gas via MD simulation and reach a steady-state surface coverage. In addition to stable surface reconstructions a number of active sites are observed on which recombination occurs. Single collision MD simulations are performed where gas-phase oxygen atoms interact with the most dominant active site. Probabilities of recombination are found to have an exponential trend with gas-surface system temperature. The MD simulations are used to determine the activation energy for Eley-Rideal recombination of oxygen on a specific silica active site which is an important input parameter for the FRC model.

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

Bockris, J.O.; Devanathan, M.A.V.

The galvanostatic double charging method was applied to determine the coverage of Ni cathodes with adsorbed atomic H in 2 N NaOH solutions. Anodic current densities were varied from 0.05 to 1.8 amp/sq cm. The plateau indicating absence of readsorption was between 0.6 and 1.8 amp/sq cm, for a constant cathodic c.d. of 1/10,000 amp/sq cm. The variation of the adsorbed H over cathodic c.d.'s ranging from 10 to the -6th power to 1/10 at a constant anodic c.d. of 1 amp/sq cm were calculated and the coverage calculated. The mechanism of the H evolution reaction was elucidated. The ratemore » determining step is discharge from a water molecules followed by rapid Tafel recombination. The rate constants for these processes and the rate constant for the ionisation, calculated with the extrapolated value of coverage for the reversible H electrode, were determined. A modification of the Tafel equation which takes into account both coverage and ionisation is in harmony with the results. A new method for the determination of coverage suitable for corrodible metals is described which involves the measurement of the rate of permeation of H by electrochemical techniques which enhances the sensitivity of the method. (Author)« less

Ionic liquids coated Fe3O4 based inorganic-organic hybrid materials and their application in the simultaneous determination of DNA bases.

PubMed

Kaur, Balwinder; Srivastava, Rajendra

2014-06-01

Ionic liquids (ILs) coated Fe3O4 based inorganic-organic hybrid materials (represented as Fe3O4/ILs) were synthesized. ILs such as methylimidazolium chloride ([Hmim][Cl]) and 1-butyl-3-methylimidazolium chloride ([Bmim][Cl]) were investigated. For comparative study, quaternary ammonium salts such as choline chloride, cetyltrimethylammonium bromide [C16H33N(CH3)3][Br], and trimethylstearylammonium chloride [C18H37N(CH3)3][Cl] were also investigated. Materials were characterized by X-ray diffraction, nitrogen sorption, Fourier transform infrared and scanning/transmission electron microscopy. Electrochemical sensors based on Fe3O4/ILs modified glassy carbon electrodes were fabricated for the simultaneous determination of all four DNA bases. The electrochemical behavior of DNA bases was investigated in detail. Various reaction parameters such as effect of scan rate, number of electrons involved in the rate determining step, electron transfer coefficient, surface adsorbed concentration, and the electrode reaction standard rate constant were investigated. Catalytic activity obtained at various Fe3O4/ILs modified electrodes was explained using DFT calculation. The analytical performance of the sensor was demonstrated in the simultaneous determination of guanine, adenine, thymine, and cytosine in calf thymus DNA sample. Copyright © 2014 Elsevier B.V. All rights reserved.

5 CFR 532.203 - Structure of regular wage schedules.

Code of Federal Regulations, 2011 CFR

2011-01-01

... grade; (3) NA means a nonappropriated fund nonsupervisory grade; and (4) NL means a nonappropriated fund... schedule for the area, plus 20 percent of the rate for step 2 of NA-8; (2) For grades NS-9 through NS-15... percent, respectively, above the step 2 rate of NA-15; (f) The number of within-grade steps and the...

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

Hoang Duc, Albert K., E-mail: albert.hoangduc.ucl@gmail.com; McClelland, Jamie; Modat, Marc

Purpose: The aim of this study was to assess whether clinically acceptable segmentations of organs at risk (OARs) in head and neck cancer can be obtained automatically and efficiently using the novel “similarity and truth estimation for propagated segmentations” (STEPS) compared to the traditional “simultaneous truth and performance level estimation” (STAPLE) algorithm. Methods: First, 6 OARs were contoured by 2 radiation oncologists in a dataset of 100 patients with head and neck cancer on planning computed tomography images. Each image in the dataset was then automatically segmented with STAPLE and STEPS using those manual contours. Dice similarity coefficient (DSC) wasmore » then used to compare the accuracy of these automatic methods. Second, in a blind experiment, three separate and distinct trained physicians graded manual and automatic segmentations into one of the following three grades: clinically acceptable as determined by universal delineation guidelines (grade A), reasonably acceptable for clinical practice upon manual editing (grade B), and not acceptable (grade C). Finally, STEPS segmentations graded B were selected and one of the physicians manually edited them to grade A. Editing time was recorded. Results: Significant improvements in DSC can be seen when using the STEPS algorithm on large structures such as the brainstem, spinal canal, and left/right parotid compared to the STAPLE algorithm (all p < 0.001). In addition, across all three trained physicians, manual and STEPS segmentation grades were not significantly different for the brainstem, spinal canal, parotid (right/left), and optic chiasm (all p > 0.100). In contrast, STEPS segmentation grades were lower for the eyes (p < 0.001). Across all OARs and all physicians, STEPS produced segmentations graded as well as manual contouring at a rate of 83%, giving a lower bound on this rate of 80% with 95% confidence. Reduction in manual interaction time was on average 61% and 93% when automatic segmentations did and did not, respectively, require manual editing. Conclusions: The STEPS algorithm showed better performance than the STAPLE algorithm in segmenting OARs for radiotherapy of the head and neck. It can automatically produce clinically acceptable segmentation of OARs, with results as relevant as manual contouring for the brainstem, spinal canal, the parotids (left/right), and optic chiasm. A substantial reduction in manual labor was achieved when using STEPS even when manual editing was necessary.« less

Comparative evaluation of heart rate-based monitors: Apple Watch vs Fitbit Charge HR.

PubMed

Bai, Yang; Hibbing, Paul; Mantis, Constantine; Welk, Gregory J

2018-08-01

The purpose of this investigation was to examine the validity of energy expenditure (EE), steps, and heart rate measured with the Apple Watch 1 and Fitbit Charge HR. Thirty-nine healthy adults wore the two monitors while completing a semi-structured activity protocol consisting of 20 minutes of sedentary activity, 25 minutes of aerobic exercise, and 25 minutes of light intensity physical activity. Criterion measures were obtained from an Oxycon Mobile for EE, a pedometer for steps, and a Polar heart rate strap worn on the chest for heart rate. For estimating whole-trial EE, the mean absolute percent error (MAPE) from Fitbit Charge HR (32.9%) was more than twice that of Apple Watch 1 (15.2%). This trend was consistent for the individual conditions. Both monitors accurately assessed steps during aerobic activity (MAPE Apple : 6.2%; MAPE Fitbit : 9.4%) but overestimated steps in light physical activity. For heart rate, Fitbit Charge HR produced its smallest MAPE in sedentary behaviors (7.2%), followed by aerobic exercise (8.4%), and light activity (10.1%). The Apple Watch 1 had stronger validity than the Fitbit Charge HR for assessing overall EE and steps during aerobic exercise. The Fitbit Charge HR provided heart rate estimates that were statistically equivalent to Polar monitor.

Kinetics and mechanism of hydration of o-thioquinone methide in aqueous solution. Rate-determining protonation of sulfur.

PubMed

Chiang, Yvonne; Kresge, A Jerry; Sadovski, Oleg; Zhan, Hao-Qiang

2005-03-04

o-Thioquinone methide, 2, was generated in aqueous solution by flash photolysis of benzothiete, 1, and rates of hydration of this quinone methide to o-mercaptobenzyl alcohol, 3, were measured in perchloric acid solutions, using H2O and D2O as the solvent, and also in acetic acid and tris(hydroxymethyl)methylammonium ion buffers, using H2O as the solvent. The rate profiles constructed from these data show hydronium-ion-catalyzed and uncatalyzed hydration reaction regions, just like the rate profiles based on literature data for hydration of the oxygen analogue, o-quinone methide, of the presently examined substrate. Solvent isotope effects on hydronium-ion catalysis of hydration for the two substrates, however, are quite different: k(H)/k(D) = 0.42 for the oxygen quinone methide, whereas k(H)/k(D) = 1.66 for the sulfur substrate. The inverse nature (k(H)/k(D) < 1) of the isotope effect in the oxygen system indicates that this reaction occurs by a preequilibrium proton-transfer reaction mechanism, with protonation of the substrate on its oxygen atom being fast and reversible and capture of the benzyl-type carbocationic intermediate so formed being rate-determining. The normal direction (k(H)/k(D) > 1) of the isotope effect in the sulfur system, on the other hand, suggests that protonation of the substrate on its sulfur atom is in this case rate-determining, with carbocation capture a fast following step. A semiquantitative argument supporting this hypothesis is presented.

An Empirical Method Permitting Rapid Determination of the Area, Rate and Distribution of Water-Drop Impingement on an Airfoil of Arbitrary Section at Subsonic Speeds

NASA Technical Reports Server (NTRS)

Bergrun, N. R.

1951-01-01

An empirical method for the determination of the area, rate, and distribution of water-drop impingement on airfoils of arbitrary section is presented. The procedure represents an initial step toward the development of a method which is generally applicable in the design of thermal ice-prevention equipment for airplane wing and tail surfaces. Results given by the proposed empirical method are expected to be sufficiently accurate for the purpose of heated-wing design, and can be obtained from a few numerical computations once the velocity distribution over the airfoil has been determined. The empirical method presented for incompressible flow is based on results of extensive water-drop. trajectory computations for five airfoil cases which consisted of 15-percent-thick airfoils encompassing a moderate lift-coefficient range. The differential equations pertaining to the paths of the drops were solved by a differential analyzer. The method developed for incompressible flow is extended to the calculation of area and rate of impingement on straight wings in subsonic compressible flow to indicate the probable effects of compressibility for airfoils at low subsonic Mach numbers.

Optimization of the secondary drying step in freeze drying using TDLAS technology.

PubMed

Schneid, Stefan C; Gieseler, Henning; Kessler, William J; Luthra, Suman A; Pikal, Michael J

2011-03-01

The secondary drying phase in freeze drying is mostly developed on a trial-and-error basis due to the lack of appropriate noninvasive process analyzers. This study describes for the first time the application of Tunable Diode Laser Absorption Spectroscopy, a spectroscopic and noninvasive sensor for monitoring secondary drying in laboratory-scale freeze drying with the overall purpose of targeting intermediate moisture contents in the product. Bovine serum albumin/sucrose mixtures were used as a model system to imitate high concentrated antibody formulations. First, the rate of water desorption during secondary drying at constant product temperatures (-22 °C, -10 °C, and 0 °C) was investigated for three different shelf temperatures. Residual moisture contents of sampled vials were determined by Karl Fischer titration. An equilibration step was implemented to ensure homogeneous distribution of moisture (within 1%) in all vials. The residual moisture revealed a linear relationship to the water desorption rate for different temperatures, allowing the evaluation of an anchor point from noninvasive flow rate measurements without removal of samples from the freeze dryer. The accuracy of mass flow integration from this anchor point was found to be about 0.5%. In a second step, the concept was successfully tested in a confirmation experiment. Here, good agreement was found for the initial moisture content (anchor point) and the subsequent monitoring and targeting of intermediate moisture contents. The present approach for monitoring secondary drying indicated great potential to find wider application in sterile operations on production scale in pharmaceutical freeze drying. © 2011 American Association of Pharmaceutical Scientists

Zeolite catalysis in the synthesis of isobutylene from hydrous ethanol

NASA Astrophysics Data System (ADS)

Phillips, Cory Bernard

1999-11-01

This work deals with the synthesis of isobutylene from a hydrous ethanol feedstock over zeolites. The synthesis is accomplished in three steps: (1) low-temperature direct ethanol conversion to ethylene on H-ZSM-5 zeolite, (2) ethylene conversion to butene products over metal-exchanged zeolites, and (3) butene skeletal rearrangement to isobutylene over FER zeolites. The key to understanding and optimizing each synthesis step lies in the ability to control and regulate the zeolite acidity (Bronsted and Lewis)---both strength and number. Therefore, the continuous temperature programmed amine desorption (CTPAD) technique was further developed to simultaneously count the Bronsted acid sites and quantitatively characterize their strength. The adsorption of ethanol, reaction products, amines, coke and ethanol-derived residue (EDR) were monitored gravimetrically using the highly sensitive, novel Tapered Element Oscillating Microreactor (TEOM) apparatus. The TEOM was also used also in conjunction with CTPAD to characterize Bronsted acidity which is a new application for the instrument. For the first synthesis step, a parallel reaction exists which simultaneously produces diethyl ether and ethylene directly over H-ZSM-5. The reaction rates for each pathway were measured directly using a differential reactor operating at low temperatures (<473 K). Water in the ethanol feed enhances the rate of ethylene formation. A mechanism and kinetic expression are proposed for this reaction over H-ZSM-5, with diethyl-ether desorption and ethylene formation as the rate limiting steps. Heat of adsorption values measured from the independent microcalorimetry work reported in the literature are incorporated into the kinetic analysis which reduces the number of regressed parameters. For the remaining synthesis steps, several zeolite structures (ZSM-5, Y, FER) partially exchanged with Pd, Ti, Ni and Au were prepared and tested. It was determined from this screening study that the zeolites containing Pd are the most efficient catalysts for the dimerization reaction. Characterization results from x-ray diffraction (XRD), electron paramagnetic resonance (EPR) spectroscopy, and CTPAD suggest a stable, Pd species with a low oxidation state as part of the active site in Pd-exchanged zeolites. Isobutylene was present in the C4 fraction at reasonable quantities for most of the catalyst candidates, especially those containing an alkali metal co-cation.

Mathematical Methods for Studying DNA and Protein Interactions

NASA Astrophysics Data System (ADS)

LeGresley, Sarah

Deoxyribnucleic Acid (DNA) damage can lead to health related issues such as developmental disorders, aging, and cancer. It has been estimated that damage rates may be as high as 100,000 per cell per day. Because of the devastating effects that DNA damage can have, DNA repair mechanisms are of great interest yet are not completely understood. To gain a better understanding of possible DNA repair mechanisms, my dissertation focused on mathematical methods for understanding the interactions between DNA and proteins. I developed a damaged DNA model to estimate the probabilities of damaged DNA being located at specific positions. Experiments were then performed that suggested that the damaged DNA may be repositioned. These experimental results were consistent with the model's prediction that damaged DNA has preferred locations. To study how proteins might be moving along the DNA, I studied the use of the uniform motion "n-step" model. The n-step model has been used to determine the kinetics parameters (e.g. rates at which a protein moves along the DNA, how much energy is required to move a protein along a specified amount of DNA, etc.) of proteins moving along the DNA. Monte Carlo methods were used to simulate proteins moving with different types of non-uniform motion (e.g. backward, jumping, etc.) along the DNA. Estimates for the kinetics parameters in the n-step model were found by fitting of the Monte Carlo simulation data. Analysis indicated that non-uniform motion of the protein may lead to over or underestimation of the kinetic parameters of this n-step model.

Prediction of work metabolism from heart rate measurements in forest work: some practical methodological issues.

PubMed

Dubé, Philippe-Antoine; Imbeau, Daniel; Dubeau, Denise; Auger, Isabelle; Leone, Mario

2015-01-01

Individual heart rate (HR) to workload relationships were determined using 93 submaximal step-tests administered to 26 healthy participants attending physical activities in a university training centre (laboratory study) and 41 experienced forest workers (field study). Predicted maximum aerobic capacity (MAC) was compared to measured MAC from a maximal treadmill test (laboratory study) to test the effect of two age-predicted maximum HR Equations (220-age and 207-0.7 × age) and two clothing insulation levels (0.4 and 0.91 clo) during the step-test. Work metabolism (WM) estimated from forest work HR was compared against concurrent work V̇O2 measurements while taking into account the HR thermal component. Results show that MAC and WM can be accurately predicted from work HR measurements and simple regression models developed in this study (1% group mean prediction bias and up to 25% expected prediction bias for a single individual). Clothing insulation had no impact on predicted MAC nor age-predicted maximum HR equations. Practitioner summary: This study sheds light on four practical methodological issues faced by practitioners regarding the use of HR methodology to assess WM in actual work environments. More specifically, the effect of wearing work clothes and the use of two different maximum HR prediction equations on the ability of a submaximal step-test to assess MAC are examined, as well as the accuracy of using an individual's step-test HR to workload relationship to predict WM from HR data collected during actual work in the presence of thermal stress.

Carbothermal Reduction of Quartz with Carbon from Natural Gas

NASA Astrophysics Data System (ADS)

Li, Fei; Tangstad, Merete

2017-04-01

Carbothermal reaction between quartz and two different carbons originating from natural gas were investigated in this paper. One of two carbons is the commercial carbon black produced from natural gas in a medium thermal production process. The other carbon is obtained from natural gas cracking at 1273 K (1000 °C) deposited directly on the quartz pellet. At the 1923 K (1650 °C) and CO atmosphere, the impact of carbon content, pellet structure, gas transfer, and heating rate are investigated in a thermo-gravimetric furnace. The reaction process can be divided into two steps: an initial SiC-producing step followed by a SiO-producing step. Higher carbon content and increased gas transfer improves the reaction rate of SiC-producing step, while the thicker carbon coating in carbon-deposited pellet hinders reaction rate. Better gas transfer of sample holder improves reaction rate but causes more SiO loss. Heating rate has almost no influence on reaction. Mass balance analysis shows that mole ratios between SiO2, free carbon, and SiC in the SiC-producing step and SiO-producing step in CO and Ar fit the reaction SiO2(s) + 3 C(s) = SiC(s) + 2 CO(g). SiC-particle and SiC-coating formation process in mixed pellet and carbon-deposited pellet are proposed. SiC whiskers formed in the voids of these two types of pellets.

Rh(I) -Catalyzed Intramolecular Carbonylative C-H/C-I Coupling of 2-Iodobiphenyls Using Furfural as a Carbonyl Source.

PubMed

Furusawa, Takuma; Morimoto, Tsumoru; Nishiyama, Yasuhiro; Tanimoto, Hiroki; Kakiuchi, Kiyomi

2016-08-19

Synthesis of fluoren-9-ones by a Rh-catalyzed intramolecular C-H/C-I carbonylative coupling of 2-iodobiphenyls using furfural as a carbonyl source is presented. The findings indicate that the rate-determining step is not a C-H bond cleavage but, rather, the oxidative addition of the C-I bond to a Rh(I) center. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Achieving the Holevo bound via a bisection decoding protocol

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

Rosati, Matteo; Giovannetti, Vittorio

2016-06-15

We present a new decoding protocol to realize transmission of classical information through a quantum channel at asymptotically maximum capacity, achieving the Holevo bound and thus the optimal communication rate. At variance with previous proposals, our scheme recovers the message bit by bit, making use of a series of “yes-no” measurements, organized in bisection fashion, thus determining which codeword was sent in log{sub 2} N steps, N being the number of codewords.

Kinetics of Electrocatalytic Reactions from First-Principles: A Critical Comparison with the Ab Initio Thermodynamics Approach.

PubMed

Exner, Kai S; Over, Herbert

2017-05-16

Multielectron processes in electrochemistry require the stabilization of reaction intermediates (RI) at the electrode surface after every elementary reaction step. Accordingly, the bond strengths of these intermediates are important for assessing the catalytic performance of an electrode material. Current understanding of microscopic processes in modern electrocatalysis research is largely driven by theory, mostly based on ab initio thermodynamics considerations, where stable reaction intermediates at the electrode surface are identified, while the actual free energy barriers (or activation barriers) are ignored. This simple approach is popular in electrochemistry in that the researcher has a simple tool at hand in successfully searching for promising electrode materials. The ab initio TD approach allows for a rough but fast screening of the parameter space with low computational cost. However, ab initio thermodynamics is also frequently employed (often, even based on a single binding energy only) to comprehend on the activity and on the mechanism of an electrochemical reaction. The basic idea is that the activation barrier of an endergonic reaction step consists of a thermodynamic part and an additional kinetically determined barrier. Assuming that the activation barrier scales with thermodynamics (so-called Brønsted-Polanyi-Evans (BEP) relation) and the kinetic part of the barrier is small, ab initio thermodynamics may provide molecular insights into the electrochemical reaction kinetics. However, for many electrocatalytic reactions, these tacit assumptions are violated so that ab initio thermodynamics will lead to contradictions with both experimental data and ab initio kinetics. In this Account, we will discuss several electrochemical key reactions, including chlorine evolution (CER), oxygen evolution reaction (OER), and oxygen reduction (ORR), where ab initio kinetics data are available in order to critically compare the results with those derived from a simple ab initio thermodynamics treatment. We show that ab initio thermodynamics leads to erroneous conclusions about kinetic and mechanistic aspects for the CER over RuO 2 (110), while the kinetics of the OER over RuO 2 (110) and ORR over Pt(111) are reasonably well described. Microkinetics of an electrocatalyzed reaction is largely simplified by the quasi-equilibria of the RI preceding the rate-determining step (rds) with the reactants. Therefore, in ab initio kinetics the rate of an electrocatalyzed reaction is governed by the transition state (TS) with the highest free energy G rds # , defining also the rate-determining step (rds). Ab initio thermodynamics may be even more powerful, when using the highest free energy of an reaction intermediate G max (RI) rather than the highest free energy difference between consecutive reaction intermediates, ΔG loss , as a descriptor for the kinetics.

Effect of Microstructure on Time Dependent Fatigue Crack Growth Behavior In a P/M Turbine Disk Alloy

NASA Technical Reports Server (NTRS)

Telesman, Ignacy J.; Gabb, T. P.; Bonacuse, P.; Gayda, J.

2008-01-01

A study was conducted to determine the processes which govern hold time crack growth behavior in the LSHR disk P/M superalloy. Nineteen different heat treatments of this alloy were evaluated by systematically controlling the cooling rate from the supersolvus solutioning step and applying various single and double step aging treatments. The resulting hold time crack growth rates varied by more than two orders of magnitude. It was shown that the associated stress relaxation behavior for these heat treatments was closely correlated with the crack growth behavior. As stress relaxation increased, the hold time crack growth resistance was also increased. The size of the tertiary gamma' in the general microstructure was found to be the key microstructural variable controlling both the hold time crack growth behavior and stress relaxation. No relationship between the presence of grain boundary M23C6 carbides and hold time crack growth was identified which further brings into question the importance of the grain boundary phases in determining hold time crack growth behavior. The linear elastic fracture mechanics parameter, Kmax, is unable to account for visco-plastic redistribution of the crack tip stress field during hold times and thus is inadequate for correlating time dependent crack growth data. A novel methodology was developed which captures the intrinsic crack driving force and was able to collapse hold time crack growth data onto a single curve.

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.

In situ high-energy synchrotron radiation study of boehmite formation, growth, and phase transformation to alumina in sub- and supercritical water.

PubMed

Lock, Nina; Bremholm, Martin; Christensen, Mogens; Almer, Jonathan; Chen, Yu-Sheng; Iversen, Bo B

2009-12-14

Boehmite (AlOOH) nanoparticles have been synthesized in subcritical (300 bar, 350 degrees C) and supercritical (300 bar, 400 degrees C) water. The formation and growth of AlOOH nanoparticles were studied in situ by small- and wide-angle X-ray scattering (SAXS and WAXS) using 80 keV synchrotron radiation. The SAXS/WAXS data were measured simultaneously with a time resolution greater than 10 s and revealed the initial nucleation of amorphous particles takes place within 10 s with subsequent crystallization after 30 s. No diffraction signals were observed from Al(OH)(3) within the time resolution of the experiment, which shows that the dehydration step of the reaction is fast and the hydrolysis step rate-determining. The sizes of the crystalline particles were determined as a function of time. The overall size evolution patterns are similar in sub- and supercritical water, but the growth is faster and the final particle size larger under supercritical conditions. After approximately 5 min, the rate of particle growth decreases in both sub- and supercritical water. Heating of the boehmite nanoparticle suspension allowed an in situ X-ray investigation of the phase transformation of boehmite to aluminium oxide. Under the wet conditions used in this work, the transition starts at 530 degrees C and gives a two-phase product of hydrated and non-hydrated aluminium oxide.

Step climbing capacity in patients with pulmonary hypertension.

PubMed

Fox, Benjamin Daniel; Langleben, David; Hirsch, Andrew; Boutet, Kim; Shimony, Avi

2013-01-01

Patients with pulmonary hypertension (PH) typically have exercise intolerance and limitation in climbing steps. To explore the exercise physiology of step climbing in PH patients, on a laboratory-based step test. We built a step oximetry system from an 'aerobics' step equipped with pressure sensors and pulse oximeter linked to a computer. Subjects mounted and dismounted from the step until their maximal exercise capacity or 200 steps was achieved. Step-count, SpO(2) and heart rate were monitored throughout exercise and recovery. We derived indices of exercise performance, desaturation and heart rate. A 6-min walk test and serum NT-proBrain Natriuretic Peptide (BNP) level were measured. Lung function tests and hemodynamic parameters were extracted from the medical record. Eighty-six subjects [52 pulmonary arterial hypertension (PAH), 14 chronic thromboembolic PH (CTEPH), 20 controls] were recruited. Exercise performance (climbing time, height gained, velocity, energy expenditure, work-rate and climbing index) on the step test was significantly worse with PH and/or worsening WHO functional class (ANOVA, p < 0.001). There was a good correlation between exercise performance on the step and 6-min walking distance-climb index (r = -0.77, p < 0.0001). The saturation deviation (mean of SpO(2) values <95 %) on the step test correlated with diffusion capacity of the lung (ρ = -0.49, p = 0.001). No correlations were found between the step test indices and other lung function tests, hemodynamic parameters or NT-proBNP levels. Patients with PAH/CTEPH have significant limitation in step climbing ability that correlates with functional class and 6-min walking distance. This is a significant impediment to their daily activities.

Experimental and Analytical Evaluation of Stressing-Rate State Evolution in Rate-State Friction Laws

NASA Astrophysics Data System (ADS)

Bhattacharya, P.; Rubin, A. M.; Bayart, E.; Savage, H. M.; Marone, C.; Beeler, N. M.

2013-12-01

Standard rate and state friction laws fail to explain the full range of observations from laboratory friction experiments. A new state evolution law has been proposed by Nagata et al. (2012) that adds a linear stressing-rate-dependent term to the Dieterich (aging) law, which may provide a remedy. They introduce a parameter c that controls the contribution of the stressing rate to state evolution. We show through analytical approximations that the new law can transition between the responses of the traditional Dieterich (aging) and Ruina (slip) laws in velocity step up/down experiments when the value of c is tuned properly. In particular, for c = 0 the response is pure aging while for finite, non-zero c one observes slip law like behavior for small velocity jumps but aging law like response for larger jumps. The magnitude of the velocity jump required to see this transition between aging and slip behaviour increases as c increases. In the limit of c >> 1 the response to velocity steps becomes purely slip law like. In this limit, numerical simulations show that this law loses its appealing time dependent healing property. An approach using Markov Chain Monte Carlo parameter search on data for large magnitude velocity step tests reveals that it is only possible to determine a lower bound on c using datasets that are well explained by the slip law. For a dataset with velocity steps of two orders of magnitude on simulated fault gouge we find this lower bound to be c ≈ 10.0. This is significantly larger than c ≈ 2.0 used by Nagata et al. (2012) to fit their data (mainly bare rock experiments with smaller excursions from steady state than our dataset). Similar parameter estimation exercises on slide hold slide data reveal that none of the state evolution laws considered - Dieterich, Ruina, Kato-Tullis and Nagata - match the relevant features of the data. In particular, even the aging law predicts only the correct rate of healing for long hold times but not the correct amount of healing. For c = 10.0, the Nagata law shows significant slip dependence in healing rate for long hold times which is at odds with the lab data and similar to the slip law response. If one accepts frictional healing observed in the laboratory as a ';proper' analog for fault strengthening over the interseismic period, we conclude that none of the investigated state evolution laws provides a comprehensive and correct constitutive relation.

The numerical evaluation of maximum-likelihood estimates of the parameters for a mixture of normal distributions from partially identified samples

NASA Technical Reports Server (NTRS)

Walker, H. F.

1976-01-01

Likelihood equations determined by the two types of samples which are necessary conditions for a maximum-likelihood estimate are considered. These equations, suggest certain successive-approximations iterative procedures for obtaining maximum-likelihood estimates. These are generalized steepest ascent (deflected gradient) procedures. It is shown that, with probability 1 as N sub 0 approaches infinity (regardless of the relative sizes of N sub 0 and N sub 1, i=1,...,m), these procedures converge locally to the strongly consistent maximum-likelihood estimates whenever the step size is between 0 and 2. Furthermore, the value of the step size which yields optimal local convergence rates is bounded from below by a number which always lies between 1 and 2.

Development, optimization and validation of gas chromatographic fingerprinting of Brazilian commercial diesel fuel for quality control.

PubMed

dos Santos, Bruno César Diniz Brito; Flumignan, Danilo Luiz; de Oliveira, José Eduardo

2012-10-01

A three-step development, optimization and validation strategy is described for gas chromatography (GC) fingerprints of Brazilian commercial diesel fuel. A suitable GC-flame ionization detection (FID) system was selected to assay a complex matrix such as diesel. The next step was to improve acceptable chromatographic resolution with reduced analysis time, which is recommended for routine applications. Full three-level factorial designs were performed to improve flow rate, oven ramps, injection volume and split ratio in the GC system. Finally, several validation parameters were performed. The GC fingerprinting can be coupled with pattern recognition and multivariate regressions analyses to determine fuel quality and fuel physicochemical parameters. This strategy can also be applied to develop fingerprints for quality control of other fuel types.

5 CFR 531.406 - Creditable service.

Code of Federal Regulations, 2010 CFR

2010-01-01

... pay is equal to or greater than the rate of basic pay for step 4 of the applicable grade and less than... period for an employee whose rate of basic pay is equal to or greater than the rate of basic pay for step....406 Administrative Personnel OFFICE OF PERSONNEL MANAGEMENT CIVIL SERVICE REGULATIONS PAY UNDER THE...

Mississippi Quality Step System: QRS Profile. The Child Care Quality Rating System (QRS)Assessment

ERIC Educational Resources Information Center

Child Trends, 2010

2010-01-01

This paper presents a profile of Mississippi's Quality Step System prepared as part of the Child Care Quality Rating System (QRS) Assessment Study. The profile consists of several sections and their corresponding descriptions including: (1) Program Information; (2) Rating Details; (3) Quality Indicators for Center-Based Programs; (4) Application…

Disilane chemisorption on Si(x)Ge(1-x)(100)-(2 x 1): molecular mechanisms and implications for film growth rates.

PubMed

Ng, Rachel Qiao-Ming; Tok, E S; Kang, H Chuan

2009-07-28

At low temperatures, hydrogen desorption is known to be the rate-limiting process in silicon germanium film growth via chemical vapor deposition. Since surface germanium lowers the hydrogen desorption barrier, Si(x)Ge((1-x)) film growth rate increases with the surface germanium fraction. At high temperatures, however, the molecular mechanisms determining the epitaxial growth rate are not well established despite much experimental work. We investigate these mechanisms in the context of disilane adsorption because disilane is an important precursor used in film growth. In particular, we want to understand the molecular steps that lead, in the high temperature regime, to a decrease in growth rate as the surface germanium increases. In addition, there is a need to consider the issue of whether disilane adsorbs via silicon-silicon bond dissociation or via silicon-hydrogen bond dissociation. It is usually assumed that disilane adsorption occurs via silicon-silicon bond dissociation, but in recent work we provided theoretical evidence that silicon-hydrogen bond dissociation is more important. In order to address these issues, we calculate the chemisorption barriers for disilane on silicon germanium using first-principles density functional theory methods. We use the calculated barriers to estimate film growth rates that are then critically compared to the experimental data. This enables us to establish a connection between the dependence of the film growth rate on the surface germanium content and the kinetics of the initial adsorption step. We show that the generally accepted mechanism where disilane chemisorbs via silicon-silicon bond dissociation is not consistent with the data for film growth kinetics. Silicon-hydrogen bond dissociation paths have to be included in order to give good agreement with the experimental data for high temperature film growth rate.

Educational intervention as an effective step for reducing blood culture contamination: a prospective cohort study.

PubMed

Park, W B; Myung, S J; Oh, M-d; Lee, J; Kim, N-J; Kim, E-C; Park, J S

2015-10-01

Contaminated blood cultures lead to diagnostic challenges and place a burden on healthcare services. To determine the impact of introducing a clinical skills test (CST) as part of the medical licensing examination and an institutional education programme on the contamination rates of blood cultures. A prospective cohort study was conducted from 2009 through 2013 in all wards of a tertiary-care teaching hospital. We evaluated the effects of the CST, which was added to the National Medical Licensing Examination in Korea (KMLE) in 2010 and our institutional education programme, which began in 2013. The medical interns in charge of collection of blood for culture were divided in three groups with presence or absence of CST and the institutional education programme. The primary outcome was the percentage of blood cultures contaminated in each group, which were compared using the Poisson regression model. Participants' self-rated scores for the blood draw procedure were also analysed. Although introduction of the CST in the KMLE failed to reduce blood culture contamination rate (1.36% vs 1.35%; P = 0.734), the institutional education programme significantly reduced the contamination rate (1.35% vs 1.00%; P < 0.0001). Most participants answered that they always followed each step correctly except for waiting the recommended contact time after applying the antiseptic. The educational intervention, not the introduction of CST in the KMLE, was effective in reducing overall contamination rates. Copyright © 2015 The Healthcare Infection Society. Published by Elsevier Ltd. All rights reserved.

Type-II generalized family-wise error rate formulas with application to sample size determination.

PubMed

Delorme, Phillipe; de Micheaux, Pierre Lafaye; Liquet, Benoit; Riou, Jérémie

2016-07-20

Multiple endpoints are increasingly used in clinical trials. The significance of some of these clinical trials is established if at least r null hypotheses are rejected among m that are simultaneously tested. The usual approach in multiple hypothesis testing is to control the family-wise error rate, which is defined as the probability that at least one type-I error is made. More recently, the q-generalized family-wise error rate has been introduced to control the probability of making at least q false rejections. For procedures controlling this global type-I error rate, we define a type-II r-generalized family-wise error rate, which is directly related to the r-power defined as the probability of rejecting at least r false null hypotheses. We obtain very general power formulas that can be used to compute the sample size for single-step and step-wise procedures. These are implemented in our R package rPowerSampleSize available on the CRAN, making them directly available to end users. Complexities of the formulas are presented to gain insight into computation time issues. Comparison with Monte Carlo strategy is also presented. We compute sample sizes for two clinical trials involving multiple endpoints: one designed to investigate the effectiveness of a drug against acute heart failure and the other for the immunogenicity of a vaccine strategy against pneumococcus. Copyright © 2016 John Wiley & Sons, Ltd. Copyright © 2016 John Wiley & Sons, Ltd.

Structure–Reactivity Studies, Characterization, and Transformation of Intermediates by Lithium Chloride in the Direct Insertion of Alkyl and Aryl Iodides to Metallic Zinc Powder

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

Feng, Chao; Easter, Quinn T.; Blum, Suzanne A.

Employment of fluorophore-tagged alkyl and aryl iodides permitted detection of persistent surface intermediates during their direct insertion to commercially available zinc powder. The sensitivity of this subensemble microscopy technique enabled structure–reactivity studies in the formation of intermediates that are present in quantities sufficiently low as to have been undetected previously by traditional ensemble analytical techniques. In these surface intermediates we transformed them using lithium chloride, which lead to the assignment of the mechanistic role of lithium chloride as changing the rate-determining step in the reaction by lowering the barrier for solubilization of these otherwise persistent surface organometallic intermediates. The temperaturemore » dependence/qualitative barrier of the direct insertion step was determined independently from the solubilization step and from the barrier for the overall reaction. Detection of these zinc surface intermediates at the single-molecule level, i.e., of individual surface organometallic species, has been achieved for the first time. Energy dispersive X-ray spectroscopy (EDS) measurements of the elemental composition of the surface of the zinc powder determined that lithium chloride does not clean the surface of the oxides; instead, pretreatment of the surface with TMSCl effects partial removal of surface oxides after the 2 h pretreatment time previously reported in the empirically optimized synthetic procedure. The current limitations of this microscopy approach are also determined and discussed with respect to the addition of solid reagents during in operando imaging. Characterization of the resulting soluble fluorophore-tagged organozinc/LiCl complex by 1H NMR spectroscopy, mass spectrometry, and fluorescence spectroscopy provided insight into its solution dynamics and chemical exchange processes.« less

Structure–Reactivity Studies, Characterization, and Transformation of Intermediates by Lithium Chloride in the Direct Insertion of Alkyl and Aryl Iodides to Metallic Zinc Powder

DOE PAGES

Feng, Chao; Easter, Quinn T.; Blum, Suzanne A.

2017-02-03

Employment of fluorophore-tagged alkyl and aryl iodides permitted detection of persistent surface intermediates during their direct insertion to commercially available zinc powder. The sensitivity of this subensemble microscopy technique enabled structure–reactivity studies in the formation of intermediates that are present in quantities sufficiently low as to have been undetected previously by traditional ensemble analytical techniques. In these surface intermediates we transformed them using lithium chloride, which lead to the assignment of the mechanistic role of lithium chloride as changing the rate-determining step in the reaction by lowering the barrier for solubilization of these otherwise persistent surface organometallic intermediates. The temperaturemore » dependence/qualitative barrier of the direct insertion step was determined independently from the solubilization step and from the barrier for the overall reaction. Detection of these zinc surface intermediates at the single-molecule level, i.e., of individual surface organometallic species, has been achieved for the first time. Energy dispersive X-ray spectroscopy (EDS) measurements of the elemental composition of the surface of the zinc powder determined that lithium chloride does not clean the surface of the oxides; instead, pretreatment of the surface with TMSCl effects partial removal of surface oxides after the 2 h pretreatment time previously reported in the empirically optimized synthetic procedure. The current limitations of this microscopy approach are also determined and discussed with respect to the addition of solid reagents during in operando imaging. Characterization of the resulting soluble fluorophore-tagged organozinc/LiCl complex by 1H NMR spectroscopy, mass spectrometry, and fluorescence spectroscopy provided insight into its solution dynamics and chemical exchange processes.« less

41 CFR 301-11.624 - What steps must my agency take to determine my ITRA?

Code of Federal Regulations, 2010 CFR

2010-07-01

... 41 Public Contracts and Property Management 4 2010-07-01 2010-07-01 false What steps must my agency take to determine my ITRA? 301-11.624 Section 301-11.624 Public Contracts and Property Management... Responsibilities § 301-11.624 What steps must my agency take to determine my ITRA? Your agency should: (a...

41 CFR 301-11.524 - What steps must my agency take to determine my ITRA?

Code of Federal Regulations, 2010 CFR

2010-07-01

... 41 Public Contracts and Property Management 4 2010-07-01 2010-07-01 false What steps must my agency take to determine my ITRA? 301-11.524 Section 301-11.524 Public Contracts and Property Management... Responsibilities § 301-11.524 What steps must my agency take to determine my ITRA? Your agency should: (a...

Nucleophilic Participation in the Solvolyses of (Arylthio)methyl Chlorides and Derivatives: Application of Simple and Extended Forms of the Grunwald-Winstein Equations

PubMed Central

Kevill, Dennis N.; Park, Young Hoon; Park, Byoung-Chun; D’Souza, Malcolm J.

2012-01-01

The specific rates of solvolysis of chloromethyl phenyl sulfide [(phenylthio)methyl chloride] and its p-chloro-derivative have been determined at 0.0 °C in a wide range of hydroxylic solvents, including several containing a fluroalcohol. Treatment in terms of a two-term Grunwald-Winstein equation, incorporating terms based on solvent ionizing power (YCl) and solvent nucleophilicity (NT) suggest a mechanism similar to that for the solvolyses of tert-butyl chloride, involving in the rate-determining step a nucleophilic solvation of the incipient carbocation in an ionization process. A previous suggestion, that a third-term governed by the aromatic ring parameter (I) is required, is shown both for the new and for the previously studied related substrates to be an artifact, resulting from an appreciable degree of multicollinearity between I values and a linear combination of NT and YCl values. PMID:22711999

Crystallization kinetics of Fe based amorphous alloy

NASA Astrophysics Data System (ADS)

Shanker Rao, T.; Lilly Shanker Rao, T.

2015-02-01

Differential Scanning Calorimetry(DSC) experimental data under non-isothermal conditions for Fe based Metglas 2605SA1 (wt% Fe=85-95, Si=5-10, B=1-5) metallic glass ribbons are reported and discussed. The DSC Scans performed at different heating rates showed two step crystallization processes and are interpreted in terms of different models like Kissinger, Ozawa, Boswell, Augis & Bennett and Gao & Wang. From the heating rate dependence of the onset temperature (To) and the crystallization peak temperature (Tp), the kinetic triplet, activation energy of crystallization (E), Avrami exponent (n) and the frequency factor (A) are determined. The determined E for peak I is 354.5 ± 2.5 kJ/mol and for the peak II is 348.2 ± 2.2 kJ/mol, respectively. The frequency factor for peak I is 1.1 × 1023sec-1 and for peak II is 6.1 × 1020sec-1.

Students Targeting Engineering and Physical Science (STEPS) at California State University Northridge (CSUN):Activities and Outcomes 2011-2016

NASA Astrophysics Data System (ADS)

Cadavid, A. C.; Pedone, V. A.; Horn, W.; Rich, H.

2016-12-01

The specific goal of STEPS at CSUN is to increase the number bachelor's degrees in STEM majors, particularly those in engineering, computer science, mathematics and the physical sciences. Prior to STEPS, only 33% of first-time freshmen in these majors graduated from CSUN within 6-7 years. We employ two main strategies: 1) fostering success in lower-division mathematics for freshmen and sophomores, 2) Summer Interdisciplinary Team Experience (SITE) for students transitioning to junior level courses. To improve success in mathematics, we have advanced initial placements in the foundational mathematics sequence by one or two semesters through improvements in the placement test (6-7% improvement) and have increased the first-time pass rate in foundational math courses through mandatory supplementary laboratories for at-risk students. Students who successfully complete the supplemental laboratories pass the lecture class at a higher rate than the total population of at-risk students (65% compared to 61%). Both approaches have been institutionalized. SITE targets students entering their junior years in a 3-week interdisciplinary team project that highlights problem solving and hands-on activities. Survey results of the 233 participants show that SITE: 1) maintained or increased desire to earn a STEM degree, 2) increased positive attitudes toward team-based problem solving, 3) increased understanding in how they will use their major in a career, and 4) increased interest in faculty-mentored research and industry internships. Our 5-year program is nearing completion and shows success in meeting our goal. We have measured a 9% point increase in the pass rate of Calculus I for post-STEPS cohorts compared to pre-STEPS cohorts. Failure to pass Calculus is a leading cause in non-completion of the majors targeted by STEPS. We have analyzed the graduation rates of two pre-STEPS cohorts that have had over 6 years to graduate. Both have a graduate rate of 28%. We expect that the 9% point increase in calculus passers will lead to a comparable increase in graduation rate, resulting in a 37% graduation rate for the post-STEPS cohorts.

Predicting the admission into medical school of African American college students who have participated in summer academic enrichment programs.

PubMed

Hesser, A; Cregler, L L; Lewis, L

1998-02-01

To identify cognitive and noncognitive variables as predictors of the admission into medical school of African American college students who have participated in summer academic enrichment programs (SAEPs). The study sample comprised 309 African American college students who participated in SAEPs at the Medical College of Georgia School of Medicine from 1980 to 1989 and whose educational and occupational statuses were determined by follow-up tracking. A three-step logistic regression was used to analyze the data (with alpha = .05); the criterion variable was admission to medical school. The 17 predictor variables studied were one of two types, cognitive and noncognitive. The cognitive variables were (1) Scholastic Aptitude Test mathematics (SAT-M) score, (2) SAT verbal score, (3) college grade-point average (GPA), (4) college science GPA, (5) SAEP GPA, and (6) SAEP basic science GPA (BSGPA). The noncognitive variables were (1) gender, (2) highest college level at the time of the last SAEP application, (3) type of college attended (historically African American or predominately white), (4) number of SAEPs attended, (5) career aspiration (physician or another health science option) (6) parents who were professionals, (7) parents who were health care role models, (8) evidence of leadership, (9) evidence of community service, (10) evidence of special motivation, and (11) strength of letter of recommendation in the SAEP application. For each student the rating scores for the last four noncognitive variables were determined by averaging the ratings of two judges who reviewed relevant information in each student's file. In step 1, which explained 20% of the admission decision variance, SAT-M score, SAEP BSGPA, and college GPA were the three significant cognitive predictors identified. In step 2, which explained 31% of the variance, the three cognitive predictors identified in step 1 were joined by three noncognitive predictors: career aspiration, type of college, and number of SAEPs attended. In step 3, which explained 29% of the variance, two cognitive variables (SAT-M score and SAEP BSGPA) and two noncognitive variables (career aspiration and strength of recommendation letter) were identified. The results support the concept of using both cognitive and noncognitive variables when selecting African American students for pre-medical school SAEPs.

Relationships between heart rate target determined in different exercise testing in COPD patients to prescribed with individualized exercise training.

PubMed

Fabre, Claudine; Chehere, Baptiste; Bart, Frédéric; Mucci, Patrick; Wallaert, Benoit; Grosbois, Jean Marie

2017-01-01

It has been scientifically proven that pulmonary rehabilitation improves exercise tolerance and facilitates the carrying out of daily physical activities. To optimize the physical and physiological benefits, it is necessary to individualize the training intensity for each patient. The aim of this study is to compare the heart rate (HR) responses to three exercise modalities measuring aerobic fitness in chronic obstructive pulmonary disease patients, in order to easily prescribe individual target HRs for endurance training. Fifty COPD patients (mean age: 60.1±8.5 years) were included in the study. Each patient carried out a cardiopulmonary exercise test, a 6-minute walk test (6MWT) and a 6-minute stepper test (6MST). During these tests, HR was recorded continuously. After the cardiopulmonary exercise test, the HR was noted at the ventilatory threshold (VT) and at the end of the two exercise field tests (6MWT peak and 6MST peak ). The values of the HR during the last 3 minutes of both field tests were averaged (6MWT 456 and 6MST 456 ). Finally, the HR at 60% of the HR reserve was calculated with the values of the HR measured during 6MWT and 6MST (HRr 60%walk , HRr 60%step ). The HRs measured during the 6MST were significantly higher than those measured during the 6MWT. The HRr 60%step was not significantly different from 6MWT 456 and 6MWT peak HR ( P =0.51; P =0.48). A significant correlation was observed between 6MWT 456 and 6MWT peak ( r =0.58). The 6MWT 456 and 6MWT peak HR were correlated with HRr 60%step ( r =0.68 and r =0.62). The VT could be determined in 28 patients. The HR VT was not different from 6MWT 456 , 6MWT peak , and HRr 60%step ( P =0.57, P =0.41 and P =0.88) and was correlated to 6MWT 456 , 6MWT peak , and HRr 60%step ( r =0.45, r =0.40, r =0.48). An individualized target HR for endurance training can be prescribed from the HR measured during routine tests, such as 6MWT or 6MST.

Relationships between heart rate target determined in different exercise testing in COPD patients to prescribed with individualized exercise training

PubMed Central

Fabre, Claudine; Chehere, Baptiste; Bart, Frédéric; Mucci, Patrick; Wallaert, Benoit; Grosbois, Jean Marie

2017-01-01

Background It has been scientifically proven that pulmonary rehabilitation improves exercise tolerance and facilitates the carrying out of daily physical activities. To optimize the physical and physiological benefits, it is necessary to individualize the training intensity for each patient. The aim of this study is to compare the heart rate (HR) responses to three exercise modalities measuring aerobic fitness in chronic obstructive pulmonary disease patients, in order to easily prescribe individual target HRs for endurance training. Patients and method Fifty COPD patients (mean age: 60.1±8.5 years) were included in the study. Each patient carried out a cardiopulmonary exercise test, a 6-minute walk test (6MWT) and a 6-minute stepper test (6MST). During these tests, HR was recorded continuously. After the cardiopulmonary exercise test, the HR was noted at the ventilatory threshold (VT) and at the end of the two exercise field tests (6MWTpeak and 6MSTpeak). The values of the HR during the last 3 minutes of both field tests were averaged (6MWT456 and 6MST456). Finally, the HR at 60% of the HR reserve was calculated with the values of the HR measured during 6MWT and 6MST (HRr60%walk, HRr60%step). Results The HRs measured during the 6MST were significantly higher than those measured during the 6MWT. The HRr60%step was not significantly different from 6MWT456 and 6MWTpeak HR (P=0.51; P=0.48). A significant correlation was observed between 6MWT456 and 6MWTpeak (r=0.58). The 6MWT456 and 6MWTpeak HR were correlated with HRr60%step (r=0.68 and r=0.62). The VT could be determined in 28 patients. The HRVT was not different from 6MWT456, 6MWTpeak, and HRr60%step (P=0.57, P=0.41 and P=0.88) and was correlated to 6MWT456, 6MWTpeak, and HRr60%step (r=0.45, r=0.40, r=0.48). Conclusion An individualized target HR for endurance training can be prescribed from the HR measured during routine tests, such as 6MWT or 6MST. PMID:28553100

H2CO3 forms via HCO3- in water.

PubMed

Stirling, András; Pápai, Imre

2010-12-23

According to the generally accepted picture of CO(2) dissolution in water, the formation of H(2)CO(3) proceeds in a single step that involves the attack of a water oxygen on the CO(2) carbon in concert with a proton transfer to a CO(2) oxygen. In the present work, a series of ab initio molecular dynamics simulations have been carried out along with the metadynamics technique which reveals a stepwise mechanism: the reaction of a water molecule with CO(2) yields HCO(3)(-) as an intermediate and a hydronium ion, whereas the protonation of the CO(2) moiety occurs in a separate step representing a well-defined activation barrier toward the H(2)CO(3) molecule. This alternative scenario was already taken into consideration decades ago, but subsequent experiments and calculations have given preference to the concerted mechanism. Employing extended periodic models of the CO(2)-water system that mimic the bulk aqueous environment, the present simulations yield the complete free energy profile of the stepwise mechanism and provide a detailed microscopic mechanism of the elementary steps. HCO(3)(-) formation is found to be the rate-determining step of the entire CO(2) hydration process.

Measured close lightning leader-step electric-field-derivative waveforms.

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

Jordan, Doug M.; Hill, Dustin; Biagi, Christopher J.

2010-12-01

We characterize the measured electric field-derivative (dE/dt) waveforms of lightning stepped-leader steps from three negative lightning flashes at distances of tens to hundreds of meters. Electromagnetic signatures of leader steps at such close distances have rarely been documented in previous literature. Individual leader-step three-dimensional locations are determined by a dE/dt TOA system. The leader-step field derivative is typically a bipolar pulse with a sharp initial half-cycle of the same polarity as that of the return stroke, followed by an opposite polarity overshoot that decays relatively slowly to background level. This overshoot increases in amplitude relative to the initial peak andmore » becomes dominant as range decreases. The initial peak is often preceded by a 'slow front,' similar to the slow front that precedes the fast transition to peak in first return stroke dE/dt and E waveforms. The overall step-field waveform duration is typically less than 1 {micro}s. The mean initial peak of dE/dt, range-normalized to 100 km, is 7.4 V m{sup -1} {micro}s{sup -1} (standard deviation (S.D.), 3.7 V m{sup -1} {micro}s{sup -1}, N = 103), the mean half-peak width is 33.5 ns (S.D., 11.9 ns, N = 69), and the mean 10-to-90% risetime is 43.6 ns (S.D., 24.2 ns, N = 69). From modeling, we determine the properties of the leader step currents which produced two typical measured field derivatives, and we use one of these currents to calculate predicted leader step E and dE/dt as a function of source range and height, the results being in good agreement with our observations. The two modeled current waveforms had maximum rates of current rise-to-peak near 100 kA {micro}s{sup -1}, peak currents in the 5-7 kA range, current half-peak widths of about 300 ns, and charge transfers of {approx}3 mC. As part of the modeling, those currents were propagated upward at 1.5 x 10{sup 8} m s{sup -1}, with their amplitudes decaying exponentially with a decay height constant of 25 m.« less

Direct carbon-carbon coupling of furanics with acetic acid over Brønsted zeolites

PubMed Central

Gumidyala, Abhishek; Wang, Bin; Crossley, Steven

2016-01-01

Effective carbon-carbon coupling of acetic acid to form larger products while minimizing CO2 emissions is critical to achieving a step change in efficiency for the production of transportation fuels from sustainable biomass. We report the direct acylation of methylfuran with acetic acid in the presence of water, all of which can be readily produced from biomass. This direct coupling limits unwanted polymerization of furanics while producing acetyl methylfuran. Reaction kinetics and density functional theory calculations illustrate that the calculated apparent barrier for the dehydration of the acid to form surface acyl species is similar to the experimentally measured barrier, implying that this step plays a significant role in determining the net reaction rate. Water inhibits the overall rate, but selectivity to acylated products is not affected. We show that furanic species effectively stabilize the charge of the transition state, therefore lowering the overall activation barrier. These results demonstrate a promising new route to C–C bond–forming reactions for the production of higher-value products from biomass. PMID:27652345

Electride support boosts nitrogen dissociation over ruthenium catalyst and shifts the bottleneck in ammonia synthesis

DOE PAGES

Kitano, Masaaki; Kanbara, Shinji; Inoue, Yasunori; ...

2015-03-30

We actively sough novel approaches to efficient ammonia synthesis at an ambient pressure so as to reduce the cost of ammonia production and to allow for compact production facilities. It is accepted that the key is the development of a high-performance catalyst that significantly enhances dissociation of the nitrogen-nitrogen triple bond, which is generally considered a rate-determining step. Here we examine the kinetics of nitrogen and hydrogen isotope exchange and hydrogen adsorption/desorption reactions for a recently discovered efficient catalyst for ammonia synthesis --ruthenium-loaded 12CaO∙7AI 2O 3 electride (Ru/C12A7:more » $$\\bar{e}$$ )--and find that the rate controlling step of ammonia synthesis over Ru/C12A7:$$\\bar{e}$$ is not dissociation of the nitrogen-nitrogen triple bond but the subsequent formation of N-H n species. A mechanism of ammonia synthesis involving reversible storage and release of hydrogen atoms on the Ru/C12A7:$$\\bar{e}$$ surface is proposed on the basis of observed hydrogen adsorption/desorption kinetics.« less

Electride support boosts nitrogen dissociation over ruthenium catalyst and shifts the bottleneck in ammonia synthesis

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

Kitano, Masaaki; Kanbara, Shinji; Inoue, Yasunori

We actively sough novel approaches to efficient ammonia synthesis at an ambient pressure so as to reduce the cost of ammonia production and to allow for compact production facilities. It is accepted that the key is the development of a high-performance catalyst that significantly enhances dissociation of the nitrogen-nitrogen triple bond, which is generally considered a rate-determining step. Here we examine the kinetics of nitrogen and hydrogen isotope exchange and hydrogen adsorption/desorption reactions for a recently discovered efficient catalyst for ammonia synthesis --ruthenium-loaded 12CaO∙7AI 2O 3 electride (Ru/C12A7:more » $$\\bar{e}$$ )--and find that the rate controlling step of ammonia synthesis over Ru/C12A7:$$\\bar{e}$$ is not dissociation of the nitrogen-nitrogen triple bond but the subsequent formation of N-H n species. A mechanism of ammonia synthesis involving reversible storage and release of hydrogen atoms on the Ru/C12A7:$$\\bar{e}$$ surface is proposed on the basis of observed hydrogen adsorption/desorption kinetics.« less

First spin-parity constraint of the 306 keV resonance in Cl 35 for nova nucleosynthesis

DOE PAGES

Chipps, K. A.; Rutgers Univ., New Brunswick, NJ; Pain, S. D.; ...

2017-04-28

Something of particular interest in astrophysics is the 34 S ( p , γ ) 35 Cl reaction, which serves as a stepping stone in thermonuclear runaway reaction chains during a nova explosion. Although the isotopes involved are all stable, the reaction rate of this significant step is not well known, due to a lack of experimental spectroscopic information on states within the Gamow window above the proton separation threshold of 35 Cl . Furthermore, measurements of level spins and parities provide input for the calculation of resonance strengths, which ultimately determine the astrophysical reaction rate of the 34 Smore » ( p , γ ) 35 Cl proton capture reaction. By performing the 37 Cl ( p , t ) 35 Cl reaction in normal kinematics at the Holifield Radioactive Ion Beam Facility at Oak Ridge National Laboratory, we have conducted a study of the region of astrophysical interest in 35 Cl , and have made the first-ever constraint on the spin and parity assignment for a level at 6677 ± 15 keV ( E r = 306 keV), inside the Gamow window for novae.« less

First spin-parity constraint of the 306 keV resonance in 35Cl for nova nucleosynthesis

NASA Astrophysics Data System (ADS)

Chipps, K. A.; Pain, S. D.; Kozub, R. L.; Bardayan, D. W.; Cizewski, J. A.; Chae, K. Y.; Liang, J. F.; Matei, C.; Moazen, B. H.; Nesaraja, C. D.; O'Malley, P. D.; Peters, W. A.; Pittman, S. T.; Schmitt, K. T.; Smith, M. S.

2017-04-01

Of particular interest in astrophysics is the 34S(p ,γ )35Cl reaction, which serves as a stepping stone in thermonuclear runaway reaction chains during a nova explosion. Though the isotopes involved are all stable, the reaction rate of this significant step is not well known, due to a lack of experimental spectroscopic information on states within the Gamow window above the proton separation threshold of 35Cl. Measurements of level spins and parities provide input for the calculation of resonance strengths, which ultimately determine the astrophysical reaction rate of the 34S(p ,γ )35Cl proton capture reaction. By performing the 37Cl(p ,t )35Cl reaction in normal kinematics at the Holifield Radioactive Ion Beam Facility at Oak Ridge National Laboratory, we have conducted a study of the region of astrophysical interest in 35Cl, and have made the first-ever constraint on the spin and parity assignment for a level at 6677 ±15 keV (Er=306 keV), inside the Gamow window for novae.

Direct carbon-carbon coupling of furanics with acetic acid over Bronsted zeolites

DOE PAGES

Gumidyala, Abhishek; Wang, Bin; Crossley, Steven

2016-09-16

Effective carbon-carbon coupling of acetic acid to form larger products while minimizing CO 2 emissions is critical to achieving a step change in efficiency for the production of transportation fuels from sustainable biomass. Here, we report the direct acylation of methylfuran with acetic acid in the presence ofwater, all ofwhich can be readily produced from biomass. This direct coupling limits unwanted polymerization of furanics while producing acetyl methylfuran. Reaction kinetics and density functional theory calculations illustrate that the calculated apparent barrier for the dehydration of the acid to form surface acyl species is similar to the experimentally measured barrier, implyingmore » that this step plays a significant role in determining the net reaction rate. Water inhibits the overall rate, but selectivity to acylated products is not affected.We show that furanic species effectively stabilize the charge of the transition state, therefore lowering the overall activation barrier. These results demonstrate a promising new route to C–C bond–forming reactions for the production of higher-value products from biomass.« less

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.

Time-dependent rheological behavior of natural polysaccharide xanthan gum solutions in interrupted shear and step-incremental/reductional shear flow fields

NASA Astrophysics Data System (ADS)

Lee, Ji-Seok; Song, Ki-Won

2015-11-01

The objective of the present study is to systematically elucidate the time-dependent rheological behavior of concentrated xanthan gum systems in complicated step-shear flow fields. Using a strain-controlled rheometer (ARES), step-shear flow behaviors of a concentrated xanthan gum model solution have been experimentally investigated in interrupted shear flow fields with a various combination of different shear rates, shearing times and rest times, and step-incremental and step-reductional shear flow fields with various shearing times. The main findings obtained from this study are summarized as follows. (i) In interrupted shear flow fields, the shear stress is sharply increased until reaching the maximum stress at an initial stage of shearing times, and then a stress decay towards a steady state is observed as the shearing time is increased in both start-up shear flow fields. The shear stress is suddenly decreased immediately after the imposed shear rate is stopped, and then slowly decayed during the period of a rest time. (ii) As an increase in rest time, the difference in the maximum stress values between the two start-up shear flow fields is decreased whereas the shearing time exerts a slight influence on this behavior. (iii) In step-incremental shear flow fields, after passing through the maximum stress, structural destruction causes a stress decay behavior towards a steady state as an increase in shearing time in each step shear flow region. The time needed to reach the maximum stress value is shortened as an increase in step-increased shear rate. (iv) In step-reductional shear flow fields, after passing through the minimum stress, structural recovery induces a stress growth behavior towards an equilibrium state as an increase in shearing time in each step shear flow region. The time needed to reach the minimum stress value is lengthened as a decrease in step-decreased shear rate.

[A Quality Assurance (QA) System with a Web Camera for High-dose-rate Brachytherapy].

PubMed

Hirose, Asako; Ueda, Yoshihiro; Oohira, Shingo; Isono, Masaru; Tsujii, Katsutomo; Inui, Shouki; Masaoka, Akira; Taniguchi, Makoto; Miyazaki, Masayoshi; Teshima, Teruki

2016-03-01

The quality assurance (QA) system that simultaneously quantifies the position and duration of an (192)Ir source (dwell position and time) was developed and the performance of this system was evaluated in high-dose-rate brachytherapy. This QA system has two functions to verify and quantify dwell position and time by using a web camera. The web camera records 30 images per second in a range from 1,425 mm to 1,505 mm. A user verifies the source position from the web camera at real time. The source position and duration were quantified with the movie using in-house software which was applied with a template-matching technique. This QA system allowed verification of the absolute position in real time and quantification of dwell position and time simultaneously. It was evident from the verification of the system that the mean of step size errors was 0.31±0.1 mm and that of dwell time errors 0.1±0.0 s. Absolute position errors can be determined with an accuracy of 1.0 mm at all dwell points in three step sizes and dwell time errors with an accuracy of 0.1% in more than 10.0 s of the planned time. This system is to provide quick verification and quantification of the dwell position and time with high accuracy at various dwell positions without depending on the step size.

Insoluble Coatings for Stirling Engine Heat Pipe Condenser Surfaces

NASA Technical Reports Server (NTRS)

Dussinger, Peter M.; Lindemuth, James E.

1997-01-01

The principal objective of this Phase 2 SBIR program was to develop and demonstrate a practically insoluble coating for nickel-based superalloys for Stirling engine heat pipe applications. Specific technical objectives of the program were: (1) Determine the solubility corrosion rates for Nickel 200, Inconel 718, and Udimet 72OLI in a simulated Stirling engine heat pipe environment, (2) Develop coating processes and techniques for capillary groove and screen wick structures, (3) Evaluate the durability and solubility corrosion rates for capillary groove and screen wick structures coated with an insoluble coating in cylindrical heat pipes operating under Stirling engine conditions, and (4) Design and fabricate a coated full-scale, partial segment of the current Stirling engine heat pipe for the Stirling Space Power Convertor program. The work effort successfully demonstrated a two-step nickel aluminide coating process for groove wick structures and interior wall surfaces in contact with liquid metals; demonstrated a one-step nickel aluminide coating process for nickel screen wick structures; and developed and demonstrated a two-step aluminum-to-nickel aluminide coating process for nickel screen wick structures. In addition, the full-scale, partial segment was fabricated and the interior surfaces and wick structures were coated. The heat pipe was charged with sodium, processed, and scheduled to be life tested for up to ten years as a Phase 3 effort.

Differential utilization of enzyme-substrate interactions for acylation but not deacylation during the catalytic cycle of Kex2 protease.

PubMed

Rockwell, N C; Fuller, R S

2001-10-19

Kex2 protease from Saccharomyces cerevisiae is the prototype for a family of eukaryotic proprotein processing proteases belonging to the subtilase superfamily of serine proteases. Kex2 can be distinguished from degradative subtilisins on the basis of stringent substrate specificity and distinct pre-steady-state behavior. To better understand these mechanistic differences, we have examined the effects of substrate residues at P(1) and P(4) on individual steps in the Kex2 catalytic cycle with a systematic series of isosteric peptidyl amide and ester substrates. The results demonstrate that substrates based on known, physiological cleavage sites exhibit high acylation rates (> or =550 s(-1)) with Kex2. Substitution of Lys for the physiologically correct Arg at P(1) resulted in a > or =200-fold drop in acylation rate with almost no apparent effect on binding or deacylation. In contrast, substitution of the physiologically incorrect Ala for Nle at P(4) resulted in a much smaller defect in acylation and a modest but significant effect on binding with Lys at P(1). This substitution also had no effect on deacylation. These results demonstrate that Kex2 utilizes enzyme-substrate interactions in different ways at different steps in the catalytic cycle, with the S(1)-P(1) contact providing a key specificity determinant at the acylation step.

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.

Effects of an aft facing step on the surface of a laminar flow glider wing

NASA Technical Reports Server (NTRS)

Sandlin, Doral R.; Saiki, Neal

1993-01-01

A motor glider was used to perform a flight test study on the effects of aft facing steps in a laminar boundary layer. This study focuses on two dimensional aft facing steps oriented spanwise to the flow. The size and location of the aft facing steps were varied in order to determine the critical size that will force premature transition. Transition over a step was found to be primarily a function of Reynolds number based on step height. Both of the step height Reynolds numbers for premature and full transition were determined. A hot film anemometry system was used to detect transition.

The ice nucleation temperature determines the primary drying rate of lyophilization for samples frozen on a temperature-controlled shelf.

PubMed

Searles, J A; Carpenter, J F; Randolph, T W

2001-07-01

The objective of this study was to determine the influence of ice nucleation temperature on the primary drying rate during lyophilization for samples in vials that were frozen on a lyophilizer shelf. Aqueous solutions of 10% (w/v) hydroxyethyl starch were frozen in vials with externally mounted thermocouples and then partially lyophilized to determine the primary drying rate. Low- and high-particulate-containing samples, ice-nucleating additives silver iodide and Pseudomonas syringae, and other methods were used to obtain a wide range of nucleation temperatures. In cases where the supercooling exceeded 5 degrees C, freezing took place in the following three steps: (1) primary nucleation, (2) secondary nucleation encompassing the entire liquid volume, and (3) final solidification. The primary drying rate was dependent on the ice nucleation temperature, which is stochastic in nature but is affected by particulate content and the presence of ice nucleators. Sample cooling rates of 0.05 to 1 degrees C/min had no effect on nucleation temperatures and drying rate. We found that the ice nucleation temperature is the primary determinant of the primary drying rate. However, the nucleation temperature is not under direct control, and its stochastic nature and sensitivity to difficult-to-control parameters result in drying rate heterogeneity. Nucleation temperature heterogeneity may also result in variation in other morphology-related parameters such as surface area and secondary drying rate. Overall, these results document that factors such as particulate content and vial condition, which influence ice nucleation temperature, must be carefully controlled to avoid, for example, lot-to-lot variability during cGMP production. In addition, if these factors are not controlled and/or are inadvertently changed during process development and scaleup, a lyophilization cycle that was successful on the research scale may fail during large-scale production.

Enhancing field GP engagement in hospital-based studies. Rationale, design, main results and participation in the Diagest 3-GP motivation study.

PubMed

Berkhout, Christophe; Vandaele-Bétancourt, Marie; Robert, Stéphane; Lespinasse, Solène; Mitha, Gamil; Bradier, Quentin; Vambergue, Anne; Fontaine, Pierre

2012-06-21

Diagest 3 was a study aimed at lowering the risk of developing type 2 diabetes within 3 years after childbirth. Women with gestational diabetes were enrolled in the study. After childbirth, the subjects showed little interest in the structured education programme and did not attend workshops. Their general practitioners (GPs) were approached to help motivate the subjects to participate in Diagest 3, but the GPs were reluctant. The present study aimed to understand field GPs' attitudes towards hospital-based studies, and to develop strategies to enhance their involvement and reduce subject drop-out rates. We used a three-step process: step one used a phenomenological approach exploring the beliefs, attitudes, motivations and environmental factors contributing to the GPs' level of interest in the study. Data were collected in face-to-face interviews and coded by hand and with hermeneutic software to develop distinct GP profiles. Step two was a cross-sectional survey by questionnaire to determine the distribution of the profiles in the GP study population and whether completion of an attached case report form (CRF) was associated with a particular GP profile. In step three, we assessed the impact of the motivation study on participation rates in the main study. Fifteen interviews were conducted to achieve data saturation. Theorisation led to the definition of 4 distinct GP profiles. The response rate to the questionnaire was 73%, but dropped to 52% when a CRF was attached. The link between GP profiles and the rate of CRF completion remains to be verified. The GPs provided data on the CRF that was of comparable quality to those collected in the main trial. Our analysis showed that the motivation study increased overall participation in the main study by 23%, accounting for 16% (24/152) of all final visits for 536 patients who were initially enrolled in the Diagest 3 study. When a hospital-led study explores issues in primary care, its design must anticipate GP participation early in the trial. Based on our questionnaire response rates, we found that one in two GPs were willing to participate in our hospital-led study, regardless of their initial attitudes.

Vermont STep Ahead Recognition System: QRS Profile. The Child Care Quality Rating System (QRS) Assessment

ERIC Educational Resources Information Center

Child Trends, 2010

2010-01-01

This paper presents a profile of Vermont's STep Ahead Recognition System (STARS) prepared as part of the Child Care Quality Rating System (QRS) Assessment Study. The profile consists of several sections and their corresponding descriptions including: (1) Program Information; (2) Rating Details; (3) Quality Indicators for All Child Care Programs;…

Ohio Step Up to Quality: QRS Profile. The Child Care Quality Rating System (QRS) Assessment

ERIC Educational Resources Information Center

Child Trends, 2010

2010-01-01

This paper presents a profile of Ohio's Step Up to Quality prepared as part of the Child Care Quality Rating System (QRS) Assessment Study. The profile consists of several sections and their corresponding descriptions including: (1) Program Information; (2) Rating Details; (3) Quality Indicators for Center-Based Programs; (4) Indicators for Family…

25 CFR 39.207 - How does OIEP determine a school's funding for the school year?

Code of Federal Regulations, 2014 CFR

2014-04-01

...) Step 4. Add together the sums obtained in steps 1 through 3 to obtain each school's total WSU. (e) Step 5. Add together the total WSUs for all Bureau-funded schools. (f) Step 6. Calculate the value of a... 25 Indians 1 2014-04-01 2014-04-01 false How does OIEP determine a school's funding for the school...

25 CFR 39.207 - How does OIEP determine a school's funding for the school year?

Code of Federal Regulations, 2012 CFR

2012-04-01

...) Step 4. Add together the sums obtained in steps 1 through 3 to obtain each school's total WSU. (e) Step 5. Add together the total WSUs for all Bureau-funded schools. (f) Step 6. Calculate the value of a... 25 Indians 1 2012-04-01 2011-04-01 true How does OIEP determine a school's funding for the school...

25 CFR 39.207 - How does OIEP determine a school's funding for the school year?

Code of Federal Regulations, 2013 CFR

2013-04-01

...) Step 4. Add together the sums obtained in steps 1 through 3 to obtain each school's total WSU. (e) Step 5. Add together the total WSUs for all Bureau-funded schools. (f) Step 6. Calculate the value of a... 25 Indians 1 2013-04-01 2013-04-01 false How does OIEP determine a school's funding for the school...

Survey Methods to Optimize Response Rate in the National Dental Practice-Based Research Network.

PubMed

Funkhouser, Ellen; Vellala, Kavya; Baltuck, Camille; Cacciato, Rita; Durand, Emily; McEdward, Deborah; Sowell, Ellen; Theisen, Sarah E; Gilbert, Gregg H

2017-09-01

Surveys of health professionals typically have low response rates, and these rates have been decreasing in the recent years. We report on the methods used in a successful survey of dentist members of the National Dental Practice-Based Research Network. The objectives were to quantify the (1) increase in response rate associated with successive survey methods, (2) time to completion with each successive step, (3) contribution from the final method and personal contact, and (4) differences in response rate and mode of response by practice/practitioner characteristics. Dentist members of the network were mailed an invitation describing the study. Subsequently, up to six recruitment steps were followed: initial e-mail, two e-mail reminders at 2-week intervals, a third e-mail reminder with postal mailing a paper questionnaire, a second postal mailing of paper questionnaire, and staff follow-up. Of the 1,876 invited, 160 were deemed ineligible and 1,488 (87% of 1,716 eligible) completed the survey. Completion by step: initial e-mail, 35%; second e-mail, 15%; third e-mail, 7%; fourth e-mail/first paper, 11%; second paper, 15%; and staff follow-up, 16%. Overall, 76% completed the survey online and 24% on paper. Completion rates increased in absolute numbers and proportionally with later methods of recruitment. Participation rates varied little by practice/practitioner characteristics. Completion on paper was more likely by older dentists. Multiple methods of recruitment resulted in a high participation rate: Each step and method produced incremental increases with the final step producing the largest increase.

Stratification of eosinophilic asthma patients treated with reslizumab and GINA Step 4 or 5 therapy.

PubMed

Brusselle, Guy; Canvin, Janice; Weiss, Sivan; Sun, Shawn X; Buhl, Roland

2017-07-01

Reslizumab, an anti-interleukin-5 monoclonal antibody, significantly reduces exacerbation frequency and improves lung function, asthma control and quality of life in adults with severe eosinophilic asthma, as demonstrated in Phase III studies. This secondary analysis assessed reslizumab's efficacy in patients receiving baseline treatment per Global Initiative for Asthma (GINA) Step 4 and Step 5 guidelines. Pooled data from duplicate, Phase III, reslizumab versus placebo studies in patients with severe eosinophilic asthma (blood eosinophils ≥400 cells·µL -1 ) were stratified by baseline therapy. Efficacy assessments were exacerbation rates and changes from baseline forced expiratory volume in 1 s (FEV 1 ) and patient-reported outcomes. Of 953 patients, 69% (n=657) and 11% (n=106) were receiving Step 4 and Step 5 therapy, respectively. Compared with placebo, reslizumab reduced exacerbation rates by 53% (95% CI 0.36-0.62) and 72% (95% CI 0.15-0.52), in Step 4 and Step 5 groups respectively. By study end, reslizumab increased FEV 1 in Step 4 and Step 5 groups by 103 mL (95% CI 52-154 mL) and 237 mL (95% CI 68-407 mL), respectively. Reslizumab also improved patient-reported outcomes compared with placebo in both groups. Reslizumab reduces exacerbation rates and improves lung function and patient-reported outcomes in patients with eosinophilic asthma receiving therapy per Steps 4 and 5 of the GINA guidelines.

Stratification of eosinophilic asthma patients treated with reslizumab and GINA Step 4 or 5 therapy

PubMed Central

Weiss, Sivan; Sun, Shawn X.; Buhl, Roland

2017-01-01

Reslizumab, an anti-interleukin-5 monoclonal antibody, significantly reduces exacerbation frequency and improves lung function, asthma control and quality of life in adults with severe eosinophilic asthma, as demonstrated in Phase III studies. This secondary analysis assessed reslizumab's efficacy in patients receiving baseline treatment per Global Initiative for Asthma (GINA) Step 4 and Step 5 guidelines. Pooled data from duplicate, Phase III, reslizumab versus placebo studies in patients with severe eosinophilic asthma (blood eosinophils ≥400 cells·µL−1) were stratified by baseline therapy. Efficacy assessments were exacerbation rates and changes from baseline forced expiratory volume in 1 s (FEV1) and patient-reported outcomes. Of 953 patients, 69% (n=657) and 11% (n=106) were receiving Step 4 and Step 5 therapy, respectively. Compared with placebo, reslizumab reduced exacerbation rates by 53% (95% CI 0.36–0.62) and 72% (95% CI 0.15–0.52), in Step 4 and Step 5 groups respectively. By study end, reslizumab increased FEV1 in Step 4 and Step 5 groups by 103 mL (95% CI 52–154 mL) and 237 mL (95% CI 68–407 mL), respectively. Reslizumab also improved patient-reported outcomes compared with placebo in both groups. Reslizumab reduces exacerbation rates and improves lung function and patient-reported outcomes in patients with eosinophilic asthma receiving therapy per Steps 4 and 5 of the GINA guidelines. PMID:28845430

Dissolution-modulating mechanism of pH modifiers in solid dispersion containing weakly acidic or basic drugs with poor water solubility.

PubMed

Tran, Phuong Ha-Lien; Tran, Thao Truong-Dinh; Lee, Kyoung-Ho; Kim, Dong-Jin; Lee, Beom-Jin

2010-05-01

Although the solid dispersion method has been known to increase the dissolution rate of poorly water-soluble drugs by dispersing them in hydrophilic carriers, one obstacle of the solid dispersion method is its limited solubilization capacity, especially for pH-dependent soluble drugs. pH-modified solid dispersion, in which pH modifiers are incorporated, may be a useful method for increasing the dissolution rate of weakly acidic or basic drugs. Sufficient research, including the most recent reports, was undertaken in this review. How could the inclusion of the pH the pH modifiers in the solid dispersion system change drug structural behaviors, molecular interactions, microenvironmental pH, and/or release rate of pH modifiers, relating with the enhanced dissolution of weakly acidic or weakly basic drugs with poor water solubility? These questions have been investigated to determine the dissolution-modulating mechanism of pH modifiers in solid dispersion containing weakly acidic or basic drugs. It is believed that step-by-step mechanistic approaches could provide the ultimate solution for solubilizing several poorly water-soluble drugs with pH-dependent solubility from a solid dispersion system, as well as provide ideas for developing future dosage systems.

Investigation of a submerged membrane reactor for continuous biomass hydrolysis

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

Malmali, Mohammadmahdi; Stickel, Jonathan; Wickramasinghe, S. Ranil

Enzymatic hydrolysis of cellulose is one of the most costly steps in the bioconversion of lignocellulosic biomass. Use of a submerged membrane reactor has been investigated for continuous enzymatic hydrolysis of cellulose thus allowing for greater use of the enzyme compared to a batch process. Moreover, the submerged 0.65 μm polyethersulfone microfiltration membrane avoids the need to pump a cellulose slurry through an external loop. Permeate containing glucose is withdrawn at pressures slightly below atmospheric pressure. The membrane rejects cellulose particles and cellulase enzyme bound to cellulose. Our proof-of-concept experiments have been conducted using a modified, commercially available membrane filtrationmore » cell under low fluxes around 75 L/(m2 h). The operating flux is determined by the rate of glucose production. Maximizing the rate of glucose production involves optimizing mixing, reactor holding time, and the time the feed is held in the reactor prior to commencement of membrane filtration and continuous operation. When we maximize glucose production rates it will require that we operate it at low glucose concentration in order to minimize the adverse effects of product inhibition. Consequently practical submerged membrane systems will require a combined sugar concentration step in order to concentrate the product sugar stream prior to fermentation.« less

On the Structure Sensitivity of Formic Acid Decomposition on Cu Catalysts

DOE PAGES

Li, Sha; Scaranto, Jessica; Mavrikakis, Manos

2016-08-03

Catalytic decomposition of formic acid (HCOOH) has attracted substantial attention since HCOOH is a major by-product in biomass reforming, a promising hydrogen carrier, and also a potential low temperature fuel cell feed. Despite the abundance of experimental studies for vapor-phase HCOOH decomposition on Cu catalysts, the reaction mechanism and its structure sensitivity is still under debate. In this work, self-consistent, periodic density functional theory calculations were performed on three model surfaces of copper—Cu(111), Cu(100) and Cu(211), and both the HCOO (formate)-mediated and COOH (carboxyl)-mediated pathways were investigated for HCOOH decomposition. The energetics of both pathways suggest that the HCOO-mediated routemore » is more favorable than the COOH-mediated route on all three surfaces, and that HCOOH decomposition proceeds through two consecutive dehydrogenation steps via the HCOO intermediate followed by the recombinative desorption of H 2. On all three surfaces, HCOO dehydrogenation is the likely rate determining step since it has the highest transition state energy and also the highest activation energy among the three catalytic steps in the HCOO pathway. The reaction is structure sensitive on Cu catalysts since the examined three Cu facets have dramatically different binding strengths for the key intermediate HCOO and varied barriers for the likely rate determining step—HCOO dehydrogenation. Cu(100) and Cu(211) bind HCOO much more strongly than Cu(111), and they are also characterized by potential energy surfaces that are lower in energy than that for the Cu(111) facet. Coadsorbed HCOO and H represents the most stable state along the reaction coordinate, indicating that, under reaction conditions, there might be a substantial surface coverage of the HCOO intermediate, especially at under-coordinated step, corner or defect sites. Therefore, under reaction conditions, HCOOH decomposition is predicted to occur most readily on the terrace sites of Cu nanoparticles. Finally, as a result, we hereby present an example of a fundamentally structure-sensitive reaction, which may present itself as structure-insensitive in typical varied particle-size experiments.« less

Towards development and validation of an intraoperative assessment tool for robot-assisted radical prostatectomy training: results of a Delphi study.

PubMed

Morris, Christopher; Hoogenes, Jen; Shayegan, Bobby; Matsumoto, Edward D

2017-01-01

As urology training shifts toward competency-based frameworks, the need for tools for high stakes assessment of trainees is crucial. Validated assessment metrics are lacking for many robot-assisted radical prostatectomy (RARP). As it is quickly becoming the gold standard for treatment of localized prostate cancer, the development and validation of a RARP assessment tool for training is timely. We recruited 13 expert RARP surgeons from the United States and Canada to serve as our Delphi panel. Using an initial inventory developed via a modified Delphi process with urology residents, fellows, and staff at our institution, panelists iteratively rated each step and sub-step on a 5-point Likert scale of agreement for inclusion in the final assessment tool. Qualitative feedback was elicited for each item to determine proper step placement, wording, and suggestions. Panelist's responses were compiled and the inventory was edited through three iterations, after which 100% consensus was achieved. The initial inventory steps were decreased by 13% and a skip pattern was incorporated. The final RARP stepwise inventory was comprised of 13 critical steps with 52 sub-steps. There was no attrition throughout the Delphi process. Our Delphi study resulted in a comprehensive inventory of intraoperative RARP steps with excellent consensus. This final inventory will be used to develop a valid and psychometrically sound intraoperative assessment tool for use during RARP training and evaluation, with the aim of increasing competency of all trainees. Copyright® by the International Brazilian Journal of Urology.

Towards development and validation of an intraoperative assessment tool for robot-assisted radical prostatectomy training: results of a Delphi study

PubMed Central

Morris, Christopher; Hoogenes, Jen; Shayegan, Bobby; Matsumoto, Edward D.

2017-01-01

ABSTRACT Introduction As urology training shifts toward competency-based frameworks, the need for tools for high stakes assessment of trainees is crucial. Validated assessment metrics are lacking for many robot-assisted radical prostatectomy (RARP). As it is quickly becoming the gold standard for treatment of localized prostate cancer, the development and validation of a RARP assessment tool for training is timely. Materials and methods We recruited 13 expert RARP surgeons from the United States and Canada to serve as our Delphi panel. Using an initial inventory developed via a modified Delphi process with urology residents, fellows, and staff at our institution, panelists iteratively rated each step and sub-step on a 5-point Likert scale of agreement for inclusion in the final assessment tool. Qualitative feedback was elicited for each item to determine proper step placement, wording, and suggestions. Results Panelist’s responses were compiled and the inventory was edited through three iterations, after which 100% consensus was achieved. The initial inventory steps were decreased by 13% and a skip pattern was incorporated. The final RARP stepwise inventory was comprised of 13 critical steps with 52 sub-steps. There was no attrition throughout the Delphi process. Conclusions Our Delphi study resulted in a comprehensive inventory of intraoperative RARP steps with excellent consensus. This final inventory will be used to develop a valid and psychometrically sound intraoperative assessment tool for use during RARP training and evaluation, with the aim of increasing competency of all trainees. PMID:28379668

Stepped Care Versus Direct Face-to-Face Cognitive Behavior Therapy for Social Anxiety Disorder and Panic Disorder: A Randomized Effectiveness Trial.

PubMed

Nordgreen, Tine; Haug, Thomas; Öst, Lars-Göran; Andersson, Gerhard; Carlbring, Per; Kvale, Gerd; Tangen, Tone; Heiervang, Einar; Havik, Odd E

2016-03-01

The aim of this study was to assess the effectiveness of a cognitive behavioral therapy (CBT) stepped care model (psychoeducation, guided Internet treatment, and face-to-face CBT) compared with direct face-to-face (FtF) CBT. Patients with panic disorder or social anxiety disorder were randomized to either stepped care (n=85) or direct FtF CBT (n=88). Recovery was defined as meeting two of the following three criteria: loss of diagnosis, below cut-off for self-reported symptoms, and functional improvement. No significant differences in intention-to-treat recovery rates were identified between stepped care (40.0%) and direct FtF CBT (43.2%). The majority of the patients who recovered in the stepped care did so at the less therapist-demanding steps (26/34, 76.5%). Moderate to large within-groups effect sizes were identified at posttreatment and 1-year follow-up. The attrition rates were high: 41.2% in the stepped care condition and 27.3% in the direct FtF CBT condition. These findings indicate that the outcome of a stepped care model for anxiety disorders is comparable to that of direct FtF CBT. The rates of improvement at the two less therapist-demanding steps indicate that stepped care models might be useful for increasing patients' access to evidence-based psychological treatments for anxiety disorders. However, attrition in the stepped care condition was high, and research regarding the factors that can improve adherence should be prioritized. Copyright © 2015. Published by Elsevier Ltd.

Extractive alkylation of 6-mercaptopurine and determination in plasma by gas chromatography-mass spectrometry.

PubMed

Floberg, S; Hartvig, P; Lindström, B; Lönner-Holm, G; Odlind, B

1981-09-11

An analytical procedure was developed for the determination of 6-mercaptopurine in plasma. Owing to the polar character and low plasma concentration of the compound, extraction and derivatization was carried out directly from the plasma sample by extractive alkylation. Determination was made using gas chromatography-mass spectrometry with multiple-ion detection. Conditions with respect to the rate of formation and the stability of the derivative formed in the extractive alkylation step were evaluated. The selectively of the method to azathioprine and to metabolites was thoroughly investigated. No 6-mercaptopurine was formed from azathioprine added to water or plasma and run through the method. The method enables the detection of 2 ng of 6 mercaptopurine in a 1.0-ml plasma sample. Quantitative determinations were done down to 10 ng/ml 6 mercaptopurine in plasma.

Aquifer response to stream-stage and recharge variations. II. Convolution method and applications

NASA Astrophysics Data System (ADS)

Barlow, P. M.; DeSimone, L. A.; Moench, A. F.

2000-05-01

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 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 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.

STEPS: A NARRATIVE ACCOUNT OF A GABAPENTIN SEEDING TRIAL

PubMed Central

Krumholz, Samuel D.; Egilman, David S.; Ross, Joseph S.

2012-01-01

Background Seeding trials, clinical studies conducted by pharmaceutical companies for marketing purposes, have rarely been described in detail. Methods We examined all documents relating to the clinical trial Study of Neurontin: Titrate to Effect, Profile of Safety (STEPS) produced during the Neurontin marketing, sales practices and product liability litigation, including company internal and external correspondence, reports, and presentations, as well as depositions elicited in legal proceedings of Harden Manufacturing v. Pfizer and Franklin v. Warner-Lambert, the majority of which were created between 1990 and 2009. Using a systematic search strategy, we identified and reviewed all documents related to the STEPS trial, in order to identify key themes related to the trial’s conduct and determine the extent of marketing involvement in its planning and implementation. Results Documents demonstrated that STEPS was a seeding trial posing as a legitimate scientific study. Documents consistently described the trial itself, not trial results, to be a marketing tactic in the company’s marketing plans. Documents demonstrated that several external sources questioned the validity of the study before execution, and that data quality during the study was often compromised. Furthermore, documents described company analyses examining the impact of participating as a STEPS investigator on rates and dosages of gabapentin prescribing, finding a positive association. None of these findings were reported in two published papers. Conclusions The STEPS trial was a seeding trial, used to promote gabapentin and increase prescribing among investigators, and marketing was extensively involved in its planning and implementation. PMID:21709111

Study of neurontin: titrate to effect, profile of safety (STEPS) trial: a narrative account of a gabapentin seeding trial.

PubMed

Krumholz, Samuel D; Egilman, David S; Ross, Joseph S

2011-06-27

Seeding trials, clinical studies conducted by pharmaceutical companies for marketing purposes, have rarely been described in detail. We examined all documents relating to the clinical trial Study of Neurontin: Titrate to Effect, Profile of Safety (STEPS) produced during the Neurontin marketing, sales practices, and product liability litigation, including company internal and external correspondence, reports, and presentations, as well as depositions elicited in legal proceedings of Harden Manufacturing vs Pfizer and Franklin vs Warner-Lambert, most which were created between 1990 and 2009. Using a systematic search strategy, we identified and reviewed all documents related to the STEPS trial in order to identify key themes related to the trial's conduct and determine the extent of marketing involvement in its planning and implementation. Documents demonstrated that STEPS was a seeding trial posing as a legitimate scientific study. Documents consistently described the trial itself, not trial results, to be a marketing tactic in the company's marketing plans. Documents demonstrated that at least 2 external sources questioned the validity of the study before execution, and that data quality during the study was often compromised. Furthermore, documents described company analyses examining the impact of participating as a STEPS investigator on rates and dosages of gabapentin prescribing, finding a positive association. None of these findings were reported in 2 published articles. The STEPS trial was a seeding trial, used to promote gabapentin and increase prescribing among investigators, and marketing was extensively involved in its planning and implementation.

Parallel Multi-Step/Multi-Rate Integration of Two-Time Scale Dynamic Systems

NASA Technical Reports Server (NTRS)

Chang, Johnny T.; Ploen, Scott R.; Sohl, Garett. A,; Martin, Bryan J.

2004-01-01

Increasing demands on the fidelity of simulations for real-time and high-fidelity simulations are stressing the capacity of modern processors. New integration techniques are required that provide maximum efficiency for systems that are parallelizable. However many current techniques make assumptions that are at odds with non-cascadable systems. A new serial multi-step/multi-rate integration algorithm for dual-timescale continuous state systems is presented which applies to these systems, and is extended to a parallel multi-step/multi-rate algorithm. The superior performance of both algorithms is demonstrated through a representative example.

Changes in muscle activation patterns when running step rate is increased.

PubMed

Chumanov, Elizabeth S; Wille, Christa M; Michalski, Max P; Heiderscheit, Bryan C

2012-06-01

Running with a step rate 5-10% greater than one's preferred can substantially reduce lower extremity joint moments and powers, and has been suggested as a possible strategy to aid in running injury management. The purpose of this study was to examine how neuromuscular activity changes with an increase in step rate during running. Forty-five injury-free, recreational runners participated in this study. Three-dimensional motion, ground reaction forces, and electromyography (EMG) of 8 muscles (rectus femoris, vastus lateralis, medial gastrocnemius, tibialis anterior, medial and lateral hamstrings, and gluteus medius and maximus) were recorded as each subject ran at their preferred speed for three different step rate conditions: preferred, +5% and +10% of preferred. Outcome measures included mean normalized EMG activity for each muscle at specific periods during the gait cycle. Muscle activities were found to predominantly increase during late swing, with no significant change in activities during the loading response. This increased muscle activity in anticipation of foot-ground contact likely alters the landing posture of the limb and the subsequent negative work performed by the joints during stance phase. Further, the increased activity observed in the gluteus maximus and medius suggests running with a greater step rate may have therapeutic benefits to those with anterior knee pain. Copyright © 2012 Elsevier B.V. All rights reserved.

Influence of weather and atmospheric pollution on physical activity in patients with COPD.

PubMed

Alahmari, Ayedh D; Mackay, Alex J; Patel, Anant R C; Kowlessar, Beverly S; Singh, Richa; Brill, Simon E; Allinson, James P; Wedzicha, Jadwiga A; Donaldson, Gavin C

2015-06-13

Information concerning how climate and atmospheric pollutants affects physical activity in COPD patients is lacking and might be valuable in determining when physical activity should be encouraged. Seventy-three stable COPD patients recorded on daily diary cards worsening of respiratory symptoms, peak expiratory flow rate, hours spent outside the home and the number of steps taken per day. Pedometry data was recorded on 16,478 days, an average of 267 days per patient (range 29-658). Daily data for atmospheric PM10 and ozone (O3) were obtained for Bloomsbury Square, Central London from the Air Quality Information Archive databases. Daily weather data were obtained for London Heathrow from the British Atmospheric Data Archive. Colder weather below 22.5 °C, reduced daily step count by 43.3 steps day per °C (95% CI 2.14 to 84.4; p = 0.039) and activity was lower on rainy than dry days (p = 0.002) and on overcast compared to sunny days (p < 0.001). Daily step count was 434 steps per day lower on Sunday than Saturday (p < 0.001) and 353 steps per day lower on Saturday than Friday (p < 0.001). After allowance for these effects, higher O3 levels decreased activity during the whole week (-8 steps/ug/m3; p = 0.005) and at weekends (-7.8 steps/ug/m3; p = 0.032). Whilst, during the week PM10 reduced activity (p = 0.018) but not during the weekend. Inactivity of COPD patients is greatest on cold, wet and overcast days and at the weekends. This study also provides evidence of an independent effect of atmospheric pollution at high levels.

Does the MCAT predict medical school and PGY-1 performance?

PubMed

Saguil, Aaron; Dong, Ting; Gingerich, Robert J; Swygert, Kimberly; LaRochelle, Jeffrey S; Artino, Anthony R; Cruess, David F; Durning, Steven J

2015-04-01

The Medical College Admissions Test (MCAT) is a high-stakes test required for entry to most U. S. medical schools; admissions committees use this test to predict future accomplishment. Although there is evidence that the MCAT predicts success on multiple choice-based assessments, there is little information on whether the MCAT predicts clinical-based assessments of undergraduate and graduate medical education performance. This study looked at associations between the MCAT and medical school grade point average (GPA), Medical Licensing Examination (USMLE) scores, observed patient care encounters, and residency performance assessments. This study used data collected as part of the Long-Term Career Outcome Study to determine associations between MCAT scores, USMLE Step 1, Step 2 clinical knowledge and clinical skill, and Step 3 scores, Objective Structured Clinical Examination performance, medical school GPA, and PGY-1 program director (PD) assessment of physician performance for students graduating 2010 and 2011. MCAT data were available for all students, and the PGY PD evaluation response rate was 86.2% (N = 340). All permutations of MCAT scores (first, last, highest, average) were weakly associated with GPA, Step 2 clinical knowledge scores, and Step 3 scores. MCAT scores were weakly to moderately associated with Step 1 scores. MCAT scores were not significantly associated with Step 2 clinical skills Integrated Clinical Encounter and Communication and Interpersonal Skills subscores, Objective Structured Clinical Examination performance or PGY-1 PD evaluations. MCAT scores were weakly to moderately associated with assessments that rely on multiple choice testing. The association is somewhat stronger for assessments occurring earlier in medical school, such as USMLE Step 1. The MCAT was not able to predict assessments relying on direct clinical observation, nor was it able to predict PD assessment of PGY-1 performance. Reprint & Copyright © 2015 Association of Military Surgeons of the U.S.

Comparison of the anaerobic digestion at the mesophilic and thermophilic temperature regime of organic wastes from the agribusiness.

PubMed

Almeida Streitwieser, Daniela

2017-10-01

An overall kinetic power law model has been successfully applied to study the anaerobic digestion of agricultural wastes. In this comparative kinetic study feed composition, organic load rate, residence time and process temperature have been systematically varied in an automated semi-continuous fermentation system to obtain the dependency of the rate of degradation as biogas production on the organic load rate and temperature. The results show that the overall reaction order depend only on the Chemical Oxygen Demand (COD) at values between 3.6 and 3.7. The Arrhenius approach shows a shift in the rate determining step between the mesophilic and thermophilic temperature regimes. The activation energy at the temperature insensitive mesophilic regime is very small at 8.9 (kJ/mole), while the activation energy at the temperature sensitive thermophilic regime lies around 117 (kJ/mole). Copyright © 2017 Elsevier Ltd. All rights reserved.

Baselines For Land-Use Change In The Tropics: Application ToAvoided Deforestation Projects

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

Brown, Sandra; Hall, Myrna; Andrasko, Ken

2007-06-01

Although forest conservation activities particularly in thetropics offer significant potential for mitigating carbon emissions,these types of activities have faced obstacles in the policy arena causedby the difficulty in determining key elements of the project cycle,particularly the baseline. A baseline for forest conservation has twomain components: the projected land-use change and the correspondingcarbon stocks in the applicable pools such as vegetation, detritus,products and soil, with land-use change being the most difficult toaddress analytically. In this paper we focus on developing and comparingthree models, ranging from relatively simple extrapolations of pasttrends in land use based on simple drivers such as population growthmore » tomore complex extrapolations of past trends using spatially explicitmodels of land-use change driven by biophysical and socioeconomicfactors. The three models of the latter category used in the analysis atregional scale are The Forest Area Change (FAC) model, the Land Use andCarbon Sequestration (LUCS) model, and the Geographical Modeling (GEOMOD)model. The models were used to project deforestation in six tropicalregions that featured different ecological and socioeconomic conditions,population dynamics, and uses of the land: (1) northern Belize; (2) SantaCruz State, Bolivia; (3) Parana State in Brazil; (4) Campeche, Mexico;(5) Chiapas, Mexico; and (6) Michoacan, Mexico. A comparison of all modeloutputs across all six regions shows that each model produced quitedifferent deforestation baseline. In general, the simplest FAC model,applied at the national administrative-unit scale, projected the highestamount of forest loss (four out of six) and the LUCS model the leastamount of loss (four out of five). Based on simulations of GEOMOD, wefound that readily observable physical and biological factors as well asdistance to areas of past disturbance were each about twice as importantas either sociological/demographic or economic/infrastructure factors(less observable) in explaining empirical land-use patterns. We proposefrom the lessons learned, a methodology comprised of three main steps andsix tasks can be used to begin developing credible baselines. We alsopropose that the baselines be projected over a 10-year period because,although projections beyond 10 years are feasible, they are likely to beunrealistic for policy purposes. In the first step, an historic land-usechange and deforestation estimate is made by determining the analyticdomain (size of the region relative to the size of proposed project),obtaining historic data, analyzing candidate historic baseline drivers,and identifying three to four major drivers. In the second step, abaseline of where deforestation is likely to occur --a potential land-usechange (PLUC) map is produced using a spatial model such as GEOMOD thatuses the key drivers from step one. Then rates of deforestation areprojected over a 10-year baseline period using any of the three models.Using the PLUC maps, projected rates of deforestation, and carbon stockestimates, baselineprojections are developed that can be used for projectGHG accounting and crediting purposes: The final step proposes that, atagreed interval (eg, +10 years), the baseline assumptions about baselinedrivers be re-assessed. This step reviews the viability of the 10-yearbaseline in light of changes in one or more key baseline drivers (e.g.,new roads, new communities, new protected area, etc.). The potentialland-use change map and estimates of rates of deforestation could beredone at the agreed interval, allowing the rates and changes in spatialdrivers to be incorporated into a defense of the existing baseline, orderivation of a new baseline projection.« less

A modified sulfate process to lunar oxygen

NASA Technical Reports Server (NTRS)

Sullivan, Thomas A.

1992-01-01

A modified sulfate process which produces oxygen from iron oxide-bearing minerals in lunar soil is under development. Reaction rates of ilmenite in varying strength sulfuric acid have been determined. Quantitative conversion of ilmenite to ferrous sulfate was observed over a range of temperatures and concentrations. Data has also been developed on the calcination of by-product sulfates. System engineering for overall operability and simplicity has begun, suggesting that a process separating the digestion and sulfate dissolution steps may offer an optimum process.

Hybrid finite element and Brownian dynamics method for diffusion-controlled reactions.

PubMed

Bauler, Patricia; Huber, Gary A; McCammon, J Andrew

2012-04-28

Diffusion is often the rate determining step in many biological processes. Currently, the two main computational methods for studying diffusion are stochastic methods, such as Brownian dynamics, and continuum methods, such as the finite element method. This paper proposes a new hybrid diffusion method that couples the strengths of each of these two methods. The method is derived for a general multidimensional system, and is presented using a basic test case for 1D linear and radially symmetric diffusion systems.

Experimental Validation of a Time-Accurate Finite Element Model for Coupled Multibody Dynamics and Liquid Sloshing

DTIC Science & Technology

2007-04-16

velocity of the fluid mesh, P is the relative pressure, xr is the position vector, τ is the deviatoric stress tensor, D is the rate of deformation...corresponds to a slip factor of zero. The slip factor determines how much of the fluid and structure forces are mutually exchanged. Equations 22 and 23...updated from last to first. viii.Average the fluid pressure (This step eliminates the pressure checker-boarding effect and allows use of equal

A kinetic study of jack-bean urease denaturation by a new dithiocarbamate bismuth compound

NASA Astrophysics Data System (ADS)

Menezes, D. C.; Borges, E.; Torres, M. F.; Braga, J. P.

2012-10-01

A kinetic study concerning enzymatic inhibitory effect of a new bismuth dithiocarbamate complex on jack-bean urease is reported. A neural network approach is used to solve the ill-posed inverse problem arising from numerical treatment of the subject. A reaction mechanism for the urease denaturation process is proposed and the rate constants, relaxation time constants, equilibrium constants, activation Gibbs free energies for each reaction step and Gibbs free energies for the transition species are determined.

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.

Response time of mitochondrial oxygen consumption following stepwise changes in cardiac energy demand.

PubMed

van Beek, J H; Westerhof, N

1990-01-01

We determined the speed with which mitochondrial oxygen consumption and therefore the mitochondrial ATP-synthesis adapted to changes in metabolic demand in the rabbit heart. This was done by measuring the oxygen uptake of the whole heart during a stepwise change in heart rate and correcting for the time taken by diffusion and by convective transport in the blood vessels. Data for the correction for transport time were obtained from the response of venous oxygen concentration to a stepwise change of arterial oxygen concentration. The time constant of the response of mitochondrial oxygen consumption to a step change in heart rate was found to be 4-8 s.

An exploration of the effect of onsite 12‐step meetings on post‐treatment outcomes among polysubstance‐dependent outpatient clients

PubMed Central

Stanick, Virginia; Sands, Brian

2007-01-01

Rates of return to active substance use after addiction treatment tend to be high; participation in 12‐step fellowships (e.g., Alcoholics Anonymous) reduces relapse rates but many clients do not attend or attend for a short period only. This quasi‐experimental study uses repeated measurement to explore the role of presence/absence of onsite 12‐step meetings during treatment on post‐treatment outcomes. Polysubstance‐dependent clients (N = 219) recruited at a program with and one without 12‐step onsite, were followed for one year post‐treatment. Onsite 12‐step enhanced 12‐step attendance, especially during treatment, and predicted continuous abstinence for the post treatment year. Holding 12‐step meetings onsite is a low‐cost strategy that programs should consider to foster post‐treatment remission maintenance. PMID:17986710

Method and apparatus for characterizing propagation delays of integrated circuit devices

NASA Technical Reports Server (NTRS)

Blaes, Brent R. (Inventor); Buehler, Martin G. (Inventor)

1987-01-01

Propagation delay of a signal through a channel is measured by cyclically generating a first step-wave signal for transmission through the channel to a two-input logic element and a second step-wave signal with a controlled delay to the second input terminal of the logic element. The logic element determines which signal is present first at its input terminals and stores a binary signal indicative of that determination for control of the delay of the second signal which is advanced or retarded for the next cycle until both the propagation delayed first step-wave signal and the control delayed step-wave signal are coincident. The propagation delay of the channel is then determined by measuring the time between the first and second step-wave signals out of the controlled step-wave signal generator.

A deterministic method for estimating free energy genetic network landscapes with applications to cell commitment and reprogramming paths.

PubMed

Olariu, Victor; Manesso, Erica; Peterson, Carsten

2017-06-01

Depicting developmental processes as movements in free energy genetic landscapes is an illustrative tool. However, exploring such landscapes to obtain quantitative or even qualitative predictions is hampered by the lack of free energy functions corresponding to the biochemical Michaelis-Menten or Hill rate equations for the dynamics. Being armed with energy landscapes defined by a network and its interactions would open up the possibility of swiftly identifying cell states and computing optimal paths, including those of cell reprogramming, thereby avoiding exhaustive trial-and-error simulations with rate equations for different parameter sets. It turns out that sigmoidal rate equations do have approximate free energy associations. With this replacement of rate equations, we develop a deterministic method for estimating the free energy surfaces of systems of interacting genes at different noise levels or temperatures. Once such free energy landscape estimates have been established, we adapt a shortest path algorithm to determine optimal routes in the landscapes. We explore the method on three circuits for haematopoiesis and embryonic stem cell development for commitment and reprogramming scenarios and illustrate how the method can be used to determine sequential steps for onsets of external factors, essential for efficient reprogramming.

Development of a digital video-microscopy technique to study lactose crystallisation kinetics in situ.

PubMed

Arellano, María Paz; Aguilera, José Miguel; Bouchon, Pedro

2004-11-15

Polarised light microscopy was employed non-invasively to monitor lactose crystallisation from non-seeded supersaturated solutions in real time. Images were continuously recorded, processed and characterised by image analysis, and the results were compared with those obtained by refractometry. Three crystallisation temperatures (10, 20 and 30 degrees C) and three different levels of initial relative supersaturation (C/C(s)=1.95; 2.34; 3.15) were investigated. Induction times using the imaging technique proved to be substantially lower than those determined using refractive index. Lactose crystals were isolated digitally to determine geometrical parameters of interest, such as perimeter, diameter, area, roundness and Feret mean, and to derive crystal growth rates. Mean growth rates obtained for single crystals were fitted to a combined mass transfer model (R(2)=0.9766). The model allowed the effects of temperature and supersaturation on crystallisation rate to be clearly identified. It also suggested that, in this set of experiments, surface integration seemed to be the rate controlling step. It is believed that a similar experimental set-up could be implemented in a real food system to characterise a particular process where crystallisation control is of interest and where traditional techniques are difficult to implement.

A deterministic method for estimating free energy genetic network landscapes with applications to cell commitment and reprogramming paths

PubMed Central

Olariu, Victor; Manesso, Erica

2017-01-01

Depicting developmental processes as movements in free energy genetic landscapes is an illustrative tool. However, exploring such landscapes to obtain quantitative or even qualitative predictions is hampered by the lack of free energy functions corresponding to the biochemical Michaelis–Menten or Hill rate equations for the dynamics. Being armed with energy landscapes defined by a network and its interactions would open up the possibility of swiftly identifying cell states and computing optimal paths, including those of cell reprogramming, thereby avoiding exhaustive trial-and-error simulations with rate equations for different parameter sets. It turns out that sigmoidal rate equations do have approximate free energy associations. With this replacement of rate equations, we develop a deterministic method for estimating the free energy surfaces of systems of interacting genes at different noise levels or temperatures. Once such free energy landscape estimates have been established, we adapt a shortest path algorithm to determine optimal routes in the landscapes. We explore the method on three circuits for haematopoiesis and embryonic stem cell development for commitment and reprogramming scenarios and illustrate how the method can be used to determine sequential steps for onsets of external factors, essential for efficient reprogramming. PMID:28680655

Feasibility of an Electronic Survey on iPads with In-Person Data Collectors for Data Collection with Health Care Professionals and Health Care Consumers in General Emergency Departments.

PubMed

Scott, Shannon D; Albrecht, Lauren; Given, Lisa M; Arseneau, Danielle; Klassen, Terry P

2016-06-29

Translating Emergency Knowledge for Kids was established to bridge the research-practice gap in pediatric emergency care by bringing the best evidence to Canadian general emergency departments (EDs). The first step in this process was to conduct a national needs assessment to determine the information needs and preferences of health professionals and parents in this clinical setting. To describe the development and implementation of two electronic surveys, and determine the feasibility of collecting electronic survey data on iPads with in-person data collectors in a busy clinical environment. Two descriptive surveys were conducted in 32 general EDs. Specific factors were addressed in four survey development and implementation stages: survey design, survey delivery, survey completion, and survey return. Feasibility of the data collection approach was determined by evaluating participation rates, completion rates, average survey time to completion, and usability of the platform. Usability was assessed with the in-person data collectors on five key variables: interactivity, portability, innovativeness, security, and proficiency. Health professional participation rates (1561/2575, 60.62%) and completion rates (1471/1561, 94.23%) were strong. Parental participation rates (974/1099, 88.63%) and completion rates (897/974, 92.09%) were excellent. Mean time to survey completion was 28.08 minutes for health professionals and 43.23 minutes for parents. Data collectors rated the platform "positively" to "very positively" on all five usability variables. A number of design and implementation considerations were explored and integrated into this mixed-mode survey data collection approach. Feasibility was demonstrated by the robust survey participation and completion rates, reasonable survey completion times, and very positive usability evaluation results.

Combined theoretical and experimental analysis of processes determining cathode performance in solid oxide fuel cells.

PubMed

Kuklja, M M; Kotomin, E A; Merkle, R; Mastrikov, Yu A; Maier, J

2013-04-21

Solid oxide fuel cells (SOFC) are under intensive investigation since the 1980's as these devices open the way for ecologically clean direct conversion of the chemical energy into electricity, avoiding the efficiency limitation by Carnot's cycle for thermochemical conversion. However, the practical development of SOFC faces a number of unresolved fundamental problems, in particular concerning the kinetics of the electrode reactions, especially oxygen reduction reaction. We review recent experimental and theoretical achievements in the current understanding of the cathode performance by exploring and comparing mostly three materials: (La,Sr)MnO3 (LSM), (La,Sr)(Co,Fe)O3 (LSCF) and (Ba,Sr)(Co,Fe)O3 (BSCF). Special attention is paid to a critical evaluation of advantages and disadvantages of BSCF, which shows the best cathode kinetics known so far for oxides. We demonstrate that it is the combined experimental and theoretical analysis of all major elementary steps of the oxygen reduction reaction which allows us to predict the rate determining steps for a given material under specific operational conditions and thus control and improve SOFC performance.

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

Evaluating the Validity of Current Mainstream Wearable Devices in Fitness Tracking Under Various Physical Activities: Comparative Study.

PubMed

Xie, Junqing; Wen, Dong; Liang, Lizhong; Jia, Yuxi; Gao, Li; Lei, Jianbo

2018-04-12

Wearable devices have attracted much attention from the market in recent years for their fitness monitoring and other health-related metrics; however, the accuracy of fitness tracking results still plays a major role in health promotion. The aim of this study was to evaluate the accuracy of a host of latest wearable devices in measuring fitness-related indicators under various seminatural activities. A total of 44 healthy subjects were recruited, and each subject was asked to simultaneously wear 6 devices (Apple Watch 2, Samsung Gear S3, Jawbone Up3, Fitbit Surge, Huawei Talk Band B3, and Xiaomi Mi Band 2) and 2 smartphone apps (Dongdong and Ledongli) to measure five major health indicators (heart rate, number of steps, distance, energy consumption, and sleep duration) under various activity states (resting, walking, running, cycling, and sleeping), which were then compared with the gold standard (manual measurements of the heart rate, number of steps, distance, and sleep, and energy consumption through oxygen consumption) and calculated to determine their respective mean absolute percentage errors (MAPEs). Wearable devices had a rather high measurement accuracy with respect to heart rate, number of steps, distance, and sleep duration, with a MAPE of approximately 0.10, whereas poor measurement accuracy was observed for energy consumption (calories), indicated by a MAPE of up to 0.44. The measurements varied for the same indicator measured by different fitness trackers. The variation in measurement of the number of steps was the highest (Apple Watch 2: 0.42; Dongdong: 0.01), whereas it was the lowest for heart rate (Samsung Gear S3: 0.34; Xiaomi Mi Band 2: 0.12). Measurements differed insignificantly for the same indicator measured under different states of activity; the MAPE of distance and energy measurements were in the range of 0.08 to 0.17 and 0.41 to 0.48, respectively. Overall, the Samsung Gear S3 performed the best for the measurement of heart rate under the resting state (MAPE of 0.04), whereas Dongdong performed the best for the measurement of the number of steps under the walking state (MAPE of 0.01). Fitbit Surge performed the best for distance measurement under the cycling state (MAPE of 0.04), and Huawei Talk Band B3 performed the best for energy consumption measurement under the walking state (MAPE of 0.17). At present, mainstream devices are able to reliably measure heart rate, number of steps, distance, and sleep duration, which can be used as effective health evaluation indicators, but the measurement accuracy of energy consumption is still inadequate. Fitness trackers of different brands vary with regard to measurement of indicators and are all affected by the activity state, which indicates that manufacturers of fitness trackers need to improve their algorithms for different activity states. ©Junqing Xie, Dong Wen, Lizhong Liang, Yuxi Jia, Li Gao, Jianbo Lei. Originally published in JMIR Mhealth and Uhealth (http://mhealth.jmir.org), 12.04.2018.

Cryopreservation of veliger larvae of trumpet shell, Charonia sauliae: an essential preparation to artificial propagation

NASA Astrophysics Data System (ADS)

Kang, Kyoung Ho; Zhang, Zhifeng; Bao, Zhenmin; Shao, Mingyu

2009-09-01

Trumpet shell, Charonia sauliae, is an endangered and valuable species, but its artificial propagation protocol has not been successfully established. To estimate the possibility of cryopreservation for larvae of C. sauliae, which is a potential preparation for its artificial reproduction and further research, in this study a protocol for the cryopreservation of veliger larvae of trumpet shell was optimized. Through a two-step cryopreservation procedure, four kinds of cryoprotectants (ethylene glycol, 1, 2-propanediol, dimethyl sulfoxide and glycerol) were employed at three concentrations (1.0, 1.5 and 2.0 molL-1) respectively and survival rates of larvae were determined after a storage of 1h. The larvae frozen with these four cryoprotectants after 1 h storage were cultured, and then survival rates were determined at 24, 72 and 120 h after thawing. Dimethyl sulfoxide at a concentration of 1.5 molL-1 showed the best protective effect in all experiments ( p<0.05). And survival rates of larvae frozen with dimethyl sulfoxide were determined after 1, 7 and 15 d of storage. The survival rates of larvae frozen with 1.5 molL-1 dimethyl sulfoxide after 1 h, 1 d, 7 d and 15 d of storage were 80.77% ±7.51%, 80.34% ±11.28%, 83.10% ±9.14% and 77.23% ±6.22% respectively. No significant differences in survival rates of larvae frozen with dimethyl sulfoxide were observed after various storage periods ( p>0.05).

Los Angeles County Steps to Excellence Project: QRS Profile. The Child Care Quality Rating System (QRS) Assessment

ERIC Educational Resources Information Center

Child Trends, 2010

2010-01-01

This paper presents a profile of Los Angeles County's Steps to Excellence Project prepared as part of the Child Care Quality Rating System (QRS) Assessment Study. The profile consists of several sections and their corresponding descriptions including: (1) Program Information; (2) Rating Details; (3) Quality Indicators for Center-Based Programs;…

Calculated rate constants for the reaction ClO + O yields Cl + O2 between 220 and 1000 deg K. [molecular trajectories and stratospheric ozone

NASA Technical Reports Server (NTRS)

Jaffee, R. L.

1978-01-01

Classical trajectory calculations are presented for the reaction ClO + O yields Cl + O2, a reaction which is an important step in the chlorine-catalyzed destruction of ozone which is thought to occur in the 220 and 1000 K. The calculated rate constant is 4.36 x 10 to the minus 11th power exp (-191/T)cu cm molecule (-1)s(-1) and its value at 300 K is 2.3 plus or minus 10 to the 11th power cu cm molecule (-1)s(-1), about a factor of 2 lower than recent experimental data. The empirical potential energy surface used in the calculations was constructed to fit experimental data for ClO, O2 and ClOO molecules. Other important features of this potential surface, such as the barrier to reaction, were varied systematically and calculations were performed for a range of conditions to determine the best theoretical rate constants. Results demonstrate the utility of classical trajectory methods for determining activation energies and other kinetic data for important atmospheric reactions.

Transient shear viscosity of weakly aggregating polystyrene latex dispersions

NASA Astrophysics Data System (ADS)

de Rooij, R.; Potanin, A. A.; van den Ende, D.; Mellema, J.

1994-04-01

The transient behavior of the viscosity (stress growth) of a weakly aggregating polystyrene latex dispersion after a step from a high shear rate to a lower shear rate has been measured and modeled. Single particles cluster together into spherical fractal aggregates. The steady state size of these aggregates is determined by the shear stresses exerted on the latter by the flow field. The restructuring process taking place when going from a starting situation with monodisperse spherical aggregates to larger monodisperse spherical aggregates is described by the capture of primary fractal aggregates by growing aggregates until a new steady state is reached. It is assumed that the aggregation mechanism is diffusion limited. The model is valid if the radii of primary aggregates Rprim are much smaller than the radii of the growing aggregates. Fitting the model to experimental data at two volume fractions and a number of step sizes in shear rate yielded physically reasonable values of Rprim at fractal dimensions 2.1≤df≤2.2. The latter range is in good agreement with the range 2.0≤df≤2.3 obtained from steady shear results. The experimental data have also been fitted to a numerical solution of the diffusion equation for primary aggregates for a cell model with moving boundary, also yielding 2.1≤df≤2.2. The range for df found from both approaches agrees well with the range df≊2.1-2.2 determined from computer simulations on diffusion-limited aggregation including restructuring or thermal breakup after formation of bonds. Thus a simple model has been put forward which may capture the basic features of the aggregating model dispersion on a microstructural level and leads to physically acceptable parameter values.

Investigating rate-limiting barriers to nanoscale nonviral gene transfer with nanobiophotonics

NASA Astrophysics Data System (ADS)

Chen, Hunter H.

Nucleic acids are a novel class of therapeutics poised to address many unmet clinical needs. Safe and efficient delivery remains a significant challenge that has delayed the realization of the full therapeutic potential of nucleic acids. Nanoscale nonviral vectors offer an attractive alternative to viral vectors as natural and synthetic polymers or polypeptides may be rationally designed to meet the unique demands of individual applications. A mechanistic understanding of cellular barriers is necessary to develop guidelines for designing custom gene carriers which are expected to greatly impact this delivery challenge. The work herein focused on the relationships among nanocomplex stability, intracellular trafficking and unpacking kinetics, and DNA degradation. Ultrasensitive nanosensors based on QD-FRET were developed to characterize the biophysical properties of nanocomplexes and study these rate-limiting steps. Quantitative image analysis enabled the distributions of the subpopulation of condensed or released DNA to be determined within the major cellular compartments encountered during gene transfer. The steady state stability and unpacking kinetics within these compartments were found to impact transgene expression, elucidating multiple design strategies to achieve efficient gene transfer. To address enzymatic barriers, a novel two-step QD-FRET nanosensor was developed to analyze unpacking and DNA degradation simultaneously, which has not been accomplished previously. Bioresponsive strategies such as disulfide crosslinking and thermosensitivity were evaluated by QD-FRET and quantitative compartmental analysis as case studies to determine appropriate design specifications for thiolated polymers and thermoresponsive polypeptides. Relevant nanobiophotonic tools were developed as a platform to study major rate-limiting barriers to nanomedicine and demonstrated the feasibility of using mechanistic information gained from these tools to guide the rational design of gene carriers and achieve the desired properties that enable efficient gene transfer.

Mechanism of Nitrogenase H 2 Formation by Metal-Hydride Protonation Probed by Mediated Electrocatalysis and H/D Isotope Effects

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

Khadka, Nimesh; Milton, Ross D.; Shaw, Sudipta

Nitrogenase catalyzes the reduction of dinitrogen (N2) to ammonia (NH3) with obligatory reduction of protons (H+) to dihydrogen (H2) through a mechanism involving reductive elimination of two [Fe-H-Fe] bridging hydrides at its active site FeMo-cofactor. The overall rate-limiting step is associated with ATP-driven electron delivery from Fe protein, precluding isotope effect measurements on substrate reduction steps. Here, we use mediated bioelectrocatalysis to drive electron delivery to MoFe protein without Fe protein and ATP hydrolysis, thereby eliminating the normal rate-limiting step. The ratio of catalytic current in mixtures of H2O and D2O, the proton inventory, changes linearly with the D2O/H2O ratio,more » revealing that a single H/D is involved in the rate limiting step. Kinetic models, along with measurements that vary the electron/proton delivery rate and use different substrates, reveal that the rate-limiting step under these conditions is the H2 formation reaction. Altering the chemical environment around the active site FeMo-cofactor in the MoFe protein either by substituting nearby amino acids or transferring the isolated FeMo-cofactor into a different peptide matrix, changes the net isotope effect, but the proton inventory plot remains linear, consistent with an unchanging rate-limiting step. Density functional theory predicts a transition state for H2 formation where the proton from S-H+ moves to the hydride in Fe-H-, predicting the number and magnitude of the observed H/D isotope effect. This study not only reveals the mechanism of H2 formation, but also illustrates a strategy for mechanistic study that can be applied to other enzymes and to biomimetic complexes.« less

Solvent and viscosity effects on the rate-limiting product release step of glucoamylase during maltose hydrolysis.

PubMed

Sierks, M R; Sico, C; Zaw, M

1997-01-01

Release of product from the active site is the rate-limiting step in a number of enzymatic reactions, including maltose hydrolysis by glucoamylase (GA). With GA, an enzymatic conformational change has been associated with the product release step. Solvent characteristics such as viscosity can strongly influence protein conformational changes. Here we show that the rate-limiting step of GA has a rather complex dependence on solvent characteristics. Seven different cosolvents were added to the GA/maltose reaction solution. Five of the cosolvents, all having an ethylene glycol base, resulted in an increase in activity at low concentration of cosolvent and variable decreases in activity at higher concentrations. The increase in enzyme activity was dependent on polymer length of the cosolvent; the longer the polymer, the lower the concentration needed. The maximum increase in catalytic activity at 45 degrees C (40-45%) was obtained with the three longest polymers (degree of polymerization from 200 to 8000). A further increase in activity to 60-65% was obtained at 60 degrees C. The linear relationship between ln(kcat) and (viscosity)2 obtained with all the cosolvents provides further evidence that product release is the rate-limiting step in the GA catalytic mechanism. A substantial increase in the turnover rate of GA by addition of relatively small amounts of a cosolvent has potential applications for the food industry where high-fructose corn syrup (HFCS) is one of the primary products produced with GA. Since maltodextrin hydrolysis by GA is by far the slowest step in the production of HFCS, increasing the catalytic rate of GA can substantially reduce the process time.

Clomiphene Stair-Step Protocol for Women With Polycystic Ovary Syndrome.

PubMed

Jones, Tiffanny; Ho, Jacqueline R; Gualtieri, Marc; Bruno-Gaston, Janet; Chung, Karine; Paulson, Richard J; Bendikson, Kristin A

2018-01-01

To compare time to ovulation, ovulation rates, and side effect profile of traditional and the stair-step protocol for ovulation induction using clomiphene citrate in women with polycystic ovary syndrome (PCOS). We performed a retrospective study of women seeking care for infertility with a diagnosis of PCOS at a university-based infertility clinic from July 2012 to July 2014. We included patients who were resistant to the initial starting dose of 50 mg clomiphene. The primary outcome was time to ovulation. Secondary outcomes included ovulation rates, clinical pregnancy rates, and mild and moderate-to-severe side effects based on dose. For the traditional protocol, higher doses of clomiphene were used each subsequent month if no ovulation occurred. For the stair-step protocol, higher doses of clomiphene were given 7 days after the last dose if no dominant follicles were seen on ultrasonography. Our study had 80% power to detect a 20% difference in ovulation. One hundred nine patients were included in the analysis with 66 (60.6%) in the traditional and 43 (39.4%) in the stair-step protocol. Age and body mass index were similar between groups. The time to ovulation was decreased in the stair-step protocol group compared with the traditional protocol group (23.1±0.9 days vs 47.5±6.3 days). Ovulation rates were increased in the stair-step group compared with the traditional group at 150 mg (16 [37%] vs 8 [12%], P=.004) and at 200 mg (9 [21%] vs 3 [5%], P=.01). Pregnancy rates were similar between groups once ovulation was achieved (12 [18.1%] vs 7 [16.3%], P=.08). The stair-step protocol had an increased incidence of mild side effects (vasomotor flushes, headaches, gastrointestinal disturbance, mastalgia, changes in mood; 18 [41%] vs 8 [12%]), but there was no difference in the incidence of severe side effects (headaches, visual disturbances). For women with PCOS, the stair-step clomiphene protocol is associated with decreased time to ovulation and increased ovulation rates at higher doses when compared with the traditional protocol.

Validation of a single-stage fixed-rate step test for the prediction of maximal oxygen uptake in healthy adults.

PubMed

Hansen, Dominique; Jacobs, Nele; Thijs, Herbert; Dendale, Paul; Claes, Neree

2016-09-01

Healthcare professionals with limited access to ergospirometry remain in need of valid and simple submaximal exercise tests to predict maximal oxygen uptake (VO2max ). Despite previous validation studies concerning fixed-rate step tests, accurate equations for the estimation of VO2max remain to be formulated from a large sample of healthy adults between age 18-75 years (n > 100). The aim of this study was to develop a valid equation to estimate VO2max from a fixed-rate step test in a larger sample of healthy adults. A maximal ergospirometry test, with assessment of cardiopulmonary parameters and VO2max , and a 5-min fixed-rate single-stage step test were executed in 112 healthy adults (age 18-75 years). During the step test and subsequent recovery, heart rate was monitored continuously. By linear regression analysis, an equation to predict VO2max from the step test was formulated. This equation was assessed for level of agreement by displaying Bland-Altman plots and calculation of intraclass correlations with measured VO2max . Validity further was assessed by employing a Jackknife procedure. The linear regression analysis generated the following equation to predict VO2max (l min(-1) ) from the step test: 0·054(BMI)+0·612(gender)+3·359(body height in m)+0·019(fitness index)-0·012(HRmax)-0·011(age)-3·475. This equation explained 78% of the variance in measured VO2max (F = 66·15, P<0·001). The level of agreement and intraclass correlation was high (ICC = 0·94, P<0·001) between measured and predicted VO2max . From this study, a valid fixed-rate single-stage step test equation has been developed to estimate VO2max in healthy adults. This tool could be employed by healthcare professionals with limited access to ergospirometry. © 2015 Scandinavian Society of Clinical Physiology and Nuclear Medicine. Published by John Wiley & Sons Ltd.

Rapid gas chromatography with flame photometric detection of multiple organophosphorus pesticides in Salvia miltiorrhizae after ultrasonication assisted one-step extraction.

PubMed

Zhang, Shanshan; Liu, Xiaofei; Qin, Jia'an; Yang, Meihua; Zhao, Hongzheng; Wang, Yong; Guo, Weiying; Ma, Zhijie; Kong, Weijun

2017-11-15

A simple and rapid gas chromatography-flame photometric detection (GC-FPD) method was developed for the determination of 12 organophosphorus pesticides (OPPs) in Salvia miltiorrhizae by using ultrasonication assisted one-step extraction (USAE) without any clean-up steps. Some crucial parameters such as type of extraction solvent were optimized to improve the method performance for trace analysis. Any clean-up steps were negligent as no interferences were detected in the GC-FPD chromatograms for sensitive detection. Under the optimized conditions, limits of detection (LODs) and quantitation (LOQs) for all pesticides were in the range of 0.001-0.002mg/kg and 0.002-0.01mg/kg and 0.002-0.01mg/kg, respectively, which were all below the regulatory maximum residue limits suggested. RSDs for method precision (intra- and inter-day variations) were lower than 6.8% in approval with international regulations. Average recovery rates for all pesticides at three fortification levels (0.5, 1.0 and 5.0mg/kg) were in the range of 71.2-101.0% with relative standard deviations (RSDs) <13%. The developed method was evaluated for its feasibility in the simultaneous pre-concentration and determination of 12 OPPs in 32 batches of real S. miltiorrhizae samples. Only one pesticide (dimethoate) out of the 12 targets was simultaneously detected in four samples at concentrations of 0.016-0.02mg/kg. Dichlorvos and omethoate were found in the same sample from Sichuan province at 0.004 and 0.027mg/kg, respectively. Malathion and monocrotophos were determined in the other two samples at 0.014 and 0.028mg/kg, respectively. All the positive samples were confirmed by LC-MS/MS. The simple, reliable and rapid USAE-GC-FPD method with many advantages over traditional techniques would be preferred for trace analysis of multiple pesticides in more complex matrices. Copyright © 2017 Elsevier B.V. All rights reserved.

The Effect Of Pixel Size On The Detection Rate Of Early Pulmonary Sarcoidosis In Digital Chest Radiographic Systems

NASA Astrophysics Data System (ADS)

MacMahon, Heber; Vyborny, Carl; Powell, Gregory; Doi, Kunio; Metz, Charles E.

1984-08-01

In digital radiography the pixel size used determines the potential spatial resolution of the system. The need for spatial resolution varies depending on the subject matter imaged. In many areas, including the chest, the minimum spatial resolution requirements have not been determined. Sarcoidosis is a disease which frequently causes subtle interstitial infiltrates in the lungs. As the initial step in an investigation designed to determine the minimum pixel size required in digital chest radiographic systems, we have studied 1 mm pixel digitized images on patients with early pulmonary sarcoidosis. The results of this preliminary study suggest that neither mild interstitial pulmonary infiltrates nor other abnormalities such as pneumothoraces may be detected reliably with 1 mm pixel digital images.

An experimental study of combustion: The turbulent structure of a reacting shear layer formed at a rearward-facing step. Ph.D. Thesis. Final Report

NASA Technical Reports Server (NTRS)

Pitz, R. 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 were determined by LDV for both reacting and non-reacting flows. The reaching flow was visualized by high speed schlieren photography. Large scale structures dominate the reacting shear layer. The growth of the large scale structures is tied to the propagation of the flame. The linear growth rate of the reacting shear layer defined by the mean velocity profiles is unchanged by combustion but the virtual origin is shifted downstream. The reacting shear layer based on the mean velocity profiles is shifted toward the recirculation zone and the reattachments lengths are shortened by 30%.

Catalysis-Enhancement via Rotary Fluctuation of F1-ATPase

PubMed Central

Watanabe, Rikiya; Hayashi, Kumiko; Ueno, Hiroshi; Noji, Hiroyuki

2013-01-01

Protein conformational fluctuations modulate the catalytic powers of enzymes. The frequency of conformational fluctuations may modulate the catalytic rate at individual reaction steps. In this study, we modulated the rotary fluctuation frequency of F1-ATPase (F1) by attaching probes with different viscous drag coefficients at the rotary shaft of F1. Individual rotation pauses of F1 between rotary steps correspond to the waiting state of a certain elementary reaction step of ATP hydrolysis. This allows us to investigate the impact of the frequency modulation of the rotary fluctuation on the rate of the individual reaction steps by measuring the duration of rotation pauses. Although phosphate release was significantly decelerated, the ATP-binding and hydrolysis steps were less sensitive or insensitive to the viscous drag coefficient of the probe. Brownian dynamics simulation based on a model similar to the Sumi-Marcus theory reproduced the experimental results, providing a theoretical framework for the role of rotational fluctuation in F1 rate enhancement. PMID:24268150