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Sample records for rapid kinetic investigation

  1. Microfluidic mixers for the investigation of rapid protein folding kinetics using synchrotron radiation circular dichroism spectroscopy.

    PubMed

    Kane, Avinash S; Hoffmann, Armin; Baumgärtel, Peter; Seckler, Robert; Reichardt, Gerd; Horsley, David A; Schuler, Benjamin; Bakajin, Olgica

    2008-12-15

    We have developed a microfluidic mixer optimized for rapid measurements of protein folding kinetics using synchrotron radiation circular dichroism (SRCD) spectroscopy. The combination of fabrication in fused silica and synchrotron radiation allows measurements at wavelengths below 220 nm, the typical limit of commercial instrumentation. At these wavelengths, the discrimination between the different types of protein secondary structure increases sharply. The device was optimized for rapid mixing at moderate sample consumption by employing a serpentine channel design, resulting in a dead time of less than 200 micros. Here, we discuss the design and fabrication of the mixer and quantify the mixing efficiency using wide-field and confocal epi-fluorescence microscopy. We demonstrate the performance of the device in SRCD measurements of the folding kinetics of cytochrome c, a small, fast-folding protein. Our results show that the combination of SRCD with microfluidic mixing opens new possibilities for investigating rapid conformational changes in biological macromolecules that have previously been inaccessible.

  2. Kinetics of rapid covalent bond formation of aniline with humic acid: ESR investigations with nitroxide spin labels

    NASA Astrophysics Data System (ADS)

    Glinka, Kevin; Matthies, Michael; Theiling, Marius; Hideg, Kalman; Steinhoff, Heinz-Jürgen

    2016-04-01

    Sulfonamide antibiotics used in livestock farming are distributed to farmland by application of slurry as fertilizer. Previous work suggests rapid covalent binding of the aniline moiety to humic acids found in soil. In the current work, kinetics of this binding were measured in X-band EPR spectroscopy by incubating Leonardite humic acid (LHA) with a paramagnetic aniline spin label (anilino-NO (2,5,5-Trimethyl-2-(3-aminophenyl)pyrrolidin-1-oxyl)). Binding was detected by a pronounced broadening of the spectral lines after incubation of LHA with anilino-NO. The time evolution of the amplitude of this feature was used for determining the reaction kinetics. Single- and double-exponential models were fitted to the data obtained for modelling one or two first-order reactions. Reaction rates of 0.16 min-1 and 0.012 min-1, were found respectively. Addition of laccase peroxidase did not change the kinetics but significantly enhanced the reacting fraction of anilino-NO. This EPR-based method provides a technically simple and effective method for following rapid binding processes of a xenobiotic substance to humic acids.

  3. Rapid-Equilibrium Enzyme Kinetics

    ERIC Educational Resources Information Center

    Alberty, Robert A.

    2008-01-01

    Rapid-equilibrium rate equations for enzyme-catalyzed reactions are especially useful because if experimental data can be fit by these simpler rate equations, the Michaelis constants can be interpreted as equilibrium constants. However, for some reactions it is necessary to use the more complicated steady-state rate equations. Thermodynamics is…

  4. Kinetic investigation of wood pyrolysis

    SciTech Connect

    Thurner, F.; Mann, U.; Beck, S. R.

    1980-06-01

    The objective of this investigation was to determine the kinetics of the primary reactions of wood pyrolysis. A new experimental method was developed which enabled us to measure the rate of gas, tar, and char production while taking into account the temperature variations during the wood heating up. The experimental method developed did not require any sophisticated instruments. It facilitated the collection of gas, tar and residue (unreacted wood and char) as well as accurate measurement of the temperature inside the wood sample. Expressions relating the kinetic parameters to the measured variables were derived. The pyrolysis kinetics was investigated in the range of 300 to 400/sup 0/C at atmospheric pressure and under nitrogen atmosphere. Reaction temperature and mass fractions of gas, tar, and residue were measured as a function of time. Assuming first-order reactions, the kinetic parameters were determined using differential method. The measured activation energies of wood pyrolysis to gas, tar, and char were 88.6, 112.7, and 106.5 kJ/mole, respectively. These kinetic data were then used to predict the yield of the various pyrolysis products. It was found that the best prediction was obtained when an integral-mean temperature obtained from the temperature-time curve was used as reaction temperature. The pyrolysis products were analyzed to investigate the influence of the pyrolysis conditions on the composition. The gas consisted mainly of carbon dioxide, carbon monoxide, oxygen, and C/sub 3//sup +/-compounds. The gas composition depended on reaction time as well as reactor temperature. The tar analysis indicated that the tar consisted of about seven compounds. Its major compound was believed to be levoglucosan. Elemental analysis for the char showed that the carbon content increased with increasing temperature.

  5. An Introductory Level Kinetics Investigation.

    ERIC Educational Resources Information Center

    McGarvey, J. E. B.; Knipe, A. C.

    1980-01-01

    Provides a list of the reactions commonly used for introductory kinetics studies. These reactions illustrate the kinetics concepts of rate law, rate constant, and reaction order. Describes a kinetic study of the hydrolysis of 3-bromo-3-phenylpropanoic acid which offers many educational advantages. (CS)

  6. Portable centrifugal analyzer for the determination of rapid reaction kinetics

    SciTech Connect

    Bostick, W.D.; Bauer, M.L.; McCracken, R.; Mrochek, J.E.

    1980-02-01

    A portable centrifugal analyzer prototype is capable of rapidly initiating reactions and monitoring 17 optical channels as they rotate past a stationary photodetector. An advanced rotor drive permits transfer of discretely loaded sample and reagent into a cuvette within 60 ms. Various rotor designs have been employed to ensure effieicnt mixing concurrent with solution transfer, thus permitting absorbance or luminescence measurements to be made almost immediately after solution contract. Dye-dillution studies have been used to investigate transfer and mixing efficiencies. Rotor designs with parallel access for sample and reagent into the cuvette were found to promote efficient mixing during liquid transfer. The hypochlorite-luminol chemiluminescent reaction served to demonstrate the utility of the system for performing rapid kinetic analyses. Appropriate adjustment of reaction conditions allows first-order reaction half-lives as short as 0.04 s to be measured. 13 figures, 3 tables.

  7. Investigating broadband acoustic adsorption using rapid manufacturing

    NASA Astrophysics Data System (ADS)

    Godbold, O.

    The reduction of nuisance noise and the removal of unwanted sound modes within a room or component enclosure-area can be accomplished through the use of acoustic absorbers. Sound absorption can be achieved through conversion of the kinetic energy associated with pressure waves, into heat energy via viscous dissipation. This occurs within open porous materials, or by utilising resonant effects produced using simple cavity and orifice configurations. The manufacture of traditional porous and resonant absorbers is commonly realised using basic manufacturing techniques. These techniques restrict the geometry of a given resonant construction, and limit the configuration of porous absorbers. The aim of this work is to exploit new and emerging capabilities of Rapid Manufacturing (RM) to produce components with geometrical freedom, and apply it to the development of broadband acoustic absorption. New and novel absorber geometric configurations are identified and their absorption performance is determined. The capabilities and limitations of RM processes in reproducing these configurations are demonstrated. The geometric configuration of RM resonant absorbers is investigated. Cavity modifications aimed at damping the resonant effect by restricting the motion of cavity air, and adding increased viscous resistance are explored. Modifications relating to cavity shape, the addition of internal perforations and increased cavity surface area have all been shown to add acoustic resistance, thereby increasing the bandwidth of absorption. Decreasing the hydraulic radius of the cavity cross section and reducing internal feature dimensions provide improved resistance over conventional configurations..

  8. Determination of rapid chlorination rate constants by a stopped-flow spectrophotometric competition kinetics method.

    PubMed

    Song, Dean; Liu, Huijuan; Qiang, Zhimin; Qu, Jiuhui

    2014-05-15

    Free chlorine is extensively used for water and wastewater disinfection nowadays. However, it still remains a big challenge to determine the rate constants of rapid chlorination reactions although competition kinetics and stopped-flow spectrophotometric (SFS) methods have been employed individually to investigate fast reaction kinetics. In this work, we proposed an SFS competition kinetics method to determine the rapid chlorination rate constants by using a common colorimetric reagent, N,N-diethyl-p-phenylenediamine (DPD), as a reference probe. A kinetic equation was first derived to estimate the reaction rate constant of DPD towards chlorine under a given pH and temperature condition. Then, on that basis, an SFS competition kinetics method was proposed to determine directly the chlorination rate constants of several representative compounds including tetracycline, ammonia, and four α-amino acids. Although Cl2O is more reactive than HOCl, its contribution to the overall chlorination kinetics of the test compounds could be neglected in this study. Finally, the developed method was validated through comparing the experimentally measured chlorination rate constants of the selected compounds with those obtained or calculated from literature and analyzing with Taft's correlation as well. This study demonstrates that the SFS competition kinetics method can measure the chlorination rate constants of a test compound rapidly and accurately.

  9. Biochemical thermodynamics and rapid-equilibrium enzyme kinetics.

    PubMed

    Alberty, Robert A

    2010-12-30

    Biochemical thermodynamics is based on the chemical thermodynamics of aqueous solutions, but it is quite different because pH is used as an independent variable. A transformed Gibbs energy G' is used, and that leads to transformed enthalpies H' and transformed entropies S'. Equilibrium constants for enzyme-catalyzed reactions are referred to as apparent equilibrium constants K' to indicate that they are functions of pH in addition to temperature and ionic strength. Despite this, the most useful way to store basic thermodynamic data on enzyme-catalyzed reactions is to give standard Gibbs energies of formation, standard enthalpies of formation, electric charges, and numbers of hydrogen atoms in species of biochemical reactants like ATP. This makes it possible to calculate standard transformed Gibbs energies of formation, standard transformed enthalpies of formation of reactants (sums of species), and apparent equilibrium constants at desired temperatures, pHs, and ionic strengths. These calculations are complicated, and therefore, a mathematical application in a computer is needed. Rapid-equilibrium enzyme kinetics is based on biochemical thermodynamics because all reactions in the mechanism prior to the rate-determining reaction are at equilibrium. The expression for the equilibrium concentration of the enzyme-substrate complex that yields products can be derived by applying Solve in a computer to the expressions for the equilibrium constants in the mechanism and the conservation equation for enzymatic sites. In 1979, Duggleby pointed out that the minimum number of velocities of enzyme-catalyzed reactions required to estimate the values of the kinetic parameters is equal to the number of kinetic parameters. Solve can be used to do this with steady-state rate equations as well as rapid-equilibrium rate equations, provided that the rate equation is a polynomial. Rapid-equilibrium rate equations can be derived for complicated mechanisms that involve several reactants

  10. Investigation of the kinetic model equations.

    PubMed

    Liu, Sha; Zhong, Chengwen

    2014-03-01

    Currently the Boltzmann equation and its model equations are widely used in numerical predictions for dilute gas flows. The nonlinear integro-differential Boltzmann equation is the fundamental equation in the kinetic theory of dilute monatomic gases. By replacing the nonlinear fivefold collision integral term by a nonlinear relaxation term, its model equations such as the famous Bhatnagar-Gross-Krook (BGK) equation are mathematically simple. Since the computational cost of solving model equations is much less than that of solving the full Boltzmann equation, the model equations are widely used in predicting rarefied flows, multiphase flows, chemical flows, and turbulent flows although their predictions are only qualitatively right for highly nonequilibrium flows in transitional regime. In this paper the differences between the Boltzmann equation and its model equations are investigated aiming at giving guidelines for the further development of kinetic models. By comparing the Boltzmann equation and its model equations using test cases with different nonequilibrium types, two factors (the information held by nonequilibrium moments and the different relaxation rates of high- and low-speed molecules) are found useful for adjusting the behaviors of modeled collision terms in kinetic regime. The usefulness of these two factors are confirmed by a generalized model collision term derived from a mathematical relation between the Boltzmann equation and BGK equation that is also derived in this paper. After the analysis of the difference between the Boltzmann equation and the BGK equation, an attempt at approximating the collision term is proposed.

  11. An experimental investigation of rapid boiling of

    NASA Astrophysics Data System (ADS)

    Tosse, S.; Vaagsaether, K.; Bjerketvedt, D.

    2015-05-01

    Storage of pressurized liquified gases is a growing safety concern in many industries. Knowledge of the thermodynamics and kinetics involved in the rapid depressurization and evaporation of such substances is key to the design and implementation of effective safety measures in storage and transportation situations. In the present study, experiments on the rapid depressurization of liquid are conducted in a vertical transparent shock tube which enables the observation of evaporation waves and other structures. The depressurization was initiated by puncturing a membrane in one end of the tube. The thermodynamic mechanisms that govern the evaporation process are not unique to , and the same principles can be applied to any liquified gas. The experiments were photographed by a high-speed camera. Evaporation waves propagating into the liquid were observed, traveling at a near constant velocity on the order of 20-30 m/s. A contact surface between the vapor and the liquid-vapor mixture was also observed, accelerating out of the tube. Pressure readings in the tube suggest that the evaporation wave could be similar to a spinodal decomposition wave, but further experiments are needed to confirm this. When the membrane was in direct contact with the liquified , some indications of homogeneous nucleation were observed.

  12. Probing fast ribozyme reactions under biological conditions with rapid quench-flow kinetics.

    PubMed

    Bingaman, Jamie L; Messina, Kyle J; Bevilacqua, Philip C

    2017-03-14

    Reaction kinetics on the millisecond timescale pervade the protein and RNA fields. To study such reactions, investigators often perturb the system with abiological solution conditions or substrates in order to slow the rate to timescales accessible by hand mixing; however, such perturbations can change the rate-limiting step and obscure key folding and chemical steps that are found under biological conditions. Mechanical methods for collecting data on the millisecond timescale, which allow these perturbations to be avoided, have been developed over the last few decades. These methods are relatively simple and can be conducted on affordable and commercially available instruments. Here, we focus on using the rapid quench-flow technique to study the fast reaction kinetics of RNA enzymes, or ribozymes, which often react on the millisecond timescale under biological conditions. Rapid quench of ribozymes is completely parallel to the familiar hand-mixing approach, including the use of radiolabeled RNAs and fractionation of reactions on polyacrylamide gels. We provide tips on addressing and preventing common problems that can arise with the rapid-quench technique. Guidance is also offered on ensuring the ribozyme is properly folded and fast-reacting. We hope that this article will facilitate the broader use of rapid-quench instrumentation to study fast-reacting ribozymes under biological reaction conditions.

  13. The nonextensive gas: a kinetic approach [rapid communication

    NASA Astrophysics Data System (ADS)

    Lima, J. A. S.; Silva, R.

    2005-05-01

    We discuss a kinetic nonextensive generalization of the Maxwellian ideal gas. The analysis rests on two basic assumptions: (i) instead of the standard Gaussian form, the q-gas is described by a power-law velocity distribution as suggested in the nonextensive Tsallis' framework (ii) the q-nonextensive generalization of the Boltzmann entropy formula governs the behavior of the q-gas. In this context, we show that the pressure and the internal energy are kinetically modified, but the general equation of state, PV=2U/3, remains valid. The adiabatic index is now a function of the nonextensive parameter, γ=Cp/CV=5/3q. However, the standard expression relating the specific heats (at constant pressure and volume) with the coefficient of expansion and the isothermal compressibility, CP-CV=TVα2/κT, is not modified.

  14. Wound infection kinetics probed by MALDI-MS: rapid profiling of Staphylococcus aureus in mice.

    PubMed

    Narayana, Jayaram Lakshmaiah; Gopal, Judy; Wu, Hui-Fen

    2012-07-21

    Using direct matrix assisted laser desorption/ionization mass spectrometry (MALDI-MS), we were able to investigate the role of the clinically important bacteria, Staphylococcus aureus, in wound infections using mice. The infection kinetics of S. aureus at the wound site and the host immune response has been investigated using MALDI-MS. In this study, for the first time, we report the growth pattern of S. aureus infection at a wound site. Using mice wound infection models; the following study fingerprints the bacterial-host (mice) response at the wound site as a function of increasing wound infection in order to establish the infection pattern of Staphylococcus aureus in wounds. The current approach is extremely simple, rapid, highly selective, sensitive and established MALDI-MS as a versatile tool for detecting bacteria in clinical samples, such as those collected from wound sites.

  15. Investigation of Kinetics of MOCVD Systems

    DTIC Science & Technology

    1991-12-01

    growth rate was also observed by other investigators [81,95,96] when a threshold amount of HCI was exceeded. Jurgensen et al. [95] demonstrated that...Electrochem. Soc., 126, 1400 (1979). 94. Weyburne, D.W. and Quinlan, K.P., Report RADC-TR-85-238 (1985). 95. Jurgensen , H., Schmitz, D., Heyen, M. and

  16. Microbial pesticide removal in rapid sand filters for drinking water treatment--potential and kinetics.

    PubMed

    Hedegaard, Mathilde J; Albrechtsen, Hans-Jørgen

    2014-01-01

    Filter sand samples, taken from aerobic rapid sand filters used for treating groundwater at three Danish waterworks, were investigated for their pesticide removal potential and to assess the kinetics of the removal process. Microcosms were set up with filter sand, treated water, and the pesticides or metabolites mecoprop (MCPP), bentazone, glyphosate and p-nitrophenol were applied in initial concentrations of 0.03-2.4 μg/L. In all the investigated waterworks the concentration of pesticides in the water decreased - MCPP decreased to 42-85%, bentazone to 15-35%, glyphosate to 7-14% and p-nitrophenol 1-3% - from the initial concentration over a period of 6-13 days. Mineralisation of three out of four investigated pesticides was observed at Sjælsø waterworks Plant II - up to 43% of the initial glyphosate was mineralised within six days. At Sjælsø waterworks Plant II the removal kinetics of bentazone revealed that less than 30 min was needed to remove 50% of the bentazone at all the tested initial concentrations (0.1-2.4 μg/L). Increased oxygen availability led to greater and faster removal of bentazone in the microcosms. After 1 h, bentazone removal (an initial bentazone concentration of 0.1 μg/L) increased from 0.21%/g filter sand to 0.75%/g filter sand, when oxygen availability was increased from 0.28 mg O2/g filter sand to 1.09 mg O2/g filter sand. Bentazone was initially cleaved in the removal process. A metabolite, which contained the carbonyl group, was removed rapidly from the water phase and slowly mineralised after 24 h, while a metabolite which contained the benzene-ring was still present in the water phase. However, the microbial removal of this metabolite was initiated over seven days.

  17. Austenite Formation Kinetics During Rapid Heating in a Microalloyed Steel

    SciTech Connect

    BURNETT,M.E.; DYKHUIZEN,RONALD C.; KELLEY,J. BRUCE; PUSKAR,JOSEPH D.; ROBINO,CHARLES V.

    1999-09-07

    The model parameters for the normalized 1054V1 material were compared to parameters previously generated for 1026 steel, and the transformation behavior was relatively consistent. Validation of the model predictions by heating into the austenite plus undissolved ferrite phase field and rapidly quenching resulted in reasonable predictions when compared to the measured volume fractions from optical metallography. The hot rolled 1054V1 material, which had a much coarser grain size and a non-equilibrium volume fraction of pearlite, had significantly different model parameters and the on heating transformation behavior of this material was less predictable with the established model. The differences in behavior is consistent with conventional wisdom that normalized micro-structure produce a more consistent response to processing, and it reinforces the need for additional work in this area.

  18. Kinetic Controls on Formation of Textures in Rapidly Cooled Rocks

    NASA Technical Reports Server (NTRS)

    Lofgren, Gary E.

    2006-01-01

    The crystallization of silicate melts is a complex process involving melts usually produced by partial melting and cooling environments that are rapid in volcanic lavas or so slow as to be auto-metamorphic in plutonic regimes. The volcanic lavas are amenable to laboratory study as are chondrules that comprise the bulk of chondritic meteorites. Dynamic crystallization studies of basalt and chondrule melts have shown that nucleation has a more profound effect on the final texture than the cooling or crystal growth rates. The sequence of crystal shapes grown at increasing degrees of supercooling (DELTA T) or cooling rate demonstrates the effect of increasing growth rate. Equant or euhedral crystals become skeletal, then dendritic and ultimately spherulitic indicating the nucleation temperature and the DELTA T when growth began. Because crystals cannot grow until they nucleate, cooling rate does not always correlate with crystal growth rate and thus crystal shape. Silicate melts cooled at the same rate can have drastically different textures depending on the temperature of nucleation. A dynamic crystallization study of basaltic rocks shows that basaltic lavas must erupt with sufficient crystals present in the melt to act as nuclei and foster growth. With nuclei present, growth will begin when the temperature drops below the liquidus temperature and typical basaltic textures such as intersertal, intergranular or subophitic will form. If nuclei are not present, crystallization will not begin immediately and the DELTA T will increase until embryos in the melts become nuclei. The DELTA T present when grow begins dictates the growth rate and the crystal shapes and thus the rock texture. If nucleation is delayed, growth will take place at high DELTA T and the crystals will favor skeletal or dendritic shapes. Chondrules are usually considered crystallized melt droplets and clearly some are, but most are not. Most chondrules have porphyritic textures that cannot develop from

  19. Purification and characterization of Fab fragments with rapid reaction kinetics against myoglobin.

    PubMed

    Song, Hyung-Nam; Kim, Dong-Hyung; Park, Sung-Goo; Lee, Myung Kyu; Paek, Se-Hwan; Woo, Eui-Jeon

    2015-01-01

    Myoglobin is an early biomarker for acute myocardial infarction. Recently, we isolated the antibody IgG-Myo2-7ds, which exhibits unique rapid reaction kinetics toward human myoglobin antigen. Antibodies with rapid dissociation kinetics are thought to be premature IgG forms that are produced during the early stage of in vivo immunization. In the present study, we identified the epitope region of the IgG-Myo2-7ds antibody to be the C-terminal region of myoglobin, which corresponds to 144-154 aa. The Fab fragment was directly purified by papain cleavage and protein G affinity chromatography and demonstrated kinetics of an association constant of 4.02 × 10(4) M(-1) s(-1) and a dissociation constant of 2.28 × 10(-2) s(-1), which retained the unique reaction kinetics of intact IgG-Myo2-7ds antibodies. Because a rapid dissociation antibody can be utilized for antibody recycling, the results from this study would provide a platform for the development of antibody engineering in potential diagnostic areas such as a continuous monitoring system for heart disease.

  20. Construction of an antimyoglobin single-chain variable fragment with rapid reaction kinetics.

    PubMed

    Jang, Jun-Hyuck; Kim, Dong-Hyung; Paek, Se-Hwan; Woo, Eui-Jeon; Kim, Young-Wan

    2016-01-01

    Antibodies with rapid reaction kinetics (high association and dissociation rates), named reversible antibodies, are used to perform continuous monitoring of sensitive disease biomarkers. In cases of acute myocardial infarction (AMI), continuous monitoring and early diagnosis are important. Human myoglobin (Myo) is a useful biomarker for AMI during the early stage after the onset of symptoms. In this study, a single-chain variable fragment (scFv) specific to Myo was derived from an IgG antibody that has rapid reaction kinetics. Enzyme-linked immunosorbent assay revealed that recombinant scFv exhibited 3.8-fold reduced affinity compared with the parent IgG antibody based on the antibody concentration necessary for 50% of the maximum signal. The scFv retained the rapid reaction kinetic mode with average kon and koff of 2.63 × 10(5) M(-1) Sec(-1) and 3.25 × 10(-3) Sec(-1) , respectively, which were reduced to 10- and 2.3-fold compared with those of the parent antibody. The equilibrium constant for the association of the scFv (KA = 8.09 × 10(7) M(-1) ) was 4.6-fold lower than that of its parent IgG antibody. This scFv may be a starting point for further mutagenesis/kinetic and structural analyses providing valuable insight into the mechanism of reversible antibodies.

  1. Kinetics of the B1-B2 phase transition in KCl under rapid compression

    SciTech Connect

    Lin, Chuanlong; Smith, Jesse S.; Sinogeikin, Stanislav V.; Park, Changyong; Kono, Yoshio; Kenney-Benson, Curtis; Rod, Eric; Shen, Guoyin

    2016-01-28

    Kinetics of the B1-B2 phase transition in KCl has been investigated under various compression rates (0.03–13.5 GPa/s) in a dynamic diamond anvil cell using time-resolved x-ray diffraction and fast imaging. Our experimental data show that the volume fraction across the transition generally gives sigmoidal curves as a function of pressure during rapid compression. Based upon classical nucleation and growth theories (Johnson-Mehl-Avrami-Kolmogorov theories), we propose a model that is applicable for studying kinetics for the compression rates studied. The fit of the experimental volume fraction as a function of pressure provides information on effective activation energy and average activation volume at a given compression rate. The resulting parameters are successfully used for interpreting several experimental observables that are compression-rate dependent, such as the transition time, grain size, and over-pressurization. The effective activation energy (Q{sub eff}) is found to decrease linearly with the logarithm of compression rate. When Q{sub eff} is applied to the Arrhenius equation, this relationship can be used to interpret the experimentally observed linear relationship between the logarithm of the transition time and logarithm of the compression rates. The decrease of Q{sub eff} with increasing compression rate results in the decrease of the nucleation rate, which is qualitatively in agreement with the observed change of the grain size with compression rate. The observed over-pressurization is also well explained by the model when an exponential relationship between the average activation volume and the compression rate is assumed.

  2. Refolded scFv Antibody Fragment against Myoglobin Shows Rapid Reaction Kinetics

    PubMed Central

    Song, Hyung-Nam; Jang, Jun-Hyuck; Kim, Young-Wan; Kim, Dong-Hyung; Park, Sung-Goo; Lee, Myung Kyu; Paek, Se-Hwan; Woo, Eui-Jeon

    2014-01-01

    Myoglobin is one of the early biomarkers for acute myocardial infarction. Recently, we have screened an antibody with unique rapid reaction kinetics toward human myoglobin antigen. Antibodies with rapid reaction kinetics are thought to be an early IgG form produced during early stage of in vivo immunization. We produced a recombinant scFv fragment for the premature antibody from Escherichia coli using refolding technology. The scFv gene was constructed by connection of the VH–VL sequence with a (Gly4Ser)3 linker. The scFv fragment without the pelB leader sequence was expressed at a high level, but the solubility was extremely low. A high concentration of 8 M urea was used for denaturation. The dilution refolding process in the presence of arginine and the redox reagents GSH and GSSH successfully produced a soluble scFv protein. The resultant refolded scFv protein showed association and dissociation values of 9.32 × 10−4 M−1·s−1 and 6.29 × 10−3 s−1, respectively, with an affinity value exceeding 107 M−1 (kon/koff), maintaining the original rapid reaction kinetics of the premature antibody. The refolded scFv could provide a platform for protein engineering for the clinical application for diagnosis of heart disease and the development of a continuous biosensor. PMID:25530617

  3. Arsenate adsorption on ruthenium oxides: A spectroscopic and kinetic investigation

    SciTech Connect

    Luxton, Todd P.; Eick, Matthew J.; Scheckel, Kirk G.

    2008-12-08

    Arsenate adsorption on amorphous (RuO{sub 2} {center_dot} 1.1H{sub 2}O) and crystalline (RuO{sub 2}) ruthenium oxides was evaluated using spectroscopic and kinetic methods to elucidate the adsorption mechanism. Extended X-ray absorption fine structure spectroscopy (EXAFS) was used to determine the local coordination environment of adsorbed arsenate. Additionally, pressure-jump (p-jump) relaxation spectroscopy was used to investigate the kinetics of arsenate adsorption/desorption on ruthenium oxides. Chemical relaxations resulting from the induced pressure change were monitored via electrical conductivity detection. EXAFS data were collected for two initial arsenate solution concentrations, 3 and 33 mM at pH 5. The collected spectra indicated a similar coordination environment for arsenate adsorbed to RuO{sub 2} {center_dot} 1.1H{sub 2}O for both arsenate concentrations. In contrast the EXAFS spectra of RuO{sub 2} indicated differences in the local coordination environments for the crystalline material with increasing arsenate concentration. Data analysis indicated that both mono- and bidentate surfaces complexes were present on both RuO{sub 2} {center_dot} 1.1H{sub 2}O and RuO{sub 2}. Relaxation spectra from the pressure-jump experiments of both ruthenium oxides resulted in a double relaxation event. Based on the relaxation spectra, a two step reaction mechanism for arsenate adsorption is proposed resulting in the formation of a bidentate surface complex. Analysis of the kinetic and spectroscopic data suggested that while there were two relaxation events, arsenate adsorbed to ruthenium oxide surfaces through both mono- and bidentate surface complexes.

  4. Experimental investigation of kinetics and rheology during diagenesis

    SciTech Connect

    Liou, J.G.; Hacker, B.R.

    1998-09-01

    Two processes of enormous economic consequence occur within the upper to middle crust: the formation, migration, entrapment, and degradation of hydrocarbons, and hazardous seismicity. Substantial scientific evidence suggests that both these processes are influenced by devolatilization reactions during diagenesis. However, surprisingly few laboratory studies have been conducted on materials actively undergoing low-grade metamorphism or diagenesis. Because of this, there exists no suitable basis for understanding the rates at which devolatilization occurs, and what effects this process has on deformation at shallow to moderate depths in the crust. The authors are conducting a coordinated deformation and kinetic study of an important devolatilization reaction: the breakdown of laumontite. Laumontite is a common zeolite whose equilibrium phase relations and room-temperature frictional behavior are well understood. Besides serving as a model system for more complicated rocks, laumontite is an important mineral in its own right, particularly for hydrocarbon fields in sandstones and for fault zones in the crust. Hydrostatic experiments are being conducted to investigate the kinetics and mechanism of laumontite dehydration, and triaxial deformation experiments will enable characterization of the effect of differential stress on the reaction and the effect of synkinematic dehydration on the mechanical behavior of rock. The authors anticipate results of significant import for hydrocarbon exploration and recovery and for understanding the strength and seismic potential of crustal fault zones.

  5. Investigation of kinetic friction using an iPhone

    NASA Astrophysics Data System (ADS)

    Baldock, Clive; Johnson, Roger

    2016-11-01

    The iPhone is particularly suitable for mechanics experiments using the in-built acceleration sensor or accelerometer in-conjunction with the on-board data collection facility and a downloadable so-called ‘app’. In this work the iPhone has been used to investigate the acceleration due to gravity and determine the coefficient of kinetic friction, μ k of the iPhone as an object sliding down an inclined plane. This method is more accurate than that usually employed in the laboratory where the ‘fits and starts’ of the block sliding down the inclined plane potentially invalidate the required assumption that the velocity is constant. In its simplest form the measurement of acceleration is required to be undertaken for only 2 angles.

  6. Experimental investigation on oxidation kinetics of germanium by ozone

    NASA Astrophysics Data System (ADS)

    Wang, Xiaolei; Zhao, Zhiqian; Xiang, Jinjuan; Wang, Wenwu; Zhang, Jing; Zhao, Chao; Ye, Tianchun

    2016-12-01

    Oxidation kinetics of germanium surface by ozone at low temperature (≤400 °C) is experimentally investigated. The growth process contains two regions: initial linear growth region and following parabolic growth region. The GeOx thickness vs. oxidation time plot obeys the well-known Deal-Grove or linear parabolic model. The linear growth region contains reaction of oxygen atoms with surface bond and back bonds of outmost Ge layer. And the activation energy is experimentally estimated to be 0.06 eV. Such small activation energy indicates that the linear growth region is nearly barrier-less. The parabolic growth region starts when the oxygen atoms diffuse into back bonds of second outmost Ge layers. And the activation energy for this process is found to be 0.54 eV. Furthermore, in the ozone oxidation it is not O3 molecules but O radicals that go through the GeOx film.

  7. Kinetic study of rapid transfer of tetraethylammonium at the 1,2-dichloroethane/water interface by nanopipet voltammetry of common ions.

    PubMed

    Wang, Yixian; Velmurugan, Jeyavel; Mirkin, Michael V; Rodgers, Patrick J; Kim, Jiyeon; Amemiya, Shigeru

    2010-01-01

    Steady-state voltammetry at the pipet-supported liquid/liquid interface has previously been used to measure kinetics of simple and facilitated ion transfer (IT) processes. Recently, we showed that the conventional experimental protocol and data analysis produce large uncertainties in kinetic parameters of rapid IT processes extracted from pipet voltammograms. Here, we used a new mode of nanopipet voltammetry, in which a transferable ion is initially present as a common ion in both liquid phases, and improved methodology for silanization of the outer pipet wall to investigate the kinetics of the rapid transfer of tetraethylammonium (TEA(+)) at the 1,2-dichloroethane/water interface. This reaction was often employed as a model system to check the IT theory. The determined standard rate constant and transfer coefficient of the TEA(+) transfer are compared with previously reported values to demonstrate limitations of conventional nanopipet voltammetry with a transferrable ion present only in one liquid phase.

  8. Investigation kinetics mechanisms of adsorption malachite green onto activated carbon.

    PubMed

    Onal, Y; Akmil-Başar, C; Sarici-Ozdemir, C

    2007-07-19

    Lignite was used to prepare activated carbon (T3K618) by chemical activation with KOH. Pore properties of the activated carbon such as BET surface area, pore volume, pore size distribution, and pore diameter were characterized by t-plot based on N2 adsorption isotherm. BET surface area of activated carbon is determined as 1000 m2/g. Adsorption capacity of malachite green (MG) onto T3K618 activated carbon was investigated in a batch system by considering the effects of various parameters like initial concentration (100, 150 and 200 mg/L) and temperature (25, 40 and 50 degrees C). The adsorption process was relatively fast and equilibrium was reached after about 20 min for 100, 150 mg/L at all adsorption temperature. Equilibrium time for 200 mg/L was determined as 20 min and 40 min at 298, 313 and 323 K, respectively. Simple mass and kinetic models were applied to the experimental data to examine the mechanisms of adsorption and potential rate controlling steps such as external mass transfer, intraparticle diffusion. Pseudo second-order model was found to explain the kinetics of MG adsorption most effectively. It was found that both mass transfer and pore diffusion are important in determining the adsorption rates. The intraparticle diffusion rate constant, external mass transfer coefficient, film and pore diffusion coefficient at various temperatures were evaluated. The activation energy (Ea) was determined as 48.56, 63.16, 67.93 kJ/mol for 100, 150, 200 mg/L, respectively. The Langmiur and Freundlich isotherm were used to describe the adsorption equilibrium studies at different temperatures. Langmiur isotherm shows better fit than Freundlich isotherm in the temperature range studied. The thermodynamic parameters, such as DeltaG degrees, DeltaS and DeltaH degrees were calculated. The thermodynamics of dyes-T3K618 system indicates endothermic process.

  9. Sensitive and rapid laser diagnostic for shock tube kinetics studies using cavity-enhanced absorption spectroscopy.

    PubMed

    Sun, Kai; Wang, Shengkai; Sur, Ritobrata; Chao, Xing; Jeffries, Jay B; Hanson, Ronald K

    2014-04-21

    We report the first application of cavity-enhanced absorption spectroscopy (CEAS) using a coherent light source for sensitive and rapid gaseous species time-history measurements in a shock tube. Off-axis alignment and fast scanning of the laser wavelength were used to minimize coupling noise in a low-finesse cavity. An absorption gain factor of 83 with a measurement time resolution of 20 µs was demonstrated for C2H2 detection using a near-infrared transition near 1537 nm, corresponding to a noise-equivalent detection limit of 20 ppm at 296 K and 76 ppm at 906 K at 50 kHz. This substantial gain in signal, relative to conventional single-pass absorption, will enable ultra-sensitive species detection in shock tube kinetics studies, particularly useful for measurements of minor species and for studies of dilute reactive systems.

  10. Rapid kinetics of 2-adrenergic agonist binding and inhibition of adenylate cyclase

    SciTech Connect

    Thomsen, W.; Neubig, R.R.

    1987-05-01

    Activation of 2-adrenergic receptors in human platelets results in inhibition of adenylate cyclase (AC). To elucidate the relation between agonist binding and response, the authors have used a novel rapid-mix quench method to compare the kinetics of binding and response. At functionally effective concentrations, the time course of binding of the full 2-agonist, (TH)UK14,304 (UK), to purified platelet membranes was faster than could be measured manually. Using the rapid-mix quench method, agonist binding was quantitated for times for 0.3 to 60 seconds. UK binding exhibited biexponential kinetics. The rate constant of the fast binding component increases linearly with agonist concentration from 1 to 100 nM with a second order rate constant and 7 x 10WM s (at 25C). The slow rate constant was nearly independent of agonist concentration. The half times of the fast and slow components of binding for 100 nM UK are 1.5 seconds and approximately 2 minutes respectively. The rate and magnitude of the fast binding was unaffected by 10 M GTP whereas the magnitude of the slow phase was markedly reduced. Inhibition of forskolin stimulated AC by 100 M epinephrine occurs with a lag of 5-10 seconds in the presence of 10 M GTP. At lower GTP concentrations, this lag is prolonged. The observation that the fast component of agonist binding precedes inhibition even at agonist concentrations 20-fold lower than the EC40 for responses indicates that the rate limiting step in inhibition of AC is distal to the binding of agonist.

  11. [New relations for steady-state enzyme kinetics and their application to rapid equilibrium assumption].

    PubMed

    Vrzheshch, P V

    2013-01-01

    With the use of a graph theory new relations for steady-state enzyme kinetics are derived and strictly proved for the arbitrary mechanism of an enzyme-catalysed reaction containing a reversible segment. Using these relations, a general principle for rapid equilibrium assumption is formulated and proved: the reversible bound segment can be considered as an equilibrium segment only when the values of the base trees that are not proper to this segment can be neglected (within a prescribed accuracy) in relation to the values of the base trees that belong to this segment. In contrast with the foreign base trees the base trees that are proper to the segment have the following properties: the tree that is directed to the base within this segment does not contain the edges leaving this segment; and the tree that is directed to the base outside the segment contains only one edge leaving this segment. Equilibrium variations are assessed for steady-state intermediates concentrations of the equilibrium segment, numerical expressions are obtained for the accuracy of determination of the intermediates concentrations as well as for the accuracy of determination of the rate of enzyme-catalysed reaction in case of using rapid equilibrium assumption.

  12. Arsenate Adsorption On Ruthenium Oxides: A Spectroscopic And Kinetic Investigation

    EPA Science Inventory

    Arsenate adsorption on amorphous (RuO2•1.1H2O) and crystalline (RuO2) ruthenium oxides was evaluated using spectroscopic and kinetic methods to elucidate the adsorption mechanism. Extended X-ray absorption fine structure spectroscopy (EXAFS) was ...

  13. Unusual Kinetic and Structural Properties Control Rapid Assembly and Turnover of Actin in the Parasite Toxoplasma gondiiD⃞

    PubMed Central

    Sahoo, Nivedita; Beatty, Wandy; Heuser, John; Sept, David; Sibley, L. David

    2006-01-01

    Toxoplasma is a protozoan parasite in the phylum Apicomplexa, which contains a number of medically important parasites that rely on a highly unusual form of motility termed gliding to actively penetrate their host cells. Parasite actin filaments regulate gliding motility, yet paradoxically filamentous actin is rarely detected in these parasites. To investigate the kinetics of this unusual parasite actin, we expressed TgACT1 in baculovirus and purified it to homogeneity. Biochemical analysis showed that Toxoplasma actin (TgACT1) rapidly polymerized into filaments at a critical concentration that was 3-4-fold lower than conventional actins, yet it failed to copolymerize with mammalian actin. Electron microscopic analysis revealed that TgACT1 filaments were 10 times shorter and less stable than rabbit actin. Phylogenetic comparison of actins revealed a limited number of apicomplexan-specific residues that likely govern the unusual behavior of parasite actin. Molecular modeling identified several key alterations that affect interactions between monomers and that are predicted to destabilize filaments. Our findings suggest that conserved molecular differences in parasite actin favor rapid cycles of assembly and disassembly that govern the unusual form of gliding motility utilized by apicomplexans. PMID:16319175

  14. Rapid kinetics of serum IgA after vaccination with Prevnar(®)13 followed by Pneumovax(®)23.

    PubMed

    Crowther, Rebecca R; Collins, Christine M; Conley, Cheryl; Lopez, Osvaldo J

    2017-02-01

    Streptococcus pneumoniae is a causative agent of community-acquired pneumonias. The recommendations of the 2012 Advisory Committee on Immunization Practices include vaccination with Prevnar(®)13 (protein-polysaccharide conjugate vaccine; PCV), followed by Pneumovax(®)23 (polysaccharide-based vaccine; PSV) in adults 65+ or the immunocompromised. In this experiment, a group of 4 healthy volunteers were vaccinated with PCV followed by PSV 60 days later. ELISAs were optimized to study kinetics of IgA, IgM, total IgG and its four subclasses against 14 polysaccharides of the pneumococcal capsule. Although this is a small sample, results from volunteers consistently showed that rapid induction of monomeric IgA followed by rapid decline is typical for both vaccines. IgA was not detected after PSV vaccination in those serotypes present in PCV, suggesting the population of B cells secreting IgA is not renewed within 60 days of activation by PCV. In contrast to mice, human neutrophils expressed a functional receptor for the constant region of monomeric IgA. Thus, the role of IgA early in the human immune response should be further investigated.

  15. Rapid quantification and analysis of kinetic • OH radical footprinting data using SAFA

    PubMed Central

    Simmons, Katrina; Martin, Joshua S.; Shcherbakova, Inna; Laederach, Alain

    2010-01-01

    The use of highly reactive chemical species to probe the structure and dynamics of nucleic acids is greatly simplified by software that enables rapid quantification of the gel images that result from these experiments. SAFA (Semi-Automated Footprinting Analysis) allows a user to quickly and reproducibly quantify a chemical footprinting gel image through a series of steps that rectify, assign, and integrate the relative band intensities. The output of this procedure is raw band intensities that report on the relative reactivity of each nucleotide with the chemical probe. We describe here how to obtain these raw band intensities using SAFA and the subsequent normalization and analysis procedures required to process this data. In particular, we focus on analyzing time-resolved hydroxyl radical (•OH) data, which we use to monitor the kinetics of folding of a large RNA (the L-21 T. thermophila group I intron). Exposing the RNA to bursts of •OH radicals at specific time-points during the folding process monitors the time-progress of the reaction. Specifically, we identify protected (nucleotides that become inaccessible to the •OH radical probe when folded) and invariant (nucleotides with constant accessibility to the •OH probe) residues that we use for monitoring and normalization of the data. With this analysis, we obtain time-progress curves from which we determine kinetic rates of folding. We also report on a data visualization tool implemented in SAFA that allows users to map data onto a secondary structure diagram. PMID:20946764

  16. Detailed Chemical Kinetic Reaction Mechanisms for Autoignition of Isomers of Heptane Under Rapid Compression

    SciTech Connect

    Westbrook, C K; Pitz, W J; Boercker, J E; Curran, H J; Griffiths, J F; Mohamed, C; Ribaucour, M

    2001-12-17

    Detailed chemical kinetic reaction mechanisms are developed for combustion of all nine isomers of heptane (C{sub 7}H{sub 16}), and these mechanisms are tested by simulating autoignition of each isomer under rapid compression machine conditions. The reaction mechanisms focus on the manner in which the molecular structure of each isomer determines the rates and product distributions of possible classes of reactions. The reaction pathways emphasize the importance of alkylperoxy radical isomerizations and addition reactions of molecular oxygen to alkyl and hydroperoxyalkyl radicals. A new reaction group has been added to past models, in which hydroperoxyalkyl radicals that originated with abstraction of an H atom from a tertiary site in the parent heptane molecule are assigned new reaction sequences involving additional internal H atom abstractions not previously allowed. This process accelerates autoignition in fuels with tertiary C-H bonds in the parent fuel. In addition, the rates of hydroperoxyalkylperoxy radical isomerization reactions have all been reduced so that they are now equal to rates of analogous alkylperoxy radical isomerizations, significantly improving agreement between computed and experimental ignition delay times in the rapid compression machine. Computed ignition delay times agree well with experimental results in the few cases where experiments have been carried out for specific heptane isomers, and predictive model calculations are reported for the remaining isomers. The computed results fall into three general groups; the first consists of the most reactive isomers, including n-heptane, 2-methyl hexane and 3-methyl hexane. The second group consists of the least reactive isomers, including 2,2-dimethyl pentane, 3,3-dimethyl pentane, 2,3-dimethyl pentane, 2,4-dimethyl pentane and 2,2,3-trimethyl butane. The remaining isomer, 3-ethyl pentane, was observed computationally to have an intermediate level of reactivity. These observations are generally

  17. Rapid Kinetics of Dehalogenation Promoted by Iodotyrosine Deiodinase from Human Thyroid

    PubMed Central

    2015-01-01

    Reductive dehalogenation such as that catalyzed by iodotyrosine deiodinase (IYD) is highly unusual in aerobic organisms but necessary for iodide salvage from iodotyrosine generated during thyroxine biosynthesis. Equally unusual is the dependence of this process on flavin. Rapid kinetics have now been used to define the basic processes involved in IYD catalysis. Time-dependent quenching of flavin fluorescence was used to monitor halotyrosine association to IYD. The substrates chloro-, bromo-, and iodotyrosine bound with similar rate constants (kon) ranging from 1.3 × 106 to 1.9 × 106 M–1 s–1. Only the inert substrate analogue fluorotyrosine exhibited a significantly (5-fold) slower kon (0.3 × 106 M–1 s–1). All data fit a standard two-state model and indicated that no intermediate complex accumulated during closure of the active site lid induced by substrate. Subsequent halide elimination does not appear to limit reactions of bromo- and iodotyrosine since both fully oxidized the reduced enzyme with nearly equivalent second-order rate constants (7.3 × 103 and 8.6 × 103 M–1 s–1, respectively) despite the differing strength of their carbon–halogen bonds. In contrast to these substrates, chlorotyrosine reacted with the reduced enzyme approximately 20-fold more slowly and revealed a spectral intermediate that formed at approximately the same rate as the bromo- and iodotyrosine reactions. PMID:26151430

  18. Evolutionary optimization of peptide substrates for proteases that exhibit rapid hydrolysis kinetics.

    PubMed

    Boulware, Kevin T; Jabaiah, Abeer; Daugherty, Patrick S

    2010-06-15

    Protease cleavage site recognition motifs can be identified using protease substrate discovery methodologies, but typically exhibit non-optimal specificity and activity. To enable evolutionary optimization of substrate cleavage kinetics, a two-color cellular library of peptide substrates (CLiPS) methodology was developed. Two-color CLiPS was applied to identify peptide substrates for the tobacco etch virus (TEV) protease from a random pentapeptide library, which were then optimized by screening of a focused, extended substrate library. Quantitative library screening yielded seven amino acid substrates exhibiting rapid hydrolysis by TEV protease and high sequence similarity to the native seven-amino-acid substrate, with a strong consensus of EXLYPhiQG. Comparison of hydrolysis rates for a family of closely related substrates indicates that the native seven-residue TEV substrate co-evolved with TEV protease to facilitate highly efficient hydrolysis. Consensus motifs revealed by screening enabled database identification of a family of related, putative viral protease substrates. More generally, our results suggest that substrate evolution using CLiPS may be useful for optimizing substrate selectivity and activity to enable the design of more effective protease activity probes, molecular imaging agents, and prodrugs.

  19. Microsecond Microfluidic Mixing for Investigation of Protein Folding Kinetics

    SciTech Connect

    Hertzog, D E; Santiago, J G; Bakajin, O

    2005-02-10

    We have developed and characterized a mixer to study the reaction kinetics of protein folding on a microsecond timescale. The mixer uses hydrodynamic focusing of pressure-driven flow in a microfluidic channel to reduce diffusion times as first demonstrated by Knight et al.[1]. Features of the mixer include 1 {micro}s mixing times, sample consumptions of order 1 nl/s, loading sample volumes on the order of microliters, and the ability to manufacture in fused silica for compatibility with most spectroscopic methods.

  20. Folding Kinetics of Staphylococcal Nuclease Studied by Tryptophan Engineering and Rapid Mixing Methods

    PubMed Central

    Maki, Kosuke; Cheng, Hong; Dolgikh, Dimitry A.; Roder, Heinrich

    2007-01-01

    To monitor the development of tertiary structural contacts during folding, a unique tryptophan residue was introduced at seven partially buried locations (residues 15, 27, 61, 76, 91, 102 and 121) of a tryptophan-free variant of staphylococcal nuclease (P47G/P117G/H124L/W140H). Thermal unfolding measurements by circular dichroism indicate that the variants are destabilized, but maintain the ability to fold into a native-like structure. For the variants with Trp at positions 15, 27 and 61, the intrinsic fluorescence is significantly quenched in the native state due to close contact with polar side chains that act as intramolecular quenchers. All other variants exhibit enhanced fluorescence under native conditions consistent with burial of the tryptophans in an apolar environment. The kinetics of folding was observed by continuous- and stopped-flow fluorescence measurements over refolding times ranging from 100 μs to 10 s. The folding kinetics of all variants is quantitatively described by a mechanism involving a major pathway with a series of intermediate states and a minor parallel channel. The engineered tryptophans in the β-barrel and the N-terminal part of the α-helical domain become partially shielded from the solvent at an early stage (< 1 ms), indicating that this region of the protein undergoes a rapid specific collapse and remains uncoupled from the rest of the α-helical domain until the late stages of folding. For several variants, a major increase in fluorescence coincides with the rate-limiting step of folding on the 100 ms time scale, indicating that these tryptophans reach their buried native environment only during the late stages of folding. Other variants show more complex behavior with a transient increase in fluorescence during the 10 ms phase followed by a decrease during the rate-limiting phase. These observations are consistent with burial of these probes in a collapsed, but loosely packed intermediate, followed by the rate

  1. Antimicrobial Protegrin-1 Forms Amyloid-Like Fibrils with Rapid Kinetics Suggesting a Functional Link

    PubMed Central

    Jang, Hyunbum; Arce, Fernando Teran; Mustata, Mirela; Ramachandran, Srinivasan; Capone, Ricardo; Nussinov, Ruth; Lal, Ratnesh

    2011-01-01

    Protegrin-1 (PG-1) is an 18 residues long, cysteine-rich β-sheet antimicrobial peptide (AMP). PG-1 induces strong cytotoxic activities on cell membrane and acts as a potent antibiotic agent. Earlier we reported that its cytotoxicity is mediated by its channel-forming ability. In this study, we have examined the amyloidogenic fibril formation properties of PG-1 in comparison with a well-defined amyloid, the amyloid-β (Aβ1–42) peptide. We have used atomic force microscopy (AFM) and thioflavin-T staining to investigate the kinetics of PG-1 fibrils growth and molecular dynamics simulations to elucidate the underlying mechanism. AFM images of PG-1 on a highly hydrophilic surface (mica) show fibrils with morphological similarities to Aβ1–42 fibrils. Real-time AFM imaging of fibril growth suggests that PG-1 fibril growth follows a relatively fast kinetics compared to the Aβ1–42 fibrils. The AFM results are in close agreement with results from thioflavin-T staining data. Furthermore, the results indicate that PG-1 forms fibrils in solution. Significantly, in contrast, we do not detect fibrillar structures of PG-1 on an anionic lipid bilayer 2-dioleoyl-sn-glycero-3-phospho-L-serine/1-palmitoyl-2-oleoyl-sn-glycero-3-phosphoethanolamine; only small PG-1 oligomers can be observed. Molecular dynamics simulations are able to identify the presence of these small oligomers on the membrane bilayer. Thus, our current results show that cytotoxic AMP PG-1 is amyloidogenic and capable of forming fibrils. Overall, comparing β-rich AMPs and amyloids such as Aβ, in addition to cytotoxicity and amyloidogenicity, they share a common structural motif, and are channel forming. These combined properties support a functional relationship between amyloidogenic peptides and β-sheet-rich cytolytic AMPs, suggesting that amyloids channels may have an antimicrobial function. PMID:21463591

  2. A kinetics investigation of several reactions involving chlorine containing compounds

    NASA Technical Reports Server (NTRS)

    Davis, D. D.

    1978-01-01

    The technique of flash photolysis-resonance fluorescence was utilized to study nine reactions of stratospheric importance. The tropospheric degradation reactions of seven halogenated hydrocarbons were studied to assess their possible influx into the stratosphere. There are reactions of either Cl, OH, or O(3P) species with hydrogenated species, O3 or chlorinated compounds. Apart from the kinetic measurements, the quantum yield for the production of O(1D) from O3 in the crucial wavelength region of 293 to 316.5 nm was studied by utilizing a narrow wavelength laser as the photolysis source. The product formation was monitored by measuring the fluorescence of NO2 formed through O(1D) reaction with N2O followed by NO reaction with O3 to give NO2.

  3. Phase-field investigation on the non-equilibrium interface dynamics of rapid alloy solidification

    SciTech Connect

    Choi, Jeong

    2011-01-01

    The research program reported here is focused on critical issues that represent conspicuous gaps in current understanding of rapid solidification, limiting our ability to predict and control microstructural evolution (i.e. morphological dynamics and microsegregation) at high undercooling, where conditions depart significantly from local equilibrium. More specifically, through careful application of phase-field modeling, using appropriate thin-interface and anti-trapping corrections and addressing important details such as transient effects and a velocity-dependent (i.e. adaptive) numerics, the current analysis provides a reasonable simulation-based picture of non-equilibrium solute partitioning and the corresponding oscillatory dynamics associated with single-phase rapid solidification and show that this method is a suitable means for a self-consistent simulation of transient behavior and operating point selection under rapid growth conditions. Moving beyond the limitations of conventional theoretical/analytical treatments of non-equilibrium solute partitioning, these results serve to substantiate recent experimental findings and analytical treatments for single-phase rapid solidification. The departure from the equilibrium solid concentration at the solid-liquid interface was often observed during rapid solidification, and the energetic associated non-equilibrium solute partitioning has been treated in detail, providing possible ranges of interface concentrations for a given growth condition. Use of these treatments for analytical description of specific single-phase dendritic and cellular operating point selection, however, requires a model for solute partitioning under a given set of growth conditions. Therefore, analytical solute trapping models which describe the chemical partitioning as a function of steady state interface velocities have been developed and widely utilized in most of the theoretical investigations of rapid solidification. However, these

  4. Exact and user-friendly kinetic analysis of the two-step rapid equilibrium Michaelis-Menten mechanism.

    PubMed

    Garneau-Tsodikova, Sylvie; Shkel, Irina A; Tsodikov, Oleg V

    2009-04-15

    Most enzyme kinetic experiments are carried out under pseudo-first-order conditions, that is, when one of the reactant species (the enzyme or the substrate) is in a large excess of the other species. More accurate kinetic information about the system can be gained without the restrictions of the pseudo-first-order conditions. We present a practical and general method of analysis of the common two-step rapid equilibrium Michaelis-Menten mechanism. The formalism is exact in that it does not involve any other approximations such as the steady-state, limitations on the reactant concentrations or on reaction times. We apply this method to the global analysis of kinetic progress curves for bovine alkaline phosphatase assays carried out under both pseudo-first-order and pseudo-second-order conditions.

  5. Thermal Decomposition of 3-Bromopropene. A Theoretical Kinetic Investigation.

    PubMed

    Tucceri, María E; Badenes, María P; Bracco, Larisa L B; Cobos, Carlos J

    2016-04-21

    A detailed kinetic study of the gas-phase thermal decomposition of 3-bromopropene over wide temperature and pressure ranges was performed. Quantum chemical calculations employing the density functional theory methods B3LYP, BMK, and M06-2X and the CBS-QB3 and G4 ab initio composite models provide the relevant part of the potential energy surfaces and the molecular properties of the species involved in the CH2═CH-CH2Br → CH2═C═CH2 + HBr (1) and CH2═CH-CH2Br → CH2═CH-CH2 + Br (2) reaction channels. Transition-state theory and unimolecular reaction rate theory calculations show that the simple bond fission reaction ( 2 ) is the predominant decomposition channel and that all reported experimental studies are very close to the high-pressure limit of this process. Over the 500-1400 K range a rate constant for the primary dissociation of k2,∞ = 4.8 × 10(14) exp(-55.0 kcal mol(-1)/RT) s(-1) is predicted at the G4 level. The calculated k1,∞ values lie between 50 to 260 times smaller. A value of 10.6 ± 1.5 kcal mol(-1) for the standard enthalpy of formation of 3-bromopropene at 298 K was estimated from G4 thermochemical calculations.

  6. Investigation of blistering kinetics in hydrogen implanted aluminium nitride

    NASA Astrophysics Data System (ADS)

    Singh, R.; Scholz, R.; Christiansen, S. H.; Gösele, U.

    2008-04-01

    Epitaxial layers of aluminium nitride (AlN) grown on sapphire by hydride vapour phase epitaxy (HVPE) were implanted with 100 keV hydrogen, H+2, ions with doses in the range of 5 × 1016-2.5 × 1017 cm-2 and subsequently annealed in ambient air at temperatures between 450 and 750 °C in order to determine the kinetics of surface blister formation in AlN. The Arrhenius plot of the blistering time versus temperature shows two different activation energies for the formation of surface blisters: 0.44 eV in the higher temperature regime of 550-750 °C and 1.16 eV in the lower temperature regime of 450-550 °C. The implantation-induced damage was analyzed by cross-sectional transmission electron microscopy, which revealed a band of defects extending from 330 to 550 nm from the surface of AlN. The XTEM image of the implanted and annealed AlN displayed clearly the formation of microcracks that ultimately lead to the formation of surface blisters.

  7. Investigating Molecular Kinetics by Variationally Optimized Diffusion Maps.

    PubMed

    Boninsegna, Lorenzo; Gobbo, Gianpaolo; Noé, Frank; Clementi, Cecilia

    2015-12-08

    Identification of the collective coordinates that describe rare events in complex molecular transitions such as protein folding has been a key challenge in the theoretical molecular sciences. In the Diffusion Map approach, one assumes that the molecular configurations sampled have been generated by a diffusion process, and one uses the eigenfunctions of the corresponding diffusion operator as reaction coordinates. While diffusion coordinates (DCs) appear to provide a good approximation to the true dynamical reaction coordinates, they are not parametrized using dynamical information. Thus, their approximation quality could not, as yet, be validated, nor could the diffusion map eigenvalues be used to compute relaxation rate constants of the system. Here we combine the Diffusion Map approach with the recently proposed Variational Approach for Conformation Dynamics (VAC). Diffusion Map coordinates are used as a basis set, and their optimal linear combination is sought using the VAC, which employs time-correlation information on the molecular dynamics (MD) trajectories. We have applied this approach to ultra-long MD simulations of the Fip35 WW domain and found that the first DCs are indeed a good approximation to the true reaction coordinates of the system, but they could be further improved using the VAC. Using the Diffusion Map basis, excellent approximations to the relaxation rates of the system are obtained. Finally, we evaluate the quality of different metric spaces and find that pairwise minimal root-mean-square deviation performs poorly, while operating in the recently introduced kinetic maps based on the time-lagged independent component analysis gives the best performance.

  8. Kinetic and Mechanistic Investigations of Atom Abstraction Reactions

    NASA Astrophysics Data System (ADS)

    Stevens, Philip Stanford

    1990-01-01

    A discharge-flow system at 1-4 torr total pressure, employing resonance fluorescence detection of Br, Cl, O, H, N, and D, and laser magnetic resonance detection of OH and ClO, was used to measure the rate constants for a number of hydrogen and non-hydrogen atom abstraction reactions. The rate constants are examined within established reactivity trends in order to reveal the dominant forces governing the potential-energy surfaces. The activation energies for the F + rm H_2O/D_2O reactions are found to be smaller than that defined by the Evans-Polyani relationship between activation energy and exothermicity. The low activation energy and enhanced kinetic isotope effect for these reactions suggests that this deviation may be the result of quantum -mechanical tunneling. The rate constants for these and other heavy-light-heavy reactions are interpreted using transition-state theory and a one-dimensional tunneling model, in conjunction with ab initio calculations, to gain insight into the mechanism of these reactions. For the reactions of X + ClOCl to Products (X = Br, Cl, F, N), the rate constants correlate with the electron affinity of the radical, indicating that these mechanisms are dominated by electron transfer from ClOCl to X, similar to the reactivity of other non -hydrogen abstractions. The reactions of O and OH with ClOCl do not follow this trend, suggesting that electron transfer is not the only driving force in these reactions. These deviations are interpreted in terms of long-range attractive forces forming stable intermediates. The ClO + O_3 to ClOO + O_2 reaction has been proposed as an additional mechanism for ozone destruction within the antarctic vortex. Upper limits for the bimolecular rate constant for the ClO + O _3 reaction were measured directly between 233 and 413 K at 1-2 torr. The rate constants are several orders-of-magnitude smaller than estimated from the trend for non-hydrogen abstractions. From these results, it is concluded that this

  9. Quasigeostrophic investigations of non-hydrostatic, stably- stratified and rapidly rotating flows

    NASA Astrophysics Data System (ADS)

    Julien, Keith; Nieves, David; Grooms, Ian; Weiss, Jeffrey

    2016-11-01

    We present an investigation of rapidly rotating stratified turbulence where the stratification strength is varied from weak to strong. The investigation is set in the context of a reduced model derived from the Boussinesq equations that retains anisotropic inertia-gravity waves with order-one frequencies and highlights a regime of wave-eddy interactions. Numerical simulations are performed where energy is injected by a stochastic forcing of vertical velocity, which forces wave modes only. The simulations reveal two regimes characterized by the presence of well-formed, persistent and thin turbulent layers of locally weakened stratification at small Froude numbers, and by the absence of layers at large Froude numbers. Both regimes are characterized by a large-scale barotropic dipole enclosed by small-scale turbulence. When the Reynolds number is not too large, a direct cascade of barotropic kinetic energy is observed, leading to total energy equilibration. We examine net energy exchanges that occur through vortex stretching and vertical buoyancy flux. We find that the baroclinic motions inject energy directly to the largest scales of the barotropic mode, implying that the large-scale barotropic dipole is not the end result of an inverse cascade within the barotropic mode. NSF DMS 1317666, 1444503; NSF EAR 1067944, NSF OCE 1245944.

  10. Mechanistic investigation leads to a synthetic improvement in the hydrolytic kinetic resolution of terminal epoxides.

    PubMed

    Nielsen, Lars P C; Stevenson, Christian P; Blackmond, Donna G; Jacobsen, Eric N

    2004-02-11

    The mechanism of the hydrolytic kinetic resolution (HKR) of terminal epoxides was investigated by kinetic analysis using reaction calorimetry. The chiral (salen)Co-X complex (X = OAc, OTs, Cl) undergoes irreversible conversion to (salen)Co-OH during the course of the HKR and thus serves as both precatalyst and cocatalyst in a cooperative bimetallic catalytic mechanism. This insight led to the identification of more active catalysts for the HKR of synthetically useful terminal epoxides.

  11. The Rapid Acquisition Imaging Spectrograph Experiment (RAISE) Sounding Rocket Investigation

    NASA Astrophysics Data System (ADS)

    Laurent, Glenn T.; Hassler, Donald M.; Deforest, Craig; Slater, David D.; Thomas, Roger J.; Ayres, Thomas; Davis, Michael; de Pontieu, Bart; Diller, Jed; Graham, Roy; Michaelis, Harald; Schuele, Udo; Warren, Harry

    2016-03-01

    We present a summary of the solar observing Rapid Acquisition Imaging Spectrograph Experiment (RAISE) sounding rocket program including an overview of the design and calibration of the instrument, flight performance, and preliminary chromospheric results from the successful November 2014 launch of the RAISE instrument. The RAISE sounding rocket payload is the fastest scanning-slit solar ultraviolet imaging spectrograph flown to date. RAISE is designed to observe the dynamics and heating of the solar chromosphere and corona on time scales as short as 100-200ms, with arcsecond spatial resolution and a velocity sensitivity of 1-2km/s. Two full spectral passbands over the same one-dimensional spatial field are recorded simultaneously with no scanning of the detectors or grating. The two different spectral bands (first-order 1205-1251Å and 1524-1569Å) are imaged onto two intensified Active Pixel Sensor (APS) detectors whose focal planes are individually adjusted for optimized performance. RAISE reads out the full field of both detectors at 5-10Hz, recording up to 1800 complete spectra (per detector) in a single 6-min rocket flight. This opens up a new domain of high time resolution spectral imaging and spectroscopy. RAISE is designed to observe small-scale multithermal dynamics in Active Region (AR) and quiet Sun loops, identify the strength, spectrum and location of high frequency waves in the solar atmosphere, and determine the nature of energy release in the chromospheric network.

  12. First-Principles Investigation of Li Intercalation Kinetics in Phospho-Olivines

    NASA Astrophysics Data System (ADS)

    Malik, Rahul

    agreement with experiments on large LiFePO4 single crystals. Third, we investigate why LiFePO4 can be charged and discharged rapidly despite having to undergo a first-order phase transition. Conventional wisdom dictates that a system with strong equilibrium Li segregation behavior requires both nucleation and growth in the charge and discharge process, which should impede the overall kinetics. Rather, through first-principles calculations, we determine the minimal energy required to access a non-equilibrium transformation path entirely through the solid solution. Not only does this transformation mechanism require little driving force, but it also rationalizes how a kinetically favorable but nonequilibrium path is responsible for the extremely high rate performance associated with this material. The consequences of a rapid non-equilibrium single-particle transformation mechanism on (dis)charging a multi-particle assembly, as is the case in porous electrodes, are discussed and compared to experimental observations. (Copies available exclusively from MIT Libraries, libraries.mit.edu/docs - docs mit.edu)

  13. A hybrid computer program for rapidly solving flowing or static chemical kinetic problems involving many chemical species

    NASA Technical Reports Server (NTRS)

    Mclain, A. G.; Rao, C. S. R.

    1976-01-01

    A hybrid chemical kinetic computer program was assembled which provides a rapid solution to problems involving flowing or static, chemically reacting, gas mixtures. The computer program uses existing subroutines for problem setup, initialization, and preliminary calculations and incorporates a stiff ordinary differential equation solution technique. A number of check cases were recomputed with the hybrid program and the results were almost identical to those previously obtained. The computational time saving was demonstrated with a propane-oxygen-argon shock tube combustion problem involving 31 chemical species and 64 reactions. Information is presented to enable potential users to prepare an input data deck for the calculation of a problem.

  14. Kinetic investigation of recombinant human hyaluronidase PH20 on hyaluronic acid.

    PubMed

    Fang, Shiping; Hays Putnam, Anna-Maria A; LaBarre, Michael J

    2015-07-01

    The kinetic investigation of hyaluronidases using physiologically relevant hyaluronic acid (HA or hyaluronan) substrate will provide useful and important clues to their catalytic behavior and function in vivo. We present here a simple and sensitive method for kinetic measurement of recombinant human hyaluronidase PH20 (rHuPH20) on HA substrates with sizes ranging from 90 to 752 kDa. The method is based on 2-aminobenzamide labeling of hydrolyzed HA products combined with separation by size exclusion-ultra performance liquid chromatography coupled with fluorescence detection. rHuPH20 was found to follow Michaelis-Menten kinetics during the initial reaction time. Optimal reaction rates were observed in the pH range of 4.5-5.5. The HA substrate size did not have significant effects on the initial rate of the reaction. By studying HA substrates of 215, 357, and 752 kDa, the kinetic parameters Km, Vmax, and kcat were determined to be 0.87-0.91 mg/ml, 1.66-1.74 NM s(-1), and 40.5-42.4 s(-1), respectively. This method allows for direct measurement of kinetics using physiologically relevant HA substrates and can be applied to other hyaluronidase kinetic measurements.

  15. An investigation of the structure and function of antistaphylococcal endolysins using kinetic methods

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Peculiarities of the structures and functions of phage phi11 and phi80a antistaphylococcal endolysins were investigated by kinetic measurements. In spite of the high level of homology in their primary structures, both enzymes possess some differences in their optimal conditions for functioning. As...

  16. Investigating High-School Chemical Kinetics: The Greek Chemistry Textbook and Students' Difficulties

    ERIC Educational Resources Information Center

    Gegios, Theodoros; Salta, Katerina; Koinis, Spyros

    2017-01-01

    In this study we present an analysis of how the structure and content of the Greek school textbook approaches the concepts of chemical kinetics, and an investigation of the difficulties that 11th grade Greek students face regarding these concepts. Based on the structure and content of the Greek textbook, a tool was developed and applied to…

  17. Rapid kinetics of endocytosis at rod photoreceptor synapses depends upon endocytic load and calcium.

    PubMed

    Cork, Karlene M; Thoreson, Wallace B

    2014-05-01

    Release from rods is triggered by the opening of L-type Ca2+ channels that lie beneath synaptic ribbons. After exocytosis, vesicles are retrieved by compensatory endocytosis. Previous work showed that endocytosis is dynamin-dependent in rods but dynamin-independent in cones. We hypothesized that fast endocytosis in rods may also differ from cones in its dependence upon the amount of Ca2+ influx and/or endocytic load. We measured exocytosis and endocytosis from membrane capacitance (C m) changes evoked by depolarizing steps in voltage clamped rods from tiger salamander retinal slices. Similar to cones, the time constant for endocytosis in rods was quite fast, averaging <200 ms. We manipulated Ca2+ influx and the amount of vesicle release by altering the duration and voltage of depolarizing steps. Unlike cones, endocytosis kinetics in rods slowed after increasing Ca2+ channel activation with longer step durations or more strongly depolarized voltage steps. Endocytosis kinetics also slowed as Ca2+ buffering was decreased by replacing BAPTA (10 or 1 mM) with the slower Ca2+ buffer EGTA (5 or 0.5 mM) in the pipette solution. These data provide further evidence that endocytosis mechanisms differ in rods and cones and suggest that endocytosis in rods is regulated by both endocytic load and local Ca2+ levels.

  18. Rapid kinetics of endocytosis at rod photoreceptor synapses depends upon endocytic load and calcium

    PubMed Central

    CORK, KARLENE M.; THORESON, WALLACE B.

    2015-01-01

    Release from rods is triggered by the opening of L-type Ca2+ channels that lie beneath synaptic ribbons. After exocytosis, vesicles are retrieved by compensatory endocytosis. Previous work showed that endocytosis is dynamin-dependent in rods but dynamin-independent in cones. We hypothesized that fast endocytosis in rods may also differ from cones in its dependence upon the amount of Ca2+ influx and/or endocytic load. We measured exocytosis and endocytosis from membrane capacitance (Cm) changes evoked by depolarizing steps in voltage clamped rods from tiger salamander retinal slices. Similar to cones, the time constant for endocytosis in rods was quite fast, averaging <200 ms. We manipulated Ca2+ influx and the amount of vesicle release by altering the duration and voltage of depolarizing steps. Unlike cones, endocytosis kinetics in rods slowed after increasing Ca2+ channel activation with longer step durations or more strongly depolarized voltage steps. Endocytosis kinetics also slowed as Ca2+ buffering was decreased by replacing BAPTA (10 or 1 mM) with the slower Ca2+ buffer EGTA (5 or 0.5 mM) in the pipette solution. These data provide further evidence that endocytosis mechanisms differ in rods and cones and suggest that endocytosis in rods is regulated by both endocytic load and local Ca2+ levels. PMID:24735554

  19. Selectin-like kinetics and biomechanics promote rapid platelet adhesion in flow: the GPIb(alpha)-vWF tether bond.

    PubMed Central

    Doggett, Teresa A; Girdhar, Gaurav; Lawshé, Avril; Schmidtke, David W; Laurenzi, Ian J; Diamond, Scott L; Diacovo, Thomas G

    2002-01-01

    The ability of platelets to tether to and translocate on injured vascular endothelium relies on the interaction between the platelet glycoprotein receptor Ib alpha (GPIb(alpha)) and the A1 domain of von Willebrand factor (vWF-A1). To date, limited information exists on the kinetics that govern platelet interactions with vWF in hemodynamic flow. We now report that the GPIb(alpha)-vWF-A1 tether bond displays similar kinetic attributes as the selectins including: 1) the requirement for a critical level of hydrodynamic flow to initiate adhesion, 2) short-lived tethering events at sites of vascular injury in vivo, and 3) a fast intrinsic dissociation rate constant, k(0)(off) (3.45 +/- 0.37 s(-1)). Values for k(off), as determined by pause time analysis of transient capture/release events, were also found to vary exponentially (4.2 +/- 0.8 s(-1) to 7.3 +/- 0.4 s(-1)) as a function of the force applied to the bond (from 36 to 217 pN). The biological importance of rapid bond dissociation in platelet adhesion is demonstrated by kinetic characterization of the A1 domain mutation, I546V that is associated with type 2B von Willebrand disease (vWD), a bleeding disorder that is due to the spontaneous binding of plasma vWF to circulating platelets. This mutation resulted in a loss of the shear threshold phenomenon, a approximately sixfold reduction in k(off), but no significant alteration in the ability of the tether bond to resist shear-induced forces. Thus, flow dependent adhesion and rapid and force-dependent kinetic properties are the predominant features of the GPIb(alpha)-vWF-A1 tether bond that in part may explain the preferential binding of platelets to vWF at sites of vascular injury, the lack of spontaneous platelet aggregation in circulating blood, and a mechanism to limit thrombus formation. PMID:12080112

  20. On the thermodynamic and kinetic investigations of a [c2]daisy chain polymer

    SciTech Connect

    Hmadeh, Mohamad; Fang, Lei; Trabolsi, Ali; Elhabiri, Mourad; Albrecht-Gary, Anne-Marie; Stoddart, J. Fraser

    2010-01-01

    We report a variety of [c2]daisy chain molecules which undergo quantitative, efficient, and fully reversible molecular movements upon the addition of base/acid in organic solvents. Such externally triggered molecular movements can induce the contraction and extension of the [c2]daisy chain molecule as a whole. A linear polymer of such a bistable [c2]daisy chain exerts similar types of movements and can be looked upon as a candidate for the development of artificial muscles. The spectrophotometric investigations of both the monomeric and polymeric bistable [c2]daisy chains, as well as the corresponding model compounds, were performed in MeCN at room temperature, in order to obtain the thermodynamic parameters for these mechanically interlocked molecules. Based on their spectrophotometric and thermodynamic characteristics, kinetic analysis of the acid/base-induced contraction and extension of the [c2]daisy chain monomer and polymer were conducted by employing a stopped-flow technique. These kinetic data suggest that the rates of contraction and extension for these [c2]daisy chain molecules are determined by the thermodynamic stabilities of the corresponding kinetic intermediates. Faster switching rates for both the contraction and extension processes of the polymeric [c2]daisy chain were observed when compared to those of its monomeric counterpart. These kinetic and thermodynamic investigations on [c2]daisy chain-based muscle-like compounds provide important information for those seeking an understanding of the mechanisms of actuation in mechanically interlocked macromolecules.

  1. Microwave gallium-68 radiochemistry for kinetically stable bis(thiosemicarbazone) complexes: structural investigations and cellular uptake under hypoxia.

    PubMed

    Alam, Israt S; Arrowsmith, Rory L; Cortezon-Tamarit, Fernando; Twyman, Frazer; Kociok-Köhn, Gabriele; Botchway, Stanley W; Dilworth, Jonathan R; Carroll, Laurence; Aboagye, Eric O; Pascu, Sofia I

    2016-01-07

    We report the microwave synthesis of several bis(thiosemicarbazones) and the rapid gallium-68 incorporation to give the corresponding metal complexes. These proved kinetically stable under 'cold' and 'hot' biological assays and were investigated using laser scanning confocal microscopy, flow cytometry and radioactive cell retention studies under normoxia and hypoxia. (68)Ga complex retention was found to be 34% higher in hypoxic cells than in normoxic cells over 30 min, further increasing to 53% at 120 min. Our data suggests that this class of gallium complexes show hypoxia selectivity suitable for imaging in living cells and in vivo tests by microPET in nude athymic mice showed that they are excreted within 1 h of their administration.

  2. RAPID ARSENITE OXIDATION BY THERMUS AQUATICUS AND THERMUS THERMOPHILUS: FIELD AND LABORATORY INVESTIGATIONS. (R826189)

    EPA Science Inventory

    Thermus aquaticus and Thermus thermophilus, common inhabitants of terrestrial hot springs and thermally polluted domestic and industrial waters, have been found to rapidly oxidize arsenite to arsenate. Field investigations at a hot spring in Yellowstone National Park revealed ...

  3. Kinetics of killing Listeria monocytogenes by macrophages: rapid killing accompanying phagocytosis

    SciTech Connect

    Davies, W.A.

    1983-08-01

    The kinetics of bactericidal activity of activated macrophages can be precisely described by a mathematical model in which phagocytosis, killing, digestion, and release of degraded bacterial material are considered to occur continuously. To gain a better understanding of these events, I have determined the period of time between first contact of bacteria with macrophages and the onset of killing. Activated rat peritoneal macrophages were incubated for various times up to 15 min with Listeria monocytogenes previously labeled with /sup 3/H-thymidine and the unassociated bacteria removed by two centrifugations through a density interface. Both cell-associated radioactivity and cell-associated viable bacteria, determined as colony forming units after sonication of the cell pellet, increased with time of incubation. However, the specific viability of these bacteria, expressed as the ratio of number of viable bacteria per unit radioactivity declined with time, as an approximate inverse exponential, after a lag period of 2.9 +/- 0.8 min. Evidence is given that other possible causes for this decline in specific viability, other than death of the bacteria, such as preferential ingestion of dead Listeria, clumping of bacteria, variations in autolytic activity, or release of Listericidins are unlikely. I conclude therefore that activated macrophages kill Listeria approximately 3 min after the cell and the bacterium first make contact.

  4. Kinetic modeling of rapid enzymatic hydrolysis of crystalline cellulose after pretreatment by NMMO.

    PubMed

    Khodaverdi, Mahdi; Jeihanipour, Azam; Karimi, Keikhosro; Taherzadeh, Mohammad J

    2012-03-01

    Pretreatment of cellulose with an industrial cellulosic solvent, N-methylmorpholine-N-oxide, showed promising results in increasing the rate of subsequent enzymatic hydrolysis. Cotton linter was used as high crystalline cellulose. After the pretreatment, the cellulose was almost completely hydrolyzed in less than 12 h, using low enzyme loading (15 FPU/g cellulose). The pretreatment significantly decreased the total crystallinity of cellulose from 7.1 to 3.3, and drastically increased the enzyme adsorption capacity of cellulose by approximately 42 times. A semi-mechanistic model was used to describe the relationship between the cellulose concentration and the enzyme loading. In this model, two reactions for heterogeneous reaction of cellulose to glucose and cellobiose, and a homogenous reaction for cellobiose conversion to glucose was incorporated. The Langmuir model was applied to model the adsorption of cellulase onto the treated cellulose. The competitive inhibition was also considered for the effects of sugar inhibition on the rate of enzymatic hydrolysis. The kinetic parameters of the model were estimated by experimental results and evaluated.

  5. FLYCHK: generalized population kinetics and spectral model for rapid spectroscopic analysis for all elements

    SciTech Connect

    Chung, H; Chen, M; Morgan, W L; Ralchenko, Y; Lee, R W

    2005-06-17

    FLYCHK is a straightforward, rapid tool to provide ionization and population distributions of plasmas in zero dimension with accuracy sufficient for most initial estimates and in many cases applicable for more sophisticated analysis. FLYCHK solves rate equations for level population distributions by considering collisional and radiative atomic processes. The code is designed to be straightforward to use and yet is general enough to apply for most laboratory plasmas. Further, it can be applied for low-to-high Z ions and in either steady-state or time-dependent situations. Plasmas with arbitrary electron energy distributions, single or multiple electron temperatures can be studied as well as radiation-driven plasmas. To achieve this versatility and accuracy in a code that provides rapid response we employ schematic atomic structures, scaled hydrogenic cross-sections and read-in tables. It also employs the jj configuration averaged atomic states and oscillator strengths calculated using the Dirac-Hartree-Slater model for spectrum synthesis. Numerous experimental and calculational comparisons performed in recent years show that FLYCHK provides meaningful estimates of ionization distributions, well within a charge state for most laboratory applications.

  6. An investigation on the catalytic capacity of dolomite in transesterification and the calculation of kinetic parameters.

    PubMed

    Niu, Sheng-Li; Huo, Meng-Jia; Lu, Chun-Mei; Liu, Meng-Qi; Li, Hui

    2014-04-01

    The catalytic capacity of dolomite in transesterification was investigated and the kinetic parameters were calculated. The activated dolomites as transesterification catalyst were characterized by X-ray diffraction, nitrogen adsorption and desorption and Hammett indicator method, where the original dolomite was analyzed by thermogravimetric and X-ray fluorescence in advance. Its potential catalytic capacity was validated from aspects of the activated temperature and the reused property, where the reliability of the experimental system was also examined. Then, influences of the catalyst added amount, the mole ratio of methanol to oil, the transesterification temperature and the transesterification time on the catalytic capacity were investigated. Finally, kinetic parameters of the transesterification catalyzed by the activated dolomite were calculated.

  7. Rapid-reaction kinetic characterization of the pathway of streptokinase-plasmin catalytic complex formation.

    PubMed

    Verhamme, Ingrid M; Bock, Paul E

    2008-09-19

    Binding of the fibrinolytic proteinase plasmin (Pm) to streptokinase (SK) in a tight stoichiometric complex transforms Pm into a potent proteolytic activator of plasminogen. SK binding to the catalytic domain of Pm, with a dissociation constant of 12 pm, is assisted by SK Lys(414) binding to a Pm kringle, which accounts for a 11-20-fold affinity decrease when Pm lysine binding sites are blocked by 6-aminohexanoic acid (6-AHA) or benzamidine. The pathway of SK.Pm catalytic complex formation was characterized by stopped-flow kinetics of SK and the Lys(414) deletion mutant (SKDeltaK414) binding to Pm labeled at the active site with 5-fluorescein ([5F]FFR-Pm) and the reverse reactions by competitive displacement of [5F]FFR-Pm with active site-blocked Pm. The rate constants for the biexponential fluorescence quenching caused by SK and SKDeltaK414 binding to [5F]FFR-Pm were saturable as a function of SK concentration, reporting encounter complex affinities of 62-110 nm in the absence of lysine analogs and 4900-6500 and 1430-2200 nm in the presence of 6-AHA and benzamidine, respectively. The encounter complex with SKDeltaK414 was approximately 10-fold weaker in the absence of lysine analogs but indistinguishable from that of native SK in the presence of 6-AHA and benzamidine. The studies delineate for the first time the sequence of molecular events in the formation of the SK.Pm catalytic complex and its regulation by kringle ligands. Analysis of the forward and reverse reactions supports a binding mechanism in which SK Lys(414) binding to a Pm kringle accompanies near-diffusion-limited encounter complex formation followed by two slower, tightening conformational changes.

  8. Measurements of crystal growth kinetics at extreme deviations from equilibrium. [Rapid solidification processing

    SciTech Connect

    Aziz, M.J.

    1993-05-07

    We have measured solute trapping of Sn in Al over a wide enough range of velocities to make a quantitative test of theory. The Continuous Growth Model of Aziz is the only one-parameter model that fits the data. We have also measured the diffusive speed - the growth rate at which interfacial partitioning is in mid-transition between equilibrium partitioning and complete solute trapping - for several solutes in A1. We have found an inverse correlation between the equilibrium partition coefficient and the diffusive speed. Taken together, these results give us heretofore unprecedented predictive capability in modeling rapid solidification processing. We have also examined theoretically short-range diffusion-limited growth, characteristic of incomplete solute trapping, and interface-limited growth, characteristic of complete solute trapping, in alloy solidification and have shown that the two regimes fall naturally out of a single unified theory of solidification.

  9. RAPID BIOCATALYTIC POLYTRANSESTERIFICATION: REACTION KINETICS IN AN EXOTHERMIC REACTION. (R825338)

    EPA Science Inventory

    The perspectives, information and conclusions conveyed in research project abstracts, progress reports, final reports, journal abstracts and journal publications convey the viewpoints of the principal investigator and may not represent the views and policies of ORD and EPA. Concl...

  10. [The accuracy of rapid equilibrium assumption in steady-state enzyme kinetics is the function of equilibrium segment structure and properties].

    PubMed

    Vrzheshch, P V

    2015-01-01

    Quantitative evaluation of the accuracy of the rapid equilibrium assumption in the steady-state enzyme kinetics was obtained for an arbitrary mechanism of an enzyme-catalyzed reaction. This evaluation depends only on the structure and properties of the equilibrium segment, but doesn't depend on the structure and properties of the rest (stationary part) of the kinetic scheme. The smaller the values of the edges leaving equilibrium segment in relation to values of the edges within the equilibrium segment, the higher the accuracy of determination of intermediate concentrations and reaction velocity in a case of the rapid equilibrium assumption.

  11. Experimental Investigation and Modeling of Kinetic Processes in a KrF Laser

    NASA Astrophysics Data System (ADS)

    Bychkov, Yu. I.; Yastremskii, A. G.; Yampolskaya, S. A.; Losev, V. F.; Dudarev, V. V.; Panchenko, Yu. N.; Puchikin, A. V.

    2014-11-01

    The KrF laser with radiation pulse duration at half maximum of 20 ns is experimentally investigated. A self-consistent model is developed considering the electric circuit, the kinetic processes in the active medium, and the formation of laser radiation in a resonator. Time dependences of the discharge current and voltage on the capacitor and discharge electrodes, plasma particle concentration, and rate constants of the processes determining the characteristics of the discharge and laser radiation are presented. Processes are revealed that determines the characteristics of the space charge and laser radiation. The kinetics of the processes of production and annihilation of KrF excimer molecules is studied in detail. It is demonstrated that high rates of destruction of excimer molecules increases the time of delay of generation thereby decreasing the efficiency of laser generation and limiting the possibility of decreasing laser radiation pulse duration.

  12. Investigation of molecule-adsorption kinetics by a pulsed laser desorption technique

    NASA Astrophysics Data System (ADS)

    Varakin, V. N.; Lozovskii, A. D.; Panesh, A. M.; Simonov, A. P.

    1987-02-01

    The laser thermal desorption technique is used to measure the adsorption kinetics of SO2 and CO molecules on stainless steel with the aim of investigating the initial stage of oxidation of the steel by adsorbed CO molecules. Attention is given to the dependence of the rate of establishment of the equilibrium concentration of adsorbed molecules on SO2-gas pressure; CO adsorption kinetics on stainless steel at a gas pressure of 9 x 10 to the -8th torr; and the dependence of the concentration of adsorbed CO molecules on exposure in the gas at a pressure of 9 x 10 to the -8th torr under irradiation by laser pulses with repetition periods of 1-2, 2-4, 3-6, and 4-8 min.

  13. Investigating the kinetic stability and transformation of vapor-deposited glasses with AC nanocalorimetry experiments

    NASA Astrophysics Data System (ADS)

    Tylinski, Michael Tod

    This thesis presents experiments and discussion that advance the understanding of vapor-deposited glasses. When vapor-deposited glasses exhibit high kinetic stability, they're known as stable glasses. Stable glasses are known to transform into the liquid state via a front mechanism. My first project introduced a quantitative evaluation of the uniformity of these fronts over time and space. I found that the front velocity varies by less than 4% over the duration of the transformation. For films 280 nm thick, the transformation rates at different spatial positions in the film differ by about 25%; this quantity may be related to spatially heterogeneous dynamics in the stable glass. In my second project, I established that vapor deposition could be used to prepare stable glasses of an alcohol molecule. It was previously unknown if this was possible. I also found that while at least one alcohol molecule can be used to prepare a stable glass, several other alcohol molecules formed glasses with minimal kinetic stability when using standard deposition conditions. The wide range of kinetic stabilities is useful for investigating the factors that control stable glass formation. I compared the kinetic stability of vapor deposited glasses prepared from 14 molecules and found a correlation with the value of taualpha at 1.25 Tg. In my final research project, I performed experiments that tested various hypotheses for why 2-ethyl-1-hexanol forms vapor-deposited glasses with limited kinetic stability when using standard preparation conditions. The experiments supported the hypothesis that the surface mobility is less than for other molecules that are used to prepare stable glasses. My analysis of the data led to the estimation that at the substrate temperature commonly used to deposit stable glasses, 2-ethyl-1-hexanol molecules at the surface move more than 104 times slower compared to molecules that do form highly stable glasses using typical preparation conditions. The thesis

  14. Investigation of equilibration and growth of stepped surfaces by Kinetic Monte Carlo in one dimension

    NASA Astrophysics Data System (ADS)

    Türkan, A.; Esen, M.; Tüzemen, A. Türker; Özdemir, M.

    2017-02-01

    In this study, the equilibration and in the case of a particle flux to the surface, the growth of a one dimensional semi-conductor surface of "V" initial shape is investigated by kinetic Monte Carlo method. The initial surface is assumed to consist of atomic height steps separated by terraces. In Monte Carlo simulations, the following processes are considered: the diffusion of free particles on the surface, the attachment/detachment of particles to/from step edges from/to a terrace in front of a step or to a terrace above the step. In the simulations the Ehrlich-Schwoebel barrier is also taken into account. The equilibration of "V" initial shape at various temperatures is investigated. Moreover, the effect of particle bonding energy on the surface profile and on the evolution of the surface is also investigated. In the case of a particle flux to the surface, the surface profile and its growth kinetics are investigated at various temperatures and flux values.

  15. Hardening kinetics investigation of alkali-activated binder by small amplitude oscillatory rheometry

    NASA Astrophysics Data System (ADS)

    Rieger, D.; Kullová, L.; Čekalová, M.; Kovářík, T.

    2017-01-01

    In this study, the rheological behavior of geopolymeric inorganic binder was determined. This binder was synthesized by alkaline activation of mixture, comprising calcined claystone powder and milled blast furnace slag. As an alkaline activator of hardening process, the potassium silicate solution was used. For the investigation of hardening kinetics, the strain controlled small amplitude oscillatory rheometry was used with strain of 0.01%. The reproducibility and versatility of this method is demonstrated for determination of hardening process evolution. The changes of loss tangent shape were studied in this experiment and applied for determination of gelation time. All experiments were conducted at isothermal conditions in temperature range 27-70°C and parallel plate geometry. The results indicate that reaction kinetics is directly depending on temperature. The hardening kinetics was mathematically described and these calculations were compared with self-contained experiment conducted at 2°C. This experiment is described in details and the results of gelation time measurements confirmed calculated data.

  16. A model stomach system to investigate disintegration kinetics of solid foods during gastric digestion.

    PubMed

    Kong, F; Singh, R P

    2008-06-01

    Knowledge of the disintegration kinetics of food particulates in the human stomach is essential for assessing the bioaccessibility of nutrients in solid foods and understanding stomach emptying. The objective of this study was to develop a model stomach system and to investigate the kinetics of food disintegration. Our system consisted mainly of a turntable and a jacketed glass chamber containing simulated gastric juice in which plastic beads were added to simulate food particulates as well as provide a suitable mechanical destructive force on food samples. The mechanical force on the samples was simultaneously measured using the load cell of a TA-XT2 texture analyzer. Cylindrical carrots and ham samples were used as representative foods. The system is capable of simulating the in vivo stomach in terms of providing a wide range of continuous and periodic forces comparable to those measured in vivo. The modified power exponential function of the form y(t)= 1 - (1 -e(-kt))(beta), where y(t) is the mass retention ratio at time t, provided a reasonable description for the disintegration performance of tested foods. The mass retention curve can be either a sigmoidal decay with an initial delay or an exponential decay, which are decided largely by the hardness of the foods during digestion and the extent of physical force acting on the foods. A good match was observed between the kinetics of food disintegration and in vivo stomach emptying.

  17. Kinetics and Microstructural Investigation of High-Temperature Oxidation of IN-738LC Super Alloy

    NASA Astrophysics Data System (ADS)

    Hamidi, S.; Rahimipour, M. R.; Eshraghi, M. J.; Hadavi, S. M. M.; Esfahani, H.

    2016-12-01

    The present study was carried out to investigate the kinetics and the surface chemistry of the oxide layers formed on the IN-738LC super alloy during high-temperature oxidation at 950 °C in air from 1 to 260 h. Oxidation kinetics were studied by mass gain measurement. The oxide layers were characterized by field emission scanning electron microscope, elemental distribution map, energy-dispersive spectroscopy as well as x-ray diffractometry (XRD). The oxidation kinetics followed the parabolic law. The XRD analysis revealed that the oxide scale contained mainly NiO, Ni (Cr, Al)2O4, Al2O3, TiO2 and Cr2O3. The oxide structure, from the top surface down to the substrate, was clarified by elemental map distribution studies as Ni-Ti oxides, Cr-Ti oxides, Cr2O3 oxide band, Ni-Co-Cr-W oxide and finally a blocky Al2O3 region. The oxidation scales were composed of three distinct layers of the outer and mid layers enriched by TiO2 and Cr2O3, NiCr2O4 oxide, respectively, and the innermost layer was composed of Al2O3 and matrix alloy. The depleted gamma prime layer was formed under the oxidation scales due to the impoverishment of Al and Ti which were induced by the formation of Al2O3 and TiO2.

  18. Molecular-Level Investigations of Nucleation Mechanisms and Kinetics of Formation of Environmental Nanoparticles

    SciTech Connect

    Young-Shin Jun; Glenn A. Waychunas

    2007-04-19

    Environmental nanoparticles are often poorly-crystalline or metastable structures, whose kinetics of formation and growth are poorly understood. Further, the sorption or growth of nanoparticles on mineral surfaces may control the mineral surface's reactivity and modify its ability to influence contaminant transport. Due to the characteristic length scale, a holistic understanding of the nucleation mechanisms and kinetics of nanoparticle formation on mineral surfaces is difficult to achieve with traditional methodology. In this work, our intent is to determine the molecular nature of nucleation on surfaces, the kinetics of surface nucleation and growth, and the effect of crystal surface topology using new synchrotron-based techniques. We have approached these objectives by: (1) combining state-of-the-art crystal-truncation rod diffraction (CTR) and grazing incidence x-ray absorption fine structure spectroscopy (GIXAS) techniques to investigate the three-dimensional molecular-scale geometry of silicate monomer sorption on the r-plane of hematite; and (2) developing a new grazing-incidence small angle x-ray scattering (GISAXS) setup at SSRL (0.08 nm{sup -1} < q < 8 nm{sup -1}) to explore the initial development of environmental nanoparticles on various mineral surfaces. This study also includes complementary techniques such as atomic force microscopy (AFM), bulk SAXS, dynamic light scattering (DLS), XRD, and TEM.

  19. Kinetics and Microstructural Investigation of High-Temperature Oxidation of IN-738LC Super Alloy

    NASA Astrophysics Data System (ADS)

    Hamidi, S.; Rahimipour, M. R.; Eshraghi, M. J.; Hadavi, S. M. M.; Esfahani, H.

    2017-02-01

    The present study was carried out to investigate the kinetics and the surface chemistry of the oxide layers formed on the IN-738LC super alloy during high-temperature oxidation at 950 °C in air from 1 to 260 h. Oxidation kinetics were studied by mass gain measurement. The oxide layers were characterized by field emission scanning electron microscope, elemental distribution map, energy-dispersive spectroscopy as well as x-ray diffractometry (XRD). The oxidation kinetics followed the parabolic law. The XRD analysis revealed that the oxide scale contained mainly NiO, Ni (Cr, Al)2O4, Al2O3, TiO2 and Cr2O3. The oxide structure, from the top surface down to the substrate, was clarified by elemental map distribution studies as Ni-Ti oxides, Cr-Ti oxides, Cr2O3 oxide band, Ni-Co-Cr-W oxide and finally a blocky Al2O3 region. The oxidation scales were composed of three distinct layers of the outer and mid layers enriched by TiO2 and Cr2O3, NiCr2O4 oxide, respectively, and the innermost layer was composed of Al2O3 and matrix alloy. The depleted gamma prime layer was formed under the oxidation scales due to the impoverishment of Al and Ti which were induced by the formation of Al2O3 and TiO2.

  20. Curing kinetics of visible light curing dental resin composites investigated by dielectric analysis (DEA).

    PubMed

    Steinhaus, Johannes; Hausnerova, Berenika; Haenel, Thomas; Großgarten, Mandy; Möginger, Bernhard

    2014-03-01

    During the curing process of light curing dental composites the mobility of molecules and molecule segments is reduced leading to a significant increase of the viscosity as well as the ion viscosity. Thus, the kinetics of the curing behavior of 6 different composites was derived from dielectric analysis (DEA) using especially redesigned flat sensors with interdigit comb electrodes allowing for irradiation at the top side and measuring the ion viscosity at the bottom side. As the ion viscosities of dental composites change 1-3 orders of magnitude during the curing process, DEA provides a sensitive approach to evaluate their curing behavior, especially in the phase of undisturbed chain growth. In order to determine quantitative kinetic parameters a kinetic model is presented and examined for the evaluation of the ion viscosity curves. From the obtained results it is seen that DEA might be employed in the investigation of the primary curing process, the quality assurance of ingredients as well as the control of processing stability of the light curing dental composites.

  1. Investigation of reaction kinetics and interfacial phase formation in Ti3Al + Nb composites

    NASA Technical Reports Server (NTRS)

    Wawner, F. E.; Gundel, D. B.

    1992-01-01

    Titanium aluminide metal matrix composites are prominent materials systems being considered for high temperature aerospace applications. One of the major problems with this material is the reactivity between existing reinforcements and the matrix after prolonged thermal exposure. This paper presents results from an investigation of reaction kinetics between Ti-14Al-21Nb (wt pct) and SCS-6 fibers and SiC fibers with surface coatings of TiB2, TiC, TiN, W, and Si. Microstructural evaluation of the reaction layers as well as matrix regions around the fibers is presented.

  2. Numerical simulation on the opto-electro-kinetic patterning for rapid concentration of particles in a microchannel.

    PubMed

    Kim, Dong; Shim, Jaesool; Chuang, Han-Sheng; Kim, Kyung Chun

    2015-05-01

    This paper presents a mathematical model for laser-induced rapid electro-kinetic patterning (REP) to elucidate the mechanism for concentrating particles in a microchannel non-destructively and non-invasively. COMSOL(®)(v4.2a) multiphysics software was used to examine the effect of a variety of parameters on the focusing performance of the REP. A mathematical model of the REP was developed based on the AC electrothermal flow (ACET) equations, the dielectrophoresis (DEP) equation, the energy balance equation, the Navier-Stokes equation, and the concentration-distribution equation. The medium was assumed to be a diluted solute, and different electric potentials and laser illumination were applied to the desired place. Gold (Au) electrodes were used at the top and bottom of a microchannel. For model validation, the simulation results were compared with the experimental data. The results revealed the formation of a toroidal microvortex via the ACET effect, which was generated due to laser illumination and joule-heating in the area of interest. In addition, under some conditions, such as the frequency of AC, the DEP velocity, and the particle size, the ACET force enhances and compresses resulting in the concentration of particles. The conditions of the DEP velocity and the ACET velocity are presented in detail with a comparison of the experimental results.

  3. Numerical simulation on the opto-electro-kinetic patterning for rapid concentration of particles in a microchannel

    PubMed Central

    Kim, Dong; Shim, Jaesool; Chuang, Han-Sheng; Kim, Kyung Chun

    2015-01-01

    This paper presents a mathematical model for laser-induced rapid electro-kinetic patterning (REP) to elucidate the mechanism for concentrating particles in a microchannel non-destructively and non-invasively. COMSOL®(v4.2a) multiphysics software was used to examine the effect of a variety of parameters on the focusing performance of the REP. A mathematical model of the REP was developed based on the AC electrothermal flow (ACET) equations, the dielectrophoresis (DEP) equation, the energy balance equation, the Navier-Stokes equation, and the concentration-distribution equation. The medium was assumed to be a diluted solute, and different electric potentials and laser illumination were applied to the desired place. Gold (Au) electrodes were used at the top and bottom of a microchannel. For model validation, the simulation results were compared with the experimental data. The results revealed the formation of a toroidal microvortex via the ACET effect, which was generated due to laser illumination and joule-heating in the area of interest. In addition, under some conditions, such as the frequency of AC, the DEP velocity, and the particle size, the ACET force enhances and compresses resulting in the concentration of particles. The conditions of the DEP velocity and the ACET velocity are presented in detail with a comparison of the experimental results. PMID:26015839

  4. The investigation of kinetic and isotherm of fluoride adsorption onto functionalize pumice stone.

    PubMed

    Asgari, Ghorban; Roshani, Babak; Ghanizadeh, Ghader

    2012-05-30

    In this research work, pumice that is functionalized by the cationic surfactant, hexadecyltrimethyl ammonium (HDTMA), is used as an adsorbent for the removal of fluoride from drinking water. This work was carried out in two parts. The effects of HDTMA loading, pH (3-10), reaction time (5-60 min) and the adsorbent dosage (0.15-2.5 g L(-1)) were investigated on the removal of fluoride as a target contaminate from water through the design of different experimental sets in the first part. The results from this first part revealed that surfactant-modified pumice (SMP) exhibited the best performance at dose 0.5 g L(-1), pH 6, and it adsorbs over 96% of fluoride from a solution containing 10 mg L(-1) fluoride after 30 min of mixing time. The four linear forms of the Langmuir, Freundlich, Temkin and Dubinin-Radushkevich isotherms model were applied to determine the best fit of equilibrium expressions. Apart from the regression coefficient (R(2)), four error functions were used to validate the isotherm and kinetics data. The experimental adsorption isotherm complies with Langmuir equation model type 1. The maximum amount of adsorption (Q(max)) was 41 mg g(-1). The kinetic studies indicated that the adsorption of fluoride best fitted with the pseudo-second-order kinetic type 1. Thermodynamic parameters evaluation of fluoride adsorption on SMP showed that the adsorption process under the selected conditions was spontaneous and endothermic. The suitability of SMP in defluoridation at field condition was investigated with natural groundwater samples collected from a nearby fluoride endemic area in the second part of this study. Based on this study's results, SMP was shown to be an affordable and a promising option for the removal of fluoride in drinking water.

  5. A suggested schedule for the rapid investigation of acute haemostatic failure

    PubMed Central

    Ingram, G. I. C.

    1961-01-01

    A small group of tests is proposed for the rapid investigation of acute bleeding states. These techniques are within the compass of many clinical laboratories, and the whole scheme may be run through in one to one-and-a-half hours. PMID:13717713

  6. Investigation of the kinetics of water uptake into partially saturated shales

    NASA Astrophysics Data System (ADS)

    Roshan, H.; Andersen, M. S.; Rutlidge, H.; Marjo, C. E.; Acworth, R. I.

    2016-04-01

    Several processes have been proposed to describe the low recovery of hydraulic fracturing fluid in unconventional shale reservoirs which has caused both technical and environmental concerns. This study describes novel hydraulic experiments to quantitatively investigate the kinetics of water uptake into partially saturated shale through investigating the pressure response of injecting fluids (NaCl, KCl, MgCl2, and CaCl2 with different ionic concentrations) into crushed and sieved shale fragments. The results of the study indicate that the cumulative water uptake under pressure is likely to be controlled by three processes: surface hydration, capillary hydration including advective flow, and osmotic hydration. Each of these processes is a function of the differences between the in situ pore fluid and the injection fluid (solution chemistry and concentration) and the shale physicochemical properties, in particular the contact surface area, pore diameter, and the Cation Exchange Capacity (CEC). The uptake is not instantaneous, but is diffusion limited, with the rate governed by a number of kinetic processes. Uptake proceeds in three stages, each associated with a different process: (1) predominantly surface hydration, (2) predominantly capillary hydration and finally, (3) predominantly osmotic hydration. It was also shown that shale can take up a significant amount of water compared to its available solid volume. However, contrary to the conventional understanding, the increase in salinity of the injection fluid does not necessarily lead to reduced water uptake into shales, but is dependent on the type and concentration of cations within the shale and injecting fluid.

  7. Experimental Investigation of the Kinetics of a Ruthenium-Catalyzed Deconstruction of Lignin Model Compounds

    SciTech Connect

    Bu, L.; Nimlos, M. R.; Shirts, M. R.; Himmel, M. E.; Crowley, M. F.; Beckham, G. T.

    2012-01-01

    Lignin is a major component of plant cell walls that is typically underutilized in selective conversion strategies for renewable fuels and chemicals. The mechanisms by which thermal and catalytic treatments deconstruct lignin remain elusive. In this work, we have investigated the kinetics of the catalytic deconstruction of lignin model compounds using a ruthenium catalyst reported by Bergman et al. in 2010. A series of investigations using NMR spectroscopy and GC/MS will be presented. In addition, we propose detailed mechanisms for lignin depolymerization with ruthenium catalysts. We have also used DFT to compute transition state geometries of catalytic cycle intermediates and compare the values determined computationally with those observed experimentally. Ultimately, our objective is to apply our methods to the design of new homogeneous and heterogeneous catalysts for the effective deconstruction and valorization of lignin.

  8. Micromodel investigation of transport effect on the kinetics of reductive dissolution of hematite.

    PubMed

    Zhang, Changyong; Liu, Chongxuan; Shi, Zhi

    2013-05-07

    Reductive dissolution of hematite in porous media was investigated using a micromodel (8.1 × 4.5 × 0.028 mm) with realistic pore network structures that include distinctive advection domain, macropores and micropores created in silicon substrate. The micromodel pore surface was sputter deposited with a thin layer (230 nm) of hematite. The hematite in the micromodel was reduced by injecting pH-varying solutions (pH 5.0, 6.0, 7.0) containing a reduced form of flavin mononucleotide (FMNH2, 100 μM), a biogenic soluble electron transfer mediator produced by Shewanella species. The reduction kinetics was determined by measuring effluent Fe(II) (aq) concentration and by spectroscopically monitoring the hematite dissolution front in the micromodel. Batch experiment was also performed to estimate the hematite reduction rate under the well-mixed condition. Results showed significant spatial variation in local redox reaction rate that was controlled by the coupled transport and reaction. The overall rate of the redox reaction in the micromodel required a three-domain numerical model to effectively describe reaction kinetics either with distinctive apparent rate parameters or mass transfer coefficients in different pore domains. Results from this study demonstrated the feasibility of a domain-based modeling approach for scaling reaction rates from batch to porous media systems where reactions may be significantly limited by transport.

  9. Investigation of rehydration kinetics of open-sun dried okra samples

    NASA Astrophysics Data System (ADS)

    Gökçe Kocabay, Özlem; İsmail, Osman

    2017-01-01

    In this study rehydration kinetics of open-sun dried okra, which dried naturally and two pre-treatment, was investigated at 25 and 50 °C. By the obtained data, parameters with respect to rehydration kinetics and diffusion mechanism were calculated. In dehydration experiments, it was determined that blanching pre-treatment has influence on the drying time and okra samples were dried at 18 h. On the contrary in rehydration experiments maximum equilibrium rehydration values were achieved with the okras dried naturally. Experimental equilibrium rehydration (R eq ), theoretical equilibrium rehydration (R max ) and diffusion coefficient (D) of okra dried naturally at 50 °C were calculated as 5.57 (g water/g dry matter), 5.96 (g water/g dry matter) and 2.17 × 10-10 (m2/s), respectively. Rehydration exponent (n) value, which is also important to identify the diffusion type of dried okra, was determined as between 0.332 and 0.383. Because of the exponent value n < 0.50, diffusion was defined as natural Fick type.

  10. Use of surface plasmon resonance to investigate lateral wall deposition kinetics and properties of polydopamine films.

    PubMed

    Li, Hui; Cui, Dafu; Cai, Haoyuan; Zhang, Lulu; Chen, Xing; Sun, Jianhai; Chao, Yapeng

    2013-03-15

    Dopamine (DA) is a particularly important neurotransmitter. Polydopamine (pDA) films have been demonstrated to be important materials for the immobilization of biomolecules onto almost any type of solid substrate. In this study, a surface plasmon resonance (SPR)-based sensor system with the sensor chip surface parallel to the direction of gravity was used to investigate the lateral wall deposition kinetics and properties of pDA films. The deposition kinetics of pDA Films are limited by the oxidation process. The pDA film could not be removed from the sensor chip completely by a strongly alkaline solution, indicating that the pDA film was heterogeneous in the direction of deposition. The pDA film formed near the interior of the solution was less stable than the film formed near the gold-solution interface. Adsorption of proteins on pDA film was studied compared with that on bare gold and dextran sensor chip. The reduction of Au(111) cations by the pDA film, forming a layer of gold particles, was monitored using SPR.

  11. Numerical investigation of kinetic energy dynamics during autoignition of n-heptane/air mixture

    NASA Astrophysics Data System (ADS)

    Lucena Kreppel Paes, Paulo; Brasseur, James; Xuan, Yuan

    2015-11-01

    Many engineering applications involve complex turbulent reacting flows, where nonlinear, multi-scale turbulence-combustion couplings are important. Direct representation of turbulent reacting flow dynamics is associated with prohibitive computational costs, which makes it necessary to employ turbulent combustion models to account for the effects of unresolved scales on resolved scales. Classical turbulence models are extensively employed in reacting flow simulations. However, they rely on assumptions about the energy cascade, which are valid for incompressible, isothermal homogeneous isotropic turbulence. A better understanding of the turbulence-combustion interactions is required for the development of more accurate, physics-based sub-grid-scale models for turbulent reacting flows. In order to investigate the effects of reaction-induced density, viscosity, and pressure variations on the turbulent kinetic energy, Direct Numerical Simulation (DNS) of autoignition of partially-premixed, lean n-heptane/air mixture in three-dimensional homogeneous isotropic turbulence has been performed. This configuration represents standard operating conditions of Homogeneous-Charge Compression-Ignition (HCCI) engines. The differences in the turbulent kinetic energy balance between the present turbulent reacting flow and incompressible, isothermal homogeneous isotropic turbulence are highlighted at different stages during the autoignition process.

  12. Thermoactivated persulfate oxidation of pesticide chlorpyrifos in aquatic system: kinetic and mechanistic investigations.

    PubMed

    Zhou, Lei; Zhang, Ya; Ying, Rongrong; Wang, Guoqing; Long, Tao; Li, Jianhua; Lin, Yusuo

    2017-03-20

    The widespread occurrence of organophosphorus pesticides (OPPs) in the environment poses risks to both ecologic system as well as human health. This study investigated the oxidation kinetics of chlorpyrifos (CP), one of the typical OPPs, by thermoactivated persulfate (PS) oxidation process, and evaluated the influence of key kinetic factors, such as PS concentrations, pH, temperature, bicarbonate, and chloride ions. The reaction pathways and mechanisms were also proposed based on products identification by LC-MS techniques. Our results revealed that increasing initial PS concentration and temperature favored the decomposition of CP, whereas the oxidation efficiency was not affected by pH change ranging from 3 to 11. Bicarbonate was found to play a detrimental role on CP removal rates, while chloride showed no effect. The oxidation pathways including initial oxidation of P=S bond to P=O, dechlorination, dealkylation, and the dechlorination-hydroxylation were proposed, and the detailed underlying mechanisms were also discussed. Molecular orbital (MO) calculations indicated that P=S bond was the most favored oxidation site of the molecule. The toxicity of reaction solution was believed to increase due to the formation of products with P=O structures. This work demonstrates that OPPs can readily react with SO4(·-) and provides important information for further research on the oxidation of these contaminants.

  13. Electrochemical oxidation of an azo dye in aqueous media investigation of operational parameters and kinetics.

    PubMed

    Parsa, J Basiri; Rezaei, M; Soleymani, A R

    2009-09-15

    In this research two types of electrochemical reactors for the treatment of simulated wastewaters containing Direct blue 71 azo dye (DB71) were used: (1) Laboratory scale undivided electrolysis cell system (450 mL volume) with one 2 cm x 2 cm platinum plate as the anode placed in the middle of the cell and two 2 cm x 8 cm steel plates (SS-304) as cathodes placed in the sides of the cell 2 cm from the central anode. (2) Pilot scale reactor (9L volume), equipped with two 3 cm x 23 cm stainless steel plates as anode and cathode, with distance of 3 cm apart. The influence of supporting electrolyte, applied voltage and pH were studied. The UV-vis spectra of samples during the electrochemical oxidation showed the rapid decolorization of the dye solution. During the process, the COD and current were measured in order to evaluate the degree of mineralization, energy consumption, current and anode efficiencies. The optimum supporting electrolyte and applied voltage were NaCl (5 g L(-1)) and 15 V. Using the lab scale reactor resulted in complete decolorization and mineralization of the dye solutions after ca. 90 and 120 min, respectively. Similar results were obtained using the pilot plant reactor under the same conditions. The good fit of the data to pseudo-first-order kinetics for COD removal at all applied voltages (except 20 V) was taken as proof of the involvement of indirect oxidation pathways in the process.

  14. Incubation behavior of silicon nanowire growth investigated by laser-assisted rapid heating

    NASA Astrophysics Data System (ADS)

    Ryu, Sang-gil; Kim, Eunpa; Allen, Frances I.; Hwang, David J.; Minor, Andrew M.; Grigoropoulos, Costas P.

    2016-08-01

    We investigate the early stage of silicon nanowire growth by the vapor-liquid-solid mechanism using laser-localized heating combined with ex-situ chemical mapping analysis by energy-filtered transmission electron microscopy. By achieving fast heating and cooling times, we can precisely determine the nucleation times for nanowire growth. We find that the silicon nanowire nucleation process occurs on a time scale of ˜10 ms, i.e., orders of magnitude faster than the times reported in investigations using furnace processes. The rate-limiting step for silicon nanowire growth at temperatures in the vicinity of the eutectic temperature is found to be the gas reaction and/or the silicon crystal growth process, whereas at higher temperatures it is the rate of silicon diffusion through the molten catalyst that dictates the nucleation kinetics.

  15. Investigation of electroreduction kinetics on modified p-InP in alkaline electrolyte

    SciTech Connect

    Cook, R.L.; Dempsey, P.P.; Sammells, A.F.

    1985-06-01

    The electroreduction kinetics of surface modified p-InP were investigated. The surface was modifie by electrodeposition of Co, Ru, Rh, Pt, Co/Pt, Ru/Pt, and Rh/Pt. Exchange current densities (i/sub 0/) for hydrogen evolution were obtained both in the dark and under 100 mW/cm/sub 2/ illumination. For sequentially deposited metals i/sub 0/ values are lower compared to individually deposited metals during hydrogen evolution. Cathodic currents observed positive of the hydrogen-evolution region can be explained by electron-transfer processes involving p-InP surface states. In this latter potential region, i/sub 0/ values are higher for the sequentially deposited metals.

  16. Kinetic investigation of microbial souring in porous media using microbial consortia from oil reservoirs.

    PubMed

    Chen, C I; Reinsel, M A; Mueller, R F

    1994-07-01

    Microbial souring (H2S production) in porous media was investigated in an anaerobic upflow porous media reactor at 60 degrees C using microbial consortia obtained from oil reservoirs. Multiple carbon sources (formate, acetate, propionate, iso- and n-butyrates) found in reservoir waters as well as sulfate as the electron acceptor was used. Kinetics and rates of souring in the reactor system were analyzed. Higher volumetric substrate consumption rates (organic acids and sulfate) and a higher volumetric H(2)S production rate were found at the from part of the reactor column after H(2)S production had stabilized. Concentration gradients for the substrates (organic acids and sulfate) and H(2)S were generated along the column. Biomass accumulation throughout the entire column was observed. The average specific sulfate reduction rate (H(2)S production rate) in the present reactor after H(2)S production had stabilized was calculated to be 11062 +/-2.22 mg sulfate-S/day g biomass.

  17. A kinetic investigation of high-temperature mercury oxidation by chlorine.

    PubMed

    Wilcox, Jennifer

    2009-06-18

    First-stage mercury oxidation reactions typical of coal combustion flue gases were investigated. The present study is a determination of the kinetic and thermodynamic parameters of the bimolecular reactions, Hg + Cl(2) <--> HgCl + Cl, Hg + HCl <--> HgCl + H, and Hg + HOCl <--> HgCl + OH, at the B3LYP/RCEP60 VDZ level of theory over a temperature range of 298.15 to 2000 K at atmospheric pressure. Conventional transition state theory was used to predict the forward and reverse rate constants for each reaction and ab initio based equilibrium constant expressions were calculated as a function of temperature. Reasonable agreement was achieved between the calculated equilibrium constants and the available experimental values.

  18. A study to investigate phase transitions and nucleation kinetics of nickel and copper

    NASA Astrophysics Data System (ADS)

    Celik, F. A.; Yildiz, A. K.

    2016-04-01

    In this study, we investigate the homogeneous nucleation kinetics of copper and nickel system during cooling process using molecular dynamics simulation (MDS). The calculation is carried out for a different number of atoms consisting of 500, 2048, 8788 and 13,500 based on embedded atom method (EAM). It is observed that the melting points for the both model increases with increasing the size of systems (i.e. the number of atoms) as expected from Parrinello and Rahman MD method. The interfacial free energies and critical nucleus radius of nickel and copper are also determined by molecular dynamics, and the results are consistent with the classical nucleation theory. The structural development and phase transformation are also determined from the radial distribution function (RDF) and local bond orientational order parameters (LBOO).

  19. KMCThinFilm: A C++ Framework for the Rapid Development of Lattice Kinetic Monte Carlo (kMC) Simulations of Thin Film Growth

    DTIC Science & Technology

    2015-09-01

    Monte Carlo (kMC) Simulations of Thin Film Growth by James J Ramsey Approved for public release; distribution is...Research Laboratory KMCThinFilm: A C++ Framework for the Rapid Development of Lattice Kinetic Monte Carlo (kMC) Simulations of Thin Film Growth by...Simulations of Thin Film Growth 5a. CONTRACT NUMBER 5b. GRANT NUMBER 5c. PROGRAM ELEMENT NUMBER 6. AUTHOR(S) James J Ramsey 5d. PROJECT

  20. The BioFilm Ring Test: a Rapid Method for Routine Analysis of Pseudomonas aeruginosa Biofilm Formation Kinetics

    PubMed Central

    Olivares, Elodie; Badel-Berchoux, Stéphanie; Provot, Christian; Jaulhac, Benoît; Prévost, Gilles; Bernardi, Thierry

    2015-01-01

    Currently, few techniques are available for the evaluation of bacterial biofilm adhesion. These detection tools generally require time for culture and/or arduous handling steps. In this work, the BioFilm Ring Test (BRT), a new technology, was used to estimate the biofilm formation kinetics of 25 strains of Pseudomonas aeruginosa, isolated from the sputum of cystic fibrosis (CF) patients. The principle of the new assay is based on the mobility measurement of magnetic microbeads mixed with a bacterial suspension in a polystyrene microplate. If free to move under the magnetic action, particles gather to a visible central spot in the well bottom. Therefore, the absence of spot formation in the plate reflects the bead immobilization by a biofilm in formation. The BRT device allowed us to classify the bacterial strains into three general adhesion profiles. Group 1 consists of bacteria, which are able to form a solid biofilm in <2 h. Group 2 comprises the strains that progressively set up a biofilm during 24 h. Lastly, group 3 includes the strains that stay in a planktonic form. The grouping of our strains did not differ according to culture conditions, i.e., the use of different sets of beads or culture media. The BRT is shown to be an informative tool for the characterization of biofilm-forming bacteria. Various application perspectives may be investigated for this device, such as the addition of antibiotics to the bacterial suspension to select which would have the ability to inhibit the biofilm formation. PMID:26719437

  1. Laboratory investigation of the role of desorption kinetics on americium transport associated with bentonite colloids

    SciTech Connect

    Dittrich, Timothy Mark; Boukhalfa, Hakim; Ware, Stuart Douglas; Reimus, Paul William

    2015-07-13

    Understanding the parameters that control colloid-mediated transport of radionuclides is important for the safe disposal of used nuclear fuel. We report an experimental and reactive transport modeling examination of americium transport in a groundwater–bentonite–fracture fill material system. A series of batch sorption and column transport experiments were conducted to determine the role of desorption kinetics from bentonite colloids in the transport of americium through fracture materials. We used fracture fill material from a shear zone in altered granodiorite collected from the Grimsel Test Site (GTS) in Switzerland and colloidal suspensions generated from FEBEX bentonite, a potential repository backfill material. The colloidal suspension (100 mg L–1) was prepared in synthetic groundwater that matched the natural water chemistry at GTS and was spiked with 5.5 × 10–10 M241Am. Batch characterizations indicated that 97% of the americium in the stock suspension was adsorbed to the colloids. Breakthrough experiments conducted by injecting the americium colloidal suspension through three identical columns in series, each with mean residence times of 6 h, show that more than 95% of the bentonite colloids were transported through each of the columns, with modeled colloid filtration rates (kf) of 0.01–0.02 h–1. Am recoveries in each column were 55–60%, and Am desorption rate constants from the colloids, determined from 1-D transport modeling, were 0.96, 0.98, and 0.91 h–1 in the three columns, respectively. The consistency in Am recoveries and desorption rate constants in each column indicates that the Am was not associated with binding sites of widely-varying strengths on the colloids, as one binding site with fast kinetics represented the system accurately for all three sequential columns. As a result, our data suggest that colloid-mediated transport of Am in a bentonite-fracture fill

  2. Laboratory investigation of the role of desorption kinetics on americium transport associated with bentonite colloids.

    PubMed

    Dittrich, Timothy Mark; Boukhalfa, Hakim; Ware, Stuart Douglas; Reimus, Paul William

    2015-10-01

    Understanding the parameters that control colloid-mediated transport of radionuclides is important for the safe disposal of used nuclear fuel. We report an experimental and reactive transport modeling examination of americium transport in a groundwater-bentonite-fracture fill material system. A series of batch sorption and column transport experiments were conducted to determine the role of desorption kinetics from bentonite colloids in the transport of americium through fracture materials. We used fracture fill material from a shear zone in altered granodiorite collected from the Grimsel Test Site (GTS) in Switzerland and colloidal suspensions generated from FEBEX bentonite, a potential repository backfill material. The colloidal suspension (100 mg L(-1)) was prepared in synthetic groundwater that matched the natural water chemistry at GTS and was spiked with 5.5 × 10(-10) M (241)Am. Batch characterizations indicated that 97% of the americium in the stock suspension was adsorbed to the colloids. Breakthrough experiments conducted by injecting the americium colloidal suspension through three identical columns in series, each with mean residence times of 6 h, show that more than 95% of the bentonite colloids were transported through each of the columns, with modeled colloid filtration rates (k(f)) of 0.01-0.02 h(-1). Am recoveries in each column were 55-60%, and Am desorption rate constants from the colloids, determined from 1-D transport modeling, were 0.96, 0.98, and 0.91 h(-1) in the three columns, respectively. The consistency in Am recoveries and desorption rate constants in each column indicates that the Am was not associated with binding sites of widely-varying strengths on the colloids, as one binding site with fast kinetics represented the system accurately for all three sequential columns. Our data suggest that colloid-mediated transport of Am in a bentonite-fracture fill material system is unlikely to result in transport over long distance scales because

  3. Laboratory investigation of the role of desorption kinetics on americium transport associated with bentonite colloids

    DOE PAGES

    Dittrich, Timothy Mark; Boukhalfa, Hakim; Ware, Stuart Douglas; ...

    2015-07-13

    Understanding the parameters that control colloid-mediated transport of radionuclides is important for the safe disposal of used nuclear fuel. We report an experimental and reactive transport modeling examination of americium transport in a groundwater–bentonite–fracture fill material system. A series of batch sorption and column transport experiments were conducted to determine the role of desorption kinetics from bentonite colloids in the transport of americium through fracture materials. We used fracture fill material from a shear zone in altered granodiorite collected from the Grimsel Test Site (GTS) in Switzerland and colloidal suspensions generated from FEBEX bentonite, a potential repository backfill material. Themore » colloidal suspension (100 mg L–1) was prepared in synthetic groundwater that matched the natural water chemistry at GTS and was spiked with 5.5 × 10–10 M241Am. Batch characterizations indicated that 97% of the americium in the stock suspension was adsorbed to the colloids. Breakthrough experiments conducted by injecting the americium colloidal suspension through three identical columns in series, each with mean residence times of 6 h, show that more than 95% of the bentonite colloids were transported through each of the columns, with modeled colloid filtration rates (kf) of 0.01–0.02 h–1. Am recoveries in each column were 55–60%, and Am desorption rate constants from the colloids, determined from 1-D transport modeling, were 0.96, 0.98, and 0.91 h–1 in the three columns, respectively. The consistency in Am recoveries and desorption rate constants in each column indicates that the Am was not associated with binding sites of widely-varying strengths on the colloids, as one binding site with fast kinetics represented the system accurately for all three sequential columns. As a result, our data suggest that colloid-mediated transport of Am in a bentonite-fracture fill material system is unlikely to result in transport over long

  4. Enantioselective Supramolecular Carriers for Nucleoside Drugs. A Thermodynamic and Kinetic Gas Phase Investigation

    NASA Astrophysics Data System (ADS)

    Fraschetti, Caterina; Filippi, Antonello; Crestoni, Maria Elisa; Villani, Claudio; Roselli, Graziella; Mortera, Stefano Levi; Speranza, Maurizio

    2012-10-01

    The enantioselective interactions between chiral tetra-amidic receptors and nucleosides have been investigated by the ESI-IT-MS and ESI-FT-ICR-MS methodologies. Configurational effects on the CID fragmentation of diastereomeric [ M H 2 •H•A] + aggregates (A = 2'-deoxycytidine dC, citarabine ( ara-C) were found to be mostly offset by isotope effect in [ S X 2 •H•A] + (X = H, D) differently from the results obtained on the analogues (A = cytidine C and gemcitabine G). This result points the involvement of two different nucleoside/tetraamide isoforms. The structural differences of the [ M H 2 •H•A] + (A = C and G) complexes vs. the [ M H 2 •H•A] + ( dC and ara-C) ones is fully confirmed by the kinetics of their uptake of the 2-aminobutane enantiomers, measured by FT-ICR mass spectrometry. Indeed, uptake of the 2-aminobutane enantiomers by [ M H n •H•A] + (n = 1,2; A = dC and ara-C) complexes is reversible, while that by [ M H n •H•A] + (n = 1,2; A = C and G) is not. The most encouraging result concerning the measured fragmentation and kinetic differences between C and ara-C, that are just epimers, indicates the possibility to subtly modulate the non-covalent drug/receptor interactions, through the electronic properties of the 2'-substituent on the nucleoside furanose ring, and furthermore on its three-dimensional position.

  5. CO{sub 2} adsorption: Experimental investigation with kinetics verification and CFD reactor model validation

    SciTech Connect

    Breault, Ronald W,; Huckaby, Ernest D.; Shadle, Lawrence J; Spenik, James L.

    2013-01-01

    The National Energy Technology Laboratory is investigating a new process for CO{sub 2} capture from large sources such as utility power generation facilities as an alternative to liquid amine based absorption processes. Many, but not all of these advanced dry processes are based upon sorbents composed of supported polyamines. In this analysis, experiments have been conducted in a small facility at different temperatures and compared to CFD reactor predictions using kinetics obtained from TGA tests. This particular investigation compares the predicted performance and the experimental performance of one of these new class of sorbents in a fluidized bed reactor. In the experiment, the sorbent absorbs CO{sub 2} from simulated flue gas in a riser reactor, separates the carbonated particles from the de-carbonated flue gas in a cyclone and then regenerates the sorbent, creating a concentrated stream of pure CO{sub 2} for sequestration. In this work, experimental measurements of adsorption are compared to predictions from a 3-dimensional non-isothermal reacting multiphase flow model. The effects of the gas flow rate and reactor temperature are explored. It is shown that the time duration for CO{sub 2} adsorption decreased for an increase in the gas flow. The details of the experimental facility and the model as well as the comparative analysis between the data and the simulation results are discussed.

  6. A kinetic investigation on the gas-phase reaction of ozone with four sesquiterpenes

    NASA Astrophysics Data System (ADS)

    Richters, Stefanie; Herrmann, Hartmut; Berndt, Torsten

    2014-05-01

    Sesquiterpenes (C15H24, SQT) are emitted by plants with a global emission rate of about 15 Tg per year (Seinfeld and Pankow, 2003). They are possibly an important source of secondary organic aerosol (SOA) but their oxidation processes are scarcely examined. This study focusses on the kinetics of the reaction of ozone with four atmospherically relevant SQT: β-caryophyllene, α-humulene, α-cedrene and isolongifolene. Up to now there are only two studies available in the literature describing kinetic measurements of the ozonolysis of a series of SQT, (Shu and Atkinson, 1994; Ghalaieny et al., 2012). As a result of these studies the rate coefficients of the ozone reaction with β-caryophyllene and α-humulene differ by three orders of magnitude making a reinvestigation necessary. Both literature studies were carried out in a reaction chamber with long reaction times. Shu and Atkinson (1994) used high concentrations of [SQT] = 2.4 • 1013 molecules cm-3 and [O3] = 2.5 • 1012 molecules cm-3 making particle formation and consecutive reactions relevant. The latter study of Ghalaieny et al. (2012) investigated the reaction at even higher concentrations ([SQT] = (2.1 - 3.5) • 1014 molecules cm-3, [O3] > 2.1 • 1015 molecules cm-3) at elevated temperatures (366 K) to avoid particle formation. Our study was carried out with very low SQT concentrations ((1 - 2) • 1010 molecules cm-3), [O3] = (1 - 15) • 1011 molecules cm-3, in a flow tube at atmospheric pressure and room temperature. The relative rate coefficients were investigated by means of an online GC-MS technique allowing measuring SQT concentrations down to 109 molecules cm-3. Particle formation was detected using an ultrafine condensed particle counter (TSI-3025 with a 50% cut-off size of 2.5 - 3 nm) and was found to be negligible under the chosen reaction conditions. Our study supports the rate coefficients as given by Shu and Atkinson (1994). References: J. H. Seinfeld and J. F. Pankow, Annu. Rev. Phys

  7. In Situ Biospectroscopic Investigation of Rapid Ischemic and Postmortem Induced Biochemical Alterations in the Rat Brain

    PubMed Central

    2015-01-01

    Rapid advances in imaging technologies have pushed novel spectroscopic modalities such as Fourier transform infrared spectroscopy (FTIR) and X-ray absorption spectroscopy (XAS) at the sulfur K-edge to the forefront of direct in situ investigation of brain biochemistry. However, few studies have examined the extent to which sample preparation artifacts confound results. Previous investigations using traditional analyses, such as tissue dissection, homogenization, and biochemical assay, conducted extensive research to identify biochemical alterations that occur ex vivo during sample preparation. In particular, altered metabolism and oxidative stress may be caused by animal death. These processes were a concern for studies using biochemical assays, and protocols were developed to minimize their occurrence. In this investigation, a similar approach was taken to identify the biochemical alterations that are detectable by two in situ spectroscopic methods (FTIR, XAS) that occur as a consequence of ischemic conditions created during humane animal killing. FTIR and XAS are well suited to study markers of altered metabolism such as lactate and creatine (FTIR) and markers of oxidative stress such as aggregated proteins (FTIR) and altered thiol redox (XAS). The results are in accordance with previous investigations using biochemical assays and demonstrate that the time between animal death and tissue dissection results in ischemic conditions that alter brain metabolism and initiate oxidative stress. Therefore, future in situ biospectroscopic investigations utilizing FTIR and XAS must take into consideration that brain tissue dissected from a healthy animal does not truly reflect the in vivo condition, but rather reflects a state of mild ischemia. If studies require the levels of metabolites (lactate, creatine) and markers of oxidative stress (thiol redox) to be preserved as close as possible to the in vivo condition, then rapid freezing of brain tissue via decapitation into

  8. Micromodel Investigation of Transport Effect on the Kinetics of Reductive Dissolution of Hematite

    SciTech Connect

    Zhang, Changyong; Liu, Chongxuan; Shi, Zhi

    2013-03-13

    Reductive dissolution of hematite in porous media was investigated using a micromodel with realistic pore network structures that include distinctive advection domain, macro-pores and micro-pores created in silicon substrate. The micromodel pore surface was sputter deposited with a thin layer (230 nm) of hematite. The hematite in the micromodel was reduced by injecting pH-varying solutions containing a reduced form of flavin mononucleotide (FMNH2), a biogenic soluble electron transfer mediator produced by Shewanella species. The reduction kinetics was determined by measuring effluent Fe(II) concentration and by spectroscopically monitoring the hematite dissolution front in the micromodel. Batch experiment was also performed to estimate the hematite reduction rate under the well-mixed condition. The results showed a significant spatial variation in local redox reaction rate that was controlled by the coupled diffusion and reaction. The overall rate of the redox reaction in the micromodel required a three-domain numerical model to effectively describe with distinctive rate parameters in different pore domains. Results from this study demonstrated the important scaling effect when extrapolating geochemical or biogeochemical reaction rate from batch reactor to porous media and indicated a significant control of physical transport mechanisms on the reaction rate scaling.

  9. Kinetic investigation of microbial souring in porous media using microbial consortia from oil reservoirs

    SciTech Connect

    Chen, C.I.; Reinsel, M.A.; Mueller, R.F. . National Science Foundation Engineering Research Center for Biofilm Engineering)

    1994-07-01

    Microbial souring (H[sub 2]S production) in porous media was investigated in an anaerobic upflow porous media reactor at 60 C using microbial consortia obtained from oil reservoirs. Multiple carbon sources (formate, acetate, propionate, iso and n-butyrates) found in reservoir waters as well as sulfate as the electron acceptor were used. Kinetics and rates of souring in the reactor system were analyzed. Higher volumetric substrate consumption rates (organic acids and sulfate) and a higher volumetric H[sub 2]S production rate were found at the front part of the reactor column after H[sub 2]S production had stabilized. Concentration gradients for the substrates (organic acids and sulfate) and H[sub 2]S were generated along the column. Biomass accumulation throughout the entire column was observed. The average specific sulfate reduction rate (H[sub 2]S production rate) in the present reactor after H[sub 2]S production had stabilized was calculated to be 11.62 [+-] 2.22 mg sulfate-S/day g biomass.

  10. Investigation of the kinetics of reduction of nickel tungstate by hydrogen

    SciTech Connect

    Sridhar, S. . Dept. of Materials Science and Engineering); Du Sichen; Seetharaman, S. . Dept. of Metallurgy)

    1994-06-01

    In the present work, the kinetics of reduction of nickel tungstate, NiWO[sub 4], by hydrogen was investigated by a thermogravimetric method in the temperature range 891 to 1,141 K. The experiments were conducted under both isothermal and nonisothermal conditions. The products were examined by X-ray diffraction analysis. The results indicate that the reduction reaction proceeds in two steps; first, reduction of NiWO[sub 4] to nickel as well as WO[sub 2] and then WO[sub 2] to tungsten. From the isothermal experiments, the activation energies of the two reaction steps were calculated to be 95.3 [+-] 4.9 and 80.8 [+-] 6.4 kJ [center dot] mol[sup [minus]1], respectively. The activation energy value obtained from nonisothermal experiments for the first step is in agreement with the isothermal experiments. The values are compared with the activation energies reported in other literature for the individual oxides.

  11. Kinetic and spectral investigation of allosteric interaction of coenzymes with 2-oxo acid dehydrogenase complexes

    NASA Astrophysics Data System (ADS)

    Strumiło, S.; Czygier, M.; Kondracikowska, J.; Dobrzyń, P.; Czerniecki, J.

    2002-09-01

    The possible role of thiamine pyrophosphate (TPP) in the regulation of both multienzyme pyruvate dehydrogenase complex (PDC) and 2-oxoglutarate dehydrogenase complex (OGDC) has been investigated by kinetic and spectral methods. The purified PDC and OGDC from animal heart muscle were near saturated with endogenous TPP. The PDC containing the bound coenzyme showed hysteretic behaviour manifested in a lag phase of the catalysed reaction after the contact of PDC with substrates. Exogenous TPP added to the full reaction medium led to a disappearance of the lag phase and to strong reduction of the Michaelis constant ( Km) value for pyruvate, and more moderate decrease of Km for both coenzyme A and NAD. In the case of OGDC exogenous TPP also decreased S 0.5 ( Km) for substrate 2-oxoglutarate. In addition, exogenous TPP changed both the UV and circular dichroism spectra of PDC and last one of OGDC, and lowered the fluorescence emission of the multienzyme complexes containing bound molecules of endogenous coenzyme in their active sites. Thiamine pyrophosphate seems to play, besides its coenzyme function, the role of positive allosteric effector which causes conformational changes of the multienzyme complexes and increases their affinity to substrates.

  12. Survey of high-enthalpy shock facilities in the perspective of radiation and chemical kinetics investigations

    NASA Astrophysics Data System (ADS)

    Reynier, Philippe

    2016-08-01

    This contribution is a survey of the capabilities of the main facilities, shock-tubes, shock-tunnels, expansion tubes and hot-shots that allow the experimental investigation of chemical kinetics and radiation of hypersonic flows encountered during atmospheric entry. At first, the capabilities of the main facilities available in Australia, Asia, Europe, and United States, have been surveyed using the available literature, and the specific use of each facility identified. The second step of the study consists in an analysis of each type of shock facility to identify their advantages and drawbacks. The main objective of this analysis is to support a trade-off for the selection of the type of facility to be developed in order to give Europe a ground test with the capabilities to support future exploration and sample return missions. The last point of the study has been to identify the experimental datasets related to the targeted application, and to select the most attractive for the validation of the future facility.

  13. Purification of lactoperoxidase from bovine whey and investigation of kinetic parameters

    PubMed Central

    Borzouee, Fatemeh; Mofid, Mohammad Reza; Varshosaz, Jaleh; Samsam Shariat, Seyed Ziyae Aldin

    2016-01-01

    Background: Lactoperoxidase (LPO) is related to mammalian peroxidase family which contains a wide spectrum of biological activities. Despite the wide studies on the LPO, there is little study has been performed to simplify and shorten the procedure of enzyme purification. The aim of this project was to purify the enzyme through a simple method, and investigating enzyme kinetic parameters. Materials and Methods: LPO was purified from bovine whey through modified method of Yoshida (1990) using two steps of ammonium sulfate precipitation and ion-exchange chromatography. The purity of isolated enzyme was monitored by sodium dodecyl sulfate-polyacrylamide gel electrophoresis (SDS-PAGE). Results: The enzyme was purified 59.13-fold with a recovery of 10.26 having a specific activity of 5.78 U/mg protein and an Rz value of 0.8. The enzyme activity was measured using guaiacol as a chromogenic substrate in phosphate buffer pH 6. SDS-PAGE showed a single bond with molecular weight of 78 kDa. The purified enzyme displayed optimum activity at pH 6 in 30 mM phosphate buffer and at a temperature of 50°C, with a Km value of 178 mM and Vmax 0.63 U/ml.min for guaiacol. Conclusion: Using only one step ion-exchange chromatography, LPO was isolated from bovine whey in high purity. PMID:28028529

  14. A kinetic Monte Carlo approach to investigate antibiotic translocation through bacterial porins

    NASA Astrophysics Data System (ADS)

    Ceccarelli, Matteo; Vargiu, Attilio V.; Ruggerone, Paolo

    2012-03-01

    Many relevant biological processes take place on time scales not reachable by standard all-atom computer simulations. The translocation of antibiotics through non-specific bacterial porins is an example. Microscopic effects compete to determine penetration routes and, consequently, free energy barriers to be overcome. Since bacteria can develop resistance to treatment also by reducing their antibiotic permeability, to understand the microscopic aspects of antibiotic translocation is an important step to rationalize drug design. Here, to investigate the translocation we propose a complete numerical model that combines the diffusion-controlled rate theory and a kinetic Monte Carlo scheme based on both experimental data and microscopically well-founded all-atom simulations. Within our model, an antibiotic translocating through an hour-glass-shaped channel can be described as a molecule moving on a potential of mean force featuring several affinity sites and a high central barrier. The implications of our results for the characterization of antibiotic translocation at in vivo concentrations are discussed. The presence of an affinity site close to the mouth of the channel seems to favor the translocation of antibiotics, the affinity site acting as a particle reservoir. Possible connections between results and the appearance of mutations in clinical strains are also outlined.

  15. A Preliminary Investigation of Rapid Depressurization Phenomena Following a Sudden DLOFC in a VHTR

    SciTech Connect

    Richard C. Martineau; Ray A. Berry; Dana A. Knoll

    2009-03-01

    Air ingress has been identified as a potential threat for Very High Temperature gas-cooled Reactors (VHTR). Reactor components constructed of graphite will, at high temperatures, produce exothermic reactions in the presence of oxygen. The danger lies in the possibility of fuel element damage and core structural failure. Previous investigations of air ingress mechanisms have focused on thermal and molecular diffusion, density-driven stratified flow, and natural convection. Here, we investigate the possibility of a rapid ingress of air due to a Taylor wave expansion after a hypothetical sudden loss of coolant accident (LOCA) scenario in a VHTR. Our analysis starts with a one-dimensional shock tube simulation to simply illustrate the development of a Taylor wave with resulting reentrant flow. Then, a simulation is performed of an idealized two-dimensional axisymmetric representation of the lower plenum of General Atomics GT-MHR subjected to a hypothetical catastrophic break of the hot duct. Analysis shows the potential for significant and rapid air ingress into the reactor vessel in the case of a large break in the cooling system.

  16. A Preliminary Investigation of Rapid Depressurization Phenomena Following a Sudden DLOFC in a VHTR

    SciTech Connect

    Richard C. Martineau; Ray A. Berry

    2010-05-01

    Air ingress has been identified as a potential threat for Very High Temperature gas-cooled Reactors (VHTR). Reactor components constructed of graphite will, at high temperatures, produce exothermic reactions in the presence of oxygen. The danger lies in the possibility of fuel element damage and core structural failure. Previous investigations of air ingress mechanisms have focused on thermal and molecular diffusion, density-driven stratified flow due to hydrodynamic instability, and natural convection. Here, we investigate the possibility of a rapid flow reversal of helium coolant due to a Taylor (rarefaction) wave expansion after a hypothetical sudden Depressurized Loss of Forced Cooling (DLOFC) scenario in a VHTR. Conceivably, flow reversal of the helium coolant could entrain significant quantities of air into the reactor vessel. Our analysis starts with a one-dimensional shock tube simulation to simply illustrate the development of a Taylor wave with resulting reentrant flow. Then, a simulation is performed of an idealized two-dimensional axisymmetric representation of the lower plenum of General Atomics GT-MHR subjected to a hypothetical catastrophic break of the hot duct. Analysis shows the potential for significant and rapid air ingress into the reactor vessel in the case of a large break in the cooling system.

  17. Kinetic and thermodynamic investigation on ascorbate oxidase activity and stability of a Cucurbita maxima extract.

    PubMed

    Porto, Tatiana S; Porto, Camila S; Cavalcanti, Maria T H; Filho, José L Lima; Perego, Patrizia; Porto, Ana L F; Converti, Attilio; Pessoa, Adalberto

    2006-01-01

    The kinetic and thermodynamic properties of ascorbate oxidase (AO) activity and stability of a Cucurbita maxima extract were investigated. Activity tests performed at 25 degrees C using initial ascorbic acid concentration in the range 50-750 M allowed estimating the Michaelis constant for this substrate (Km = 126 microM) and the maximum initial rate of ascorbic acid oxidation (A0,max = 1.57 mM min-1). The main thermodynamic parameters of the enzyme reaction (DeltaH* = 10.3 kJ mol-1; DeltaG* = 87.2 kJ mol-1; DeltaS* = -258 J mol-1 K-1) were estimated through activity tests performed at 25-48 C. Within such a temperature range, no decrease in the initial reaction rate was detected. The long-term thermostability of the raw extract was then investigated by means of residual activity tests carried out at 10-70 degrees C, which allowed estimating the thermodynamic parameters of the irreversible enzyme inactivation as well (DeltaH*D = 51.7 kJ mol-1; DeltaG*D = 103 kJ mol-1; S*D = -160 J mol-1 K-1). Taking into account the specific rate of AO inactivation determined at different temperatures, we also estimated the enzyme half-life (1047 min at 10 degrees C and 21.2 min at 70 degrees C) and predicted the integral activity of a continuous system using this enzyme preparation. This work should be considered as a preliminary attempt to characterize the AO activity of a C. maxima extract before its concentration by liquid-liquid extraction techniques.

  18. Rapid kinetics of iron responsive element (IRE) RNA/iron regulatory protein 1 and IRE-RNA/eIF4F complexes respond differently to metal ions

    PubMed Central

    Khan, Mateen A.; Ma, Jia; Walden, William E.; Merrick, William C.; Theil, Elizabeth C.; Goss, Dixie J.

    2014-01-01

    Metal ion binding was previously shown to destabilize IRE-RNA/IRP1 equilibria and enhanced IRE-RNA/eIF4F equilibria. In order to understand the relative importance of kinetics and stability, we now report rapid rates of protein/RNA complex assembly and dissociation for two IRE-RNAs with IRP1, and quantitatively different metal ion response kinetics that coincide with the different iron responses in vivo. kon, for FRT IRE-RNA binding to IRP1 was eight times faster than ACO2 IRE-RNA. Mn2+ decreased kon and increased koff for IRP1 binding to both FRT and ACO2 IRE-RNA, with a larger effect for FRT IRE-RNA. In order to further understand IRE-mRNA regulation in terms of kinetics and stability, eIF4F kinetics with FRT IRE-RNA were determined. kon for eIF4F binding to FRT IRE-RNA in the absence of metal ions was 5-times slower than the IRP1 binding to FRT IRE-RNA. Mn2+ increased the association rate for eIF4F binding to FRT IRE-RNA, so that at 50 µM Mn2+ eIF4F bound more than 3-times faster than IRP1. IRP1/IRE-RNA complex has a much shorter life-time than the eIF4F/IRE-RNA complex, which suggests that both rate of assembly and stability of the complexes are important, and that allows this regulatory system to respond rapidly to change in cellular iron. PMID:24728987

  19. Very rapid virologic response and early HCV response kinetics, as quick measures to compare efficacy and guide a personalized response-guided therapy

    PubMed Central

    Yakoot, Mostafa; Abdo, Alaa M; Yousry, Ahmed; Helmy, Sherine

    2016-01-01

    Background This is the second and final report for our study designed to compare two generic sofosbuvir products for the degree and speed of virologic response to a dual anti-hepatitis C virus (HCV) treatment protocol. We aimed to test the applicability of the early virus response kinetics and the very rapid virologic response (vRVR) rate as quick outcome measures for accelerated comparative efficacy studies and as a foundation for a personalized response-guided therapy. Methods Fifty eligible chronic HCV patients were randomized to either one of two generic sofosbuvir products (Gratisovir or Grateziano) at a daily dose of one 400 mg tablet plus a weight-based ribavirin dose. Data were compared between the groups for early virus response kinetics and vRVR rates in relation to the rates of final sustained virologic response at week 12 posttreatment (SVR12). Results The Log10 transformed virus load (Log polymerase chain reaction) curves showed fairly similar rapid decline during the first 2 weeks, with no significant difference between the groups at four analysis points throughout the study by repeated-measures factorial analysis of variance test (P=0.48). The SVR12 rates were 96% (95% confidence interval, 79.6%–99.9%) in Gratisovir group (24/25) and 95.7% (95% confidence interval, 78%–99.9%) in Grateziano group (22/23). There was no statistically significant difference found by exact test (P>0.999). There was a significant association between the vRVR and the SVR12, with 100% positive predictive value (38/38 of those who had vRVR, achieved a final SVR12) and 82.6% sensitivity (among the total 46 with SVR12, 38 were having vRVR). Conclusion We can conclude from our study that the early HCV response kinetics and the vRVR rates could be used as sensitive quick markers for efficacy (with a very high positive predictive value for SVR12), based on our accelerated comparative efficacy research model. This might open the way for new models of accelerated equivalence

  20. The nature of the intermediates in the reactions of Fe(III)- and Mn(III)-microperoxidase-8 with H(2)O(2): a rapid kinetics study.

    PubMed

    Primus, Jean-Louis; Grunenwald, Sylvie; Hagedoorn, Peter-Leon; Albrecht-Gary, Anne-Marie; Mandon, Dominique; Veeger, Cees

    2002-02-20

    Kinetic studies were performed with microperoxidase-8 (Fe(III)MP-8), the proteolytic breakdown product of horse heart cytochrome c containing an octapeptide linked to an iron protoporphyrin IX. Mn(III) was substituted for Fe(III) in Mn(III)MP-8. The mechanism of formation of the reactive metal-oxo and metal-hydroperoxo intermediates of M(III)MP-8 upon reaction of H(2)O(2) with Fe(III)MP-8 and Mn(III)MP-8 was investigated by rapid-scan stopped-flow spectroscopy and transient EPR. Two steps (k(obs1) and k(obs2)) were observed and analyzed for the reaction of hydrogen peroxide with both catalysts. The plots of k(obs1) as function of [H(2)O(2)] at pH 8.0 and pH 9.1 for Fe(III)MP-8, and at pH 10.2 and pH 10.9 for Mn(III)MP-8, exhibit saturation kinetics, which reveal the accumulation of an intermediate. Double reciprocal plots of 1/k(obs1) as function of 1/[H(2)O(2)] at different pH values reveal a competitive effect of protons in the oxidation of M(III)MP-8. This effect of protons is confirmed by the linear dependence of 1/k(obs1) on [H(+)] showing that k(obs1) increases with the pH. The UV-visible spectra of the intermediates formed at the end of the first step (k(obs1)) exhibit a spectrum characteristic of a high-valent metal-oxo intermediate for both catalysts. Transient EPR of Mn(III)MP-8 incubated with an excess of H(2)O(2), at pH 11.5, shows the detection of a free radical signal at g approximately equal to 2 and of a resonance at g approximately equal to 4 characteristic of a Mn(IV) (S = 3/2) species. On the basis of these results, the following mechanism is proposed: (i) M(III)MP-8-OH(2) is deprotonated to M(III)MP-8-OH in a rapid preequilibrium step, with a pK(a) = 9.2 +/- 0.9 for Fe(III)MP-8 and a pK(a) = 11.2 +/- 0.3 for Mn(III)MP-8; (ii) M(III)MP-8-OH reacts with H(2)O(2) to form Compound 0, M(III)MP8-OOH, with a second-order rate constant k(1) = (1.3 +/- 0.6) x 10(6) M(-1) x s(-1) for Fe(III)MP-8 and k(1) = (1.6 +/- 0.9) x 10(5) M(-1) x s(-1) for Mn

  1. Investigation of the electrode kinetics in a solid oxide fuel cell and an oxygen sensor

    NASA Astrophysics Data System (ADS)

    Radhakrishnan, Rajesh

    This dissertation investigates the electrode kinetics in a solid oxide fuel cell and an oxygen sensor. The first chapter describes the basics of fuel cell and motivation behind the studies. The second chapter investigates the dependence of cathodic charge transfer reaction resistance (Rct), on three-phase boundary length (lTPB) at various temperatures and oxygen partial pressures ( pO2 ). Impedance spectra were obtained using three-electrode configuration on discs having cathodes with definite lTPB to investigate the La0.8Sr0.2MnO3 (LSM)-Y 0.16Zr0.84O2 (YSZ), platinum (Pt)-YSZ and La 0.8Sr0.2CoO3 (LSC)-Ce0.8Sm0.2 O2 (SDC) half cell reactions at temperatures between 650--800°C and pO2 between 10-3 to 1 atm. For LSM-YSZ and Pt-YSZ, 1/Rct varies linearly with lTPB. LSC-SDC system did not show any specific dependence between R ct and lTPB. The third chapter examines the use of an electrolyte supported cell with externally applied voltage to determine the single electrode overpotential and extending the parameters derived to that of an anode supported fuel cell having thin film electrolyte operating under a chemical potential gradient. Spatial distributions of the electrochemical potential of electrons (ϕ) and oxygen ions ( m˜O-2 ), and chemical potential of oxygen ( mO2 ) for these two cases were obtained. Under fuel cell operating conditions, ϕ, m˜O-2 and mO2 , decreases monotonically from higher value to lower value. For electrolyte supported cell under externally applied voltage mO2 does not vary monotonically; it reaches values above or below that of the boundary values, leading to development of internal electromotive forces (EMFs), which can in turn affect the activity of the interface. The fourth chapter describes design microfabrication and characterization of a series connected potentiometric oxygen sensor. A drawback of potentiometric sensors in general is that the output signal is low when the ratio of the partial pressures at the two electrodes is low

  2. Purification of 6-phosphogluconate dehydrogenase from parsley (Petroselinum hortense) leaves and investigation of some kinetic properties.

    PubMed

    Demir, Hülya; Ciftçi, Mehmet; Küfrevioğlu, O Irfan

    2003-02-01

    In this study, 6-phosphogluconate dehydrogenase (E.C.1.1.44; 6PGD) was purified from parsley (Petroselinum hortense) leaves, and analysis of the kinetic behavior and some properties of the enzyme were investigated. The purification consisted of three steps that are preparation of homogenate ammonium sulfate fractionation and on DEAE-Sephadex A50 ion exchange. The enzyme was obtained with a yield of 49% and had a specific activity of 18.3 U (mg proteins)(-1) (Lehninger, A.L.; Nelson, D.L.; Cox, M.M. Principles of Biochemistry, 2nd Ed.; Worth Publishers Inc.: N.Y., 2000, 558-560). The overall purification was about 339-fold. A temperature of +4 degrees C was maintained during the purification process. Enzyme activity was spectrophotometrically measured according to the Beutler method at 340 mn. In order to control the purification of the enzyme, SDS-polyacrylamide gel electrophoresis was carried out in 4% and 10% acrylamide for stacking and running gel, respectively. SDS-polyacrylamide gel electrophoresis showed a single band for enzyme. The molecular weight was found to be 97.5 kDa by Sephadex G-150 gel filtration chromatography. A protein band corresponding to a subunit molecular weight of 24.1 kDa was obtained on SDS-polyacrylamide gel electrophoresis. For the enzymes, the stable pH, optimum pH, and optimum temperature were found as 8.0, 8.0, and 50 degrees C, respectively. In addition, KM and Vmax values for NADP+ and G6-P at optimum pH and 25 degrees C were determined by means of Lineweaver-Burk plots.

  3. Ex-Situ Kinetic Investigations of the Formation of the Poly-Oxo Cluster U38.

    PubMed

    Falaise, Clément; Volkringer, Christophe; Hennig, Christoph; Loiseau, Thierry

    2015-11-09

    The ex-situ qualitative study of the kinetic formation of the poly-oxo cluster U38 , has been investigated after the solvothermal reaction. The resulting products have been characterized by means of powder XRD and scanning electron microscopy (SEM) for the solid phase and UV/Vis, X-ray absorption near edge structure (XANES), extended X-ray absorption fine structure (EXAFS), and NMR spectroscopies for the supernatant liquid phase. The analysis of the different synthesis batches, stopped at different reaction times, revealed the formation of spherical crystallites of UO2 from t=3 h, after the formation of unknown solid phases at an early stage. The crystallization of U38 occurred from t=4 h at the expense of UO2 , and is completed after t=8 h. Starting from pure uranium(IV) species in solution (t=0-1 h), oxidation reactions are observed with a U(IV) /U(VI) ratio of 70:30 for t=1-3 h. Then, the ratio is inversed with a U(IV) /U(VI) ratio of 25/75, when the precipitation of UO2 occurs. Thorough SEM observations of the U38 crystallites showed that the UO2 aggregates are embedded within. This may indicate that UO2 acts as reservoir of uranium(IV), for the formation of U38 , stabilized by benzoate and THF ligands. During the early stages of the U38 crystallization, a transient crystallized phase appeared at t=4 h. Its crystal structure revealed a new dodecanuclear moiety (U12 ), based on the inner hexanuclear core of {U6 O8 } type, decorated by three additional pairs of dinuclear U2 units. The U12 motif is stabilized by benzoate, oxalates, and glycolate ligands.

  4. Investigation of Copper Ammonia Leaching from Smelter Slags: Characterization, Leaching and Kinetics

    NASA Astrophysics Data System (ADS)

    Bidari, Ehsan; Aghazadeh, Valeh

    2015-10-01

    Although ammonia leaching of copper from slags has been reported generally as a part of copper slag utilization methods, but no detailed studies have been reported in the literature. In this research, we tried to investigate the effect of different parameters on ammonia leaching of copper from copper smelting slag by identifying different copper-bearing phases and following them during leaching time. Mineralogical characterization of the smelting slag (1.7 pct Cu) was done using X-ray fluorescence, X-ray diffraction, optical microscopy, diagnostic leaching tests, and scanning electron microscopy. The characterization studies indicated that main copper-bearing species are soluble copper oxides and chalcocite along with minor amount of covellite, bornite, blister copper particles, and chalcopyrite. It was also found that only approximately 0.2 pct Cu was present in the insoluble bulk silicate phases. These results suggest that approximately 88 pct of the total copper of slag could be extracted by ammonia sulfide leaching. Leaching tests were carried out and the effects of various parameters, namely pH, ammonia concentration, temperature, presence of oxygen, stirring speed, and pulp density were examined on copper leaching. The temperature and stirring speed had the most pronounced effect on the copper leaching, whereas ammonia affected the leaching yield at low concentrations of ammonia. It was found that 78 pct of Cu could be extracted within 4 hours and under optimum conditions: T = 343 K (70 °C), 2M ammonia, pH 10.5, stirring speed = 900 rpm, pulp density = 10 pct ( w s/ v). The kinetic data were analyzed with the shrinking core models, and it was found that the leaching process is controlled by both the interfacial transfer and diffusion across the product layer and the activation energy is calculated to be 49.4 kJ mol-1.

  5. Investigating the feasibility of rapid MRI for image-guided motion management in lung cancer radiotherapy.

    PubMed

    Sawant, Amit; Keall, Paul; Pauly, Kim Butts; Alley, Marcus; Vasanawala, Shreyas; Loo, Billy W; Hinkle, Jacob; Joshi, Sarang

    2014-01-01

    Cycle-to-cycle variations in respiratory motion can cause significant geometric and dosimetric errors in the administration of lung cancer radiation therapy. A common limitation of the current strategies for motion management is that they assume a constant, reproducible respiratory cycle. In this work, we investigate the feasibility of using rapid MRI for providing long-term imaging of the thorax in order to better capture cycle-to-cycle variations. Two nonsmall-cell lung cancer patients were imaged (free-breathing, no extrinsic contrast, and 1.5 T scanner). A balanced steady-state-free-precession (b-SSFP) sequence was used to acquire cine-2D and cine-3D (4D) images. In the case of Patient 1 (right midlobe lesion, ~40 mm diameter), tumor motion was well correlated with diaphragmatic motion. In the case of Patient 2, (left upper-lobe lesion, ~60 mm diameter), tumor motion was poorly correlated with diaphragmatic motion. Furthermore, the motion of the tumor centroid was poorly correlated with the motion of individual points on the tumor boundary, indicating significant rotation and/or deformation. These studies indicate that image quality and acquisition speed of cine-2D MRI were adequate for motion monitoring. However, significant improvements are required to achieve comparable speeds for truly 4D MRI. Despite several challenges, rapid MRI offers a feasible and attractive tool for noninvasive, long-term motion monitoring.

  6. Using the Deepwater Horizon Disaster to Investigate Natural Biogeochemical Cycling Associated with Rapid Methane Emissions (Invited)

    NASA Astrophysics Data System (ADS)

    Kessler, J. D.; Valentine, D. L.; Yvon-Lewis, S. A.; Heintz, M. B.; Hu, L.; Garcia Tigreros, F.; Du, M.; Chan, E. W.

    2010-12-01

    On April 20, a violent methane discharge severed the Deepwater Horizon rig from its well and oil and gas began spilling into the deep Gulf of Mexico at depths of ca. 1.5 km simulating a natural, rapid, and short-term methane release in deepwater. Given the estimated rates of emission of total material as well as the fraction methane by weight, one can estimate that a total of 0.1 to 0.3 Tg (10^12 g) of methane were emitted from a localized area in only 83 days. Measurements of methane oxidation and sea-air methane flux were measured in June indicating that at that time, oxidation rates were slow and sea-air fluxes were relatively insignificant. A deepwater methane plume was identified and in June 2010, the depth of the methane plume was on average from 950 - 1150 m with the maximum methane concentration measured being 183 μM. Analyses of diffusion, advective mixing, and methane oxidation were used to estimate that this plume has a lifetime of years to decades with the main controlling factor being the rate of methane oxidation. The persistent nature of this deepwater methane plume allows it to be used as a natural laboratory to investigate key hypotheses concerning the biogeochemical cycling of methane and oxygen associated with rapid, short-term methane discharges.

  7. Investigation of rapidly solidified aluminum by using diamond turning and a magnetorheological finishing process

    NASA Astrophysics Data System (ADS)

    Cheng, Yuan-Chieh; Hsu, Wei-Yao; Kuo, Ching-Hsiang; Abou-El-Hossein, Khaled; Otieno, Timothy

    2015-08-01

    The metal mirror has been widely used in optical application for a longtime. Especially the aluminum 6061 is often considered the preferred material for manufacturing optical components for ground-based astronomical applications. One reason for using this material is its high specific stiffness and excellent thermal properties. However, a large amount of data exists for this material and commercially available aluminum 6061 using single point diamond turning (SPDT) and polishing process can achieve surface roughness values of approximately 2 to 4 nm, which is adequate for applications that involve the infrared spectral range, but not for the shorter spectral range. A novel aluminum material, fabricated using a rapid solidification process that is equivalent to the conventional aluminum 6061 alloy grade has been used in optical applications in recent years because of its smaller grain size. In this study, the surface quality of the rapid solidification aluminum after single point diamond turning and followed by magnetorheological finish (MRF) process is investigated and compared with conventional aluminum 6061. Both the surface roughness Ra was evaluated using white light interferometers. Finally, indicators such as optimal fabrication parameter combination and optical performance are discussed.

  8. The development of an experimental facility and investigation of rapidly maneuvering Micro-Air-Vehicle wings

    NASA Astrophysics Data System (ADS)

    Wilson, Lee Alexander

    Vertical Takeoff-and-Landing (VTOL) Micro Air Vehicles (MAVs) provide a versatile operational platform which combines the capabilities of fixed wing and rotary wing MAVs. In order to improve performance of these vehicles, a better understanding of the rapid transition between horizontal and vertical flight is required. This study examines the flow structures around the Mini-Vertigo VTOL MAV using flow visualization techniques. This will gives an understanding of the flow structures which dominate the flight dynamics of rapid pitching maneuvers. This study consists of three objectives: develop an experimental facility, use flow visualization to investigate the flow around the experimental subject during pitching, and analyze the results. The flow around the Mini-Vertigo VTOL MAV is dominated by the slipstream from its propellers. The slipstream delays LE separation and causes drastic deflection in the flow. While the frequency of the vortices shed from the LE and TE varies with flow speed, the non-dimensional frequency does not. It does, however, vary slightly with the pitching rate. These results are applicable across a wide range of flight conditions. The results correlate to previous research done to examine the aerodynamic forces on the MAV.

  9. Investigating rapid eye movement sleep without atonia in Parkinson's disease using the rapid eye movement sleep behavior disorder screening questionnaire.

    PubMed

    Bolitho, Samuel J; Naismith, Sharon L; Terpening, Zoe; Grunstein, Ron R; Melehan, Kerri; Yee, Brendon J; Coeytaux, Alessandra; Gilat, Moran; Lewis, Simon J G

    2014-05-01

    Rapid eye movement (REM) sleep behavior disorder (RBD) is frequently observed in patients with Parkinson's disease (PD). Accurate diagnosis is essential for managing this condition. Furthermore, the emergence of idiopathic RBD in later life can represent a premotor feature, heralding the development of PD. Reliable, accurate methods for identifying RBD may offer a window for early intervention. This study sought to identify whether the RBD screening questionnaire (RBDSQ) and three questionnaires focused on dream enactment were able to correctly identify patients with REM without atonia (RWA), the neurophysiological hallmark of RBD. Forty-six patients with PD underwent neurological and sleep assessment in addition to completing the RBDSQ, the RBD single question (RBD1Q), and the Mayo Sleep Questionnaire (MSQ). The REM atonia index was derived for all participants as an objective measure of RWA. Patients identified to be RBD positive on the RBDSQ did not show increased RWA on polysomnography (80% sensitivity and 55% specificity). However, patients positive for RBD on questionnaires specific to dream enactment correctly identified higher degrees of RWA and improved the diagnostic accuracy of these questionnaires. This study suggests that the RBDSQ does not accurately identify RWA, essential for diagnosing RBD in PD. Furthermore, the results suggest that self-report measures of RBD need to focus questions on dream enactment behavior to better identify RWA and RBD. Further studies are needed to develop accurate determination and quantification of RWA in RBD to improve management of patients with PD in the future.

  10. Molecular mechanism of promoter selection in gene transcription. I. Development of a rapid mixing-photocrosslinking technique to study the kinetics of Escherichia coli RNA polymerase binding to T7 DNA.

    PubMed

    Park, C S; Hillel, Z; Wu, C W

    1982-06-25

    A combined rapid mixing-photocrosslinking technique has been developed to investigate the kinetics of the interaction between Escherichia coli RNA polymerase and T7 DNA. The reactants were rapidly mixed in a modified Durrum stopped-flow apparatus, and the intermediates formed at different stages of the binding process were "frozen" by photocrosslinking with a UV light pulse of 10-mus duration at various times after mixing. The results indicate that the initial binding between RNA polymerase and T7 DNA is a diffusion-controlled reaction. Furthermore, the extents of initial contracts with DNA made with the beta, beta', and sigma subunits of RNA polymerase are roughly proportional to the sizes of these subunits, suggesting that complex formation occurs through random collision between the two reactants. After the initial complex formation, the rate of transfer of polymerase between individual DNA molecules is slow, implying that the polymerase molecules are undergoing predominantly intramolecular transfer during the promoter search. From the kinetic studies of subunit-DNA contacts during RNA polymerase binding to T7 DNA, it can be inferred that the beta, beta', and sigma subunits are directly participating in the promoter search process.

  11. An investigation of the kinetics for hydrogen chemisorption on iron metal surfaces

    NASA Technical Reports Server (NTRS)

    Shanabarger, M. R.

    1980-01-01

    A quasi-isothermal approach was used to study the kinetics of hydrogen and hydrogen sulfide chemisorption onto iron film in an effort to understand the environmental degradation of steels. The coverage of chemisorbed hydrogen or chemisorbed sulfur was observed as a function of time for fixed conditions of substrate temperature. Auger electron spectroscopy was used to observe the sulfur and chemisorption-induced resistance change was employed to monitor hydrogen coverage. To compare the results obtained from studying the kinetics by two different techniques, the kinetics of oxygen chemisorption onto iron films was also studied. A reaction model utilized to interpret the H2/Fe2 chemisorption kinetics was applied to data from an earlier study on the desorption kinetics for H2 chemisorbed onto nicket films in the vicinity of the Curie temperature of the film. This analysis permitted a separation of the gross desorption process into individual components so that the influence of the magnetic phase transition on the rate constants could be determined.

  12. An investigation on the modelling of kinetics of thermal decomposition of hazardous mercury wastes.

    PubMed

    Busto, Yailen; M G Tack, Filip; Peralta, Luis M; Cabrera, Xiomara; Arteaga-Pérez, Luis E

    2013-09-15

    The kinetics of mercury removal from solid wastes generated by chlor-alkali plants were studied. The reaction order and model-free method with an isoconversional approach were used to estimate the kinetic parameters and reaction mechanism that apply to the thermal decomposition of hazardous mercury wastes. As a first approach to the understanding of thermal decomposition for this type of systems (poly-disperse and multi-component), a novel scheme of six reactions was proposed to represent the behaviour of mercury compounds in the solid matrix during the treatment. An integration-optimization algorithm was used in the screening of nine mechanistic models to develop kinetic expressions that best describe the process. The kinetic parameters were calculated by fitting each of these models to the experimental data. It was demonstrated that the D₁-diffusion mechanism appeared to govern the process at 250°C and high residence times, whereas at 450°C a combination of the diffusion mechanism (D₁) and the third order reaction mechanism (F3) fitted the kinetics of the conversions. The developed models can be applied in engineering calculations to dimension the installations and determine the optimal conditions to treat a mercury containing sludge.

  13. Kinetic study for phenol degradation by ZVI-assisted Fenton reaction and related iron corrosion investigated by X-ray absorption spectroscopy.

    PubMed

    Yoon, In-Ho; Yoo, Gursong; Hong, Hye-Jin; Kim, Jungmin; Kim, Min Gyu; Choi, Wang-Kyu; Yang, Ji-Won

    2016-02-01

    In this study, we investigated phenol degradation via zero-valent iron (ZVI)-assisted Fenton reaction through kinetic and spectroscopic analysis. In batch experiments, 100 mg/L of phenol was completely degraded, and 75% of TOC was removed within 3 min under an optimal hydrogen peroxide (H2O2) concentration (50 mM) via the Fenton reaction. In the absence of H2O2, oxygen (O2) was dissolved into the solution and produced H2O2, which resulted in phenol degradation. However, phenol removal efficiency was not very high compared to external H2O2 input. The Fenton reaction rapidly occurred at the surface of ZVI, and then phenol mobility from the solution to the ZVI surface was the rate determining step of the whole reaction. The pseudo-second order adsorption kinetic model well describes phenol removal, and its rate increased according to the H2O2 concentration. X-ray absorption spectroscopic analysis revealed that iron oxide (Fe-O bonding) was formed on ZVI with [H2O2] > 50 mM. A high concentration of H2O2 led to rapid degradation of phenol and caused corrosion on the ZVI surface, indicating that Fe(2+) ions were rapidly oxidized to Fe(3+) ions due to the Fenton reaction and that Fe(3+) was precipitated as iron oxide on the ZVI surface. However, ZVI did not show corroded characteristics in the absence of H2O2 due to the insufficient ZVI-assisted Fenton reaction and oxidation of Fe(2+) to Fe(3+).

  14. Experimental investigation of ≈130 keV kinetic energy antiprotons annihilation on nuclei

    NASA Astrophysics Data System (ADS)

    Aghai-Khozani, H.; Barna, D.; Corradini, M.; Hayano, R.; Hori, M.; Kobayashi, T.; Leali, M.; Lodi-Rizzini, E.; Mascagna, V.; Prest, M.; Soter, A.; Todoroki, K.; Vallazza, E.; Venturelli, L.; Zurlo, N.

    2014-04-01

    The study of the antiproton ( bar {p}) annihilation cross section on nuclei at low energies (eV-MeV region) has implications for fundamental cosmology as well as for nuclear physics. Concerning the former, different models try to explain the matter/antimatter asymmetry in the universe assuming the existence of the so-called "islands" where antinucleon-nucleon annihilations occur in the border region (Cohen et al. Astrophys. J. 495, 539-549, 1998), while, from the nuclear physics point of view, the annihilation process is a valuable tool to evaluate the neutron/proton ratio in order to probe the external region of the nucleus (Gupta et al. Nucl. Phys. B 70(3), 414-424, 1974). The existing data of antinucleon-nucleon (or -nucleus) annihilation cross-sections are mainly confined to energies above ≈1 MeV, while the cross section measured at LEAR in the 80's-90's (mostly with light targets Agnello et al. Phys. Lett. B 256, 349-353, 1991; Bertin et al. Phys. Lett. B 369, 77-85, 1996; Bertin et al. Phys. Lett. B 414, 220-228, 1997; Zenoni et al. Phys. Lett. B 461, 405-412, 1999; Bianconi et al. Phys. Lett. B 481, 194-198, 2000; Bianconi et al. Phys. Lett. B 492, 254-258, 2000) showed an unexpected behaviour for energies below 1 MeV (Bianconi et al. Phys. Lett. B 483, 353-359, 2000; Bianconi et al. Phys. Rev. C 62, 014611-7, 2000; Batty et al. Nucl. Phys. A 689, 721-740, 2001). The results showed a saturation with the atomic mass number against the A 2/3 trend which is observed for higher energies (being A the target mass number). The ASACUSA collaboration at CERN recently measured antiproton annihilation cross section on different kinds of nuclei with a bar {p} kinetic energy of 5.3 MeV (Bianconi et al. Phys. Lett. B 704, 461-466, 2011; Corradini et al. Nucl. Instr. Methods A 711, 12-20, 2013). Such results proved compatibility with the black-disk model with the Coulomb correction. But till now experimental difficulties prevented the investigation at energies below ≈1

  15. Rapid three-dimensional microfluidic mixer for high viscosity solutions to unravel earlier folding kinetics of G-quadruplex under molecular crowding conditions.

    PubMed

    Liu, Chao; Li, Ying; Li, Yiwei; Chen, Peng; Feng, Xiaojun; Du, Wei; Liu, Bi-Feng

    2016-01-01

    Rapid mixing of highly viscous solutions is a great challenge, which helps to analyze the reaction kinetics in viscous liquid phase, particularly to discover the folding kinetics of macromolecules under molecular crowding conditions mimicking the conditions inside cells. Here, we demonstrated a novel microfluidic mixer based on Dean flows with three-dimensional (3D) microchannel configuration for fast mixing of high-viscosity fluids. The main structure contained three consecutive subunits, each consisting of a "U"-type channel followed by a chamber with different width and height. Thus, the two solutions injected from the two inlets would undergo a mixing in the first "U"-type channel due to the Dean flow effect, and simultaneous vortices expansions in both horizontal and vertical directions in the following chamber. Numerical simulations and experimental characterizations confirmed that the micromixer could achieve a mixing time of 122.4μs for solutions with viscosities about 33.6 times that of pure water. It was the fastest micromixer for high viscosity solutions compared with previous reports. With this highly efficient 3D microfluidic mixer, we further characterized the early folding kinetics of human telomere G-quadruplex under molecular crowding conditions, and unravelled a new folding process within 550μs.

  16. CP: AN INVESTIGATION OF COEFFICIENT OF THERMAL EXPANSION, DECOMPOSITION KINETICS, AND REACTION TO VARIOUS STIMULI

    SciTech Connect

    Weese, R K; Burnham, A K; Fontes, A T

    2005-03-23

    The properties of pentaamine (5-cyano-2H-tetrazolato-N2) cobalt (III) perchlorate (CP), which was first synthesized in 1968, continues to be of interest for predicting behavior in handling, shipping, aging, and thermal cook-off situations. We report coefficient of thermal expansion (CTE) values over four specific temperature ranges, decomposition kinetics using linear heating rates, and the reaction to three different types of stimuli: impact, spark, and friction. The CTE was measured using a Thermal Mechanical Analyzer (TMA) for samples that were uniaxially compressed at 10,000 psi and analyzed over a dynamic temperature range of -20 C to 70 C. Using differential scanning calorimetry, DSC, CP was decomposed at linear heating rates of 1, 3, and 7 C/min and the kinetic triplet calculated using the LLNL code Kinetics05. Values are also reported for spark, friction, and impact sensitivity.

  17. 75 FR 11938 - Meridian Automotive Systems, Grand Rapids, MI; Notice of Termination of Investigation

    Federal Register 2010, 2011, 2012, 2013, 2014

    2010-03-12

    ... From the Federal Register Online via the Government Publishing Office DEPARTMENT OF LABOR Employment and Training Administration Meridian Automotive Systems, Grand Rapids, MI; Notice of Termination... Meridian Automotive Systems, Grand Rapids, Michigan (Meridian Automotive). The petitioning group of...

  18. Effects of dopamine replacement therapy on lower extremity kinetics and kinematics during a rapid force production task in persons with Parkinson disease.

    PubMed

    Foreman, K Bo; Singer, Madeline L; Addison, Odessa; Marcus, Robin L; LaStayo, Paul C; Dibble, Leland E

    2014-01-01

    Postural instability appears to be a dopamine resistance motor deficit in persons with Parkinson disease (PD); however, little is known about the effects of dopamine replacement on the relative biomechanical contributions of individual lower extremity joints during postural control tasks. To gain insight, we examined persons with PD using both clinical and laboratory measures. For a clinical measure of motor severity we utilized the Unified Parkinson Disease Rating Scale motor subsection during both OFF and ON medication conditions. For the laboratory measure we utilized data gathered during a rapid lower extremity force production task. Kinematic and kinetic variables at the hip, knee, and ankle were gathered during a counter movement jump during both OFF and ON medication conditions. Sixteen persons with PD with a median Hoehn and Yahr severity of 2.5 completed the study. Medication resulted in significant improvements of angular displacement for the hip, knee, and ankle. Furthermore, significant improvements were revealed only at the hip for peak net moments and average angular velocity compared to the OFF medication condition. These results suggest that dopamine replacement medication result in decreased clinical motor disease severity and have a greater influence on kinetics and kinematics proximally. This proximally focused improvement may be due to active recruitment of muscle force and reductions in passive restraint during lower extremity rapid force production.

  19. Identification of a novel laser dye substrate of mammalian cytochromes P450: application in rapid kinetic analysis, inhibitor screening, and directed evolution.

    PubMed

    Kumar, Santosh

    2007-08-01

    The author sought to develop a high-throughput activity screening assay to carry out rapid kinetic analysis, inhibitor screening, and directed evolution of cytochrome P450 2C enzymes. Initially, of the 9 fluorescent substrates and 10 P450 2C enzymes tested, several P450 2C enzymes showed > 1 nmol/min/nmol P450 activity in cumene hydroperoxide (CuOOH)-supported reaction with a laser dye, 7-dimethylamino-4-trifluoromethylcoumarin (C152). A high-throughput steady-state kinetic analysis of the human P450 2C8, 2C9, and 2C19 showed 1) k(cat) = 3 to 6 min(-1), 2) K(m, CuOOH) = 100 to 200 microM, and 3) S(50, C152) = 10 to 20 microM in the CuOOH system. In addition, P450 2C9 and 2C19 showed a very high k(ca)t (27 and 38 min(-1), respectively) in the nicotinamide adenine dinucleotide phosphate (NADPH)-supported reaction. Subsequently, when mammalian P450s from the other subfamilies were tested, P450 2B1dH, 2B4dH, 2B5dH, 3A4, and 3A5 exhibited a significant activity in both CuOOH and NADPH systems. Furthermore, a high-throughput activity screening assay using whole-cell suspensions of the human P450 2C8, 2C9, and 2C19 was optimized. Overall, the data suggested that C152 can be used as a model substrate for mammalian P450s in CuOOH-supported reaction to perform rapid kinetic analysis, inhibitor screening, and directed evolution.

  20. Investigation of ion kinetic effects in direct-drive exploding-pusher implosions at the NIF

    SciTech Connect

    Rosenberg, M. J. Zylstra, A. B.; Séguin, F. H.; Rinderknecht, H. G.; Frenje, J. A.; Gatu Johnson, M.; Sio, H.; Waugh, C. J.; Sinenian, N.; Li, C. K.; Petrasso, R. D.; McKenty, P. W.; Hohenberger, M.; Radha, P. B.; Delettrez, J. A.; Glebov, V. Yu.; Betti, R.; Goncharov, V. N.; Knauer, J. P.; Sangster, T. C.; and others

    2014-12-15

    Measurements of yield, ion temperature, areal density (ρR), shell convergence, and bang time have been obtained in shock-driven, D{sub 2} and D{sup 3}He gas-filled “exploding-pusher” inertial confinement fusion (ICF) implosions at the National Ignition Facility to assess the impact of ion kinetic effects. These measurements probed the shock convergence phase of ICF implosions, a critical stage in hot-spot ignition experiments. The data complement previous studies of kinetic effects in shock-driven implosions. Ion temperature and fuel ρR inferred from fusion-product spectroscopy are used to estimate the ion-ion mean free path in the gas. A trend of decreasing yields relative to the predictions of 2D DRACO hydrodynamics simulations with increasing Knudsen number (the ratio of ion-ion mean free path to minimum shell radius) suggests that ion kinetic effects are increasingly impacting the hot fuel region, in general agreement with previous results. The long mean free path conditions giving rise to ion kinetic effects in the gas are often prevalent during the shock phase of both exploding pushers and ablatively driven implosions, including ignition-relevant implosions.

  1. Investigation of ion kinetic effects in direct-drive exploding-pusher implosions at the NIF

    NASA Astrophysics Data System (ADS)

    Rosenberg, M. J.; Zylstra, A. B.; Séguin, F. H.; Rinderknecht, H. G.; Frenje, J. A.; Gatu Johnson, M.; Sio, H.; Waugh, C. J.; Sinenian, N.; Li, C. K.; Petrasso, R. D.; McKenty, P. W.; Hohenberger, M.; Radha, P. B.; Delettrez, J. A.; Glebov, V. Yu.; Betti, R.; Goncharov, V. N.; Knauer, J. P.; Sangster, T. C.; LePape, S.; Mackinnon, A. J.; Pino, J.; McNaney, J. M.; Rygg, J. R.; Amendt, P. A.; Bellei, C.; Benedetti, L. R.; Berzak Hopkins, L.; Bionta, R. M.; Casey, D. T.; Divol, L.; Edwards, M. J.; Glenn, S.; Glenzer, S. H.; Hicks, D. G.; Kimbrough, J. R.; Landen, O. L.; Lindl, J. D.; Ma, T.; MacPhee, A.; Meezan, N. B.; Moody, J. D.; Moran, M. J.; Park, H.-S.; Remington, B. A.; Robey, H.; Rosen, M. D.; Wilks, S. C.; Zacharias, R. A.; Herrmann, H. W.; Hoffman, N. M.; Kyrala, G. A.; Leeper, R. J.; Olson, R. E.; Kilkenny, J. D.; Nikroo, A.

    2014-12-01

    Measurements of yield, ion temperature, areal density (ρR), shell convergence, and bang time have been obtained in shock-driven, D2 and D3He gas-filled "exploding-pusher" inertial confinement fusion (ICF) implosions at the National Ignition Facility to assess the impact of ion kinetic effects. These measurements probed the shock convergence phase of ICF implosions, a critical stage in hot-spot ignition experiments. The data complement previous studies of kinetic effects in shock-driven implosions. Ion temperature and fuel ρR inferred from fusion-product spectroscopy are used to estimate the ion-ion mean free path in the gas. A trend of decreasing yields relative to the predictions of 2D draco hydrodynamics simulations with increasing Knudsen number (the ratio of ion-ion mean free path to minimum shell radius) suggests that ion kinetic effects are increasingly impacting the hot fuel region, in general agreement with previous results. The long mean free path conditions giving rise to ion kinetic effects in the gas are often prevalent during the shock phase of both exploding pushers and ablatively driven implosions, including ignition-relevant implosions.

  2. Investigation of Coal-biomass Catalytic Gasification using Experiments, Reaction Kinetics and Computational Fluid Dynamics

    SciTech Connect

    Battaglia, Francine; Agblevor, Foster; Klein, Michael; Sheikhi, Reza

    2015-12-31

    A collaborative effort involving experiments, kinetic modeling, and computational fluid dynamics (CFD) was used to understand co-gasification of coal-biomass mixtures. The overall goal of the work was to determine the key reactive properties for coal-biomass mixed fuels. Sub-bituminous coal was mixed with biomass feedstocks to determine the fluidization and gasification characteristics of hybrid poplar wood, switchgrass and corn stover. It was found that corn stover and poplar wood were the best feedstocks to use with coal. The novel approach of this project was the use of a red mud catalyst to improve gasification and lower gasification temperatures. An important results was the reduction of agglomeration of the biomass using the catalyst. An outcome of this work was the characterization of the chemical kinetics and reaction mechanisms of the co-gasification fuels, and the development of a set of models that can be integrated into other modeling environments. The multiphase flow code, MFIX, was used to simulate and predict the hydrodynamics and co-gasification, and results were validated with the experiments. The reaction kinetics modeling was used to develop a smaller set of reactions for tractable CFD calculations that represented the experiments. Finally, an efficient tool was developed, MCHARS, and coupled with MFIX to efficiently simulate the complex reaction kinetics.

  3. An investigation of the kinetics of hydrogen chemisorption on iron metal surfaces

    NASA Technical Reports Server (NTRS)

    Shanabarger, M. R.

    1982-01-01

    The isothermal kinetics of H2, H2S, and O2 chemisorption onto epitaxially grown (III) oriented Fe films were studied. The measurements were made using the techniques of chemisorption induced resistance change and Auger electron spectroscopy (for adsorbed sulfur and oxygen). Also the origin of the chemisorption induced resistance change for these systems and its applicability to kinetic measurements were established. The chemisorption kinetics were interpreted as dissociative chemisorption via an adsorbed molecular species. The applicable rate constants were established. In none of the studies were the rate constants observed to be coverage dependent. By comparing the temperature dependence of the rate constants with absolute rate theory, the binding energies and activation energies of all the kinetic processes were obtained for the H2/Fe system. The initial sticking coefficient was pressure dependent for both the H2/Fe and H2S/Fe systems. This results from the step between the adsorbed molecular state and the dissociated chemisorbed state being the rate limiting step for absorption at certain pressures and temperatures. Estimates were obtained for the temperature dependence of the rate constants for the O2/Fe system.

  4. A theoretical investigation of DNA dynamics and desolvation kinetics for zinc finger proteinZif268

    PubMed Central

    2015-01-01

    Background Transcription factors, regulating the expression inventory of a cell, interact with its respective DNA subjugated by a specific recognition pattern, which if well exploited may ensure targeted genome engineering. The mostly widely studied transcription factors are zinc finger proteins that bind to its target DNA via direct and indirect recognition levels at the interaction interface. Exploiting the binding specificity and affinity of the interaction between the zinc fingers and the respective DNA can help in generating engineered zinc fingers for therapeutic applications. Experimental evidences lucidly substantiate the effect of indirect interaction like DNA deformation and desolvation kinetics, in empowering ZFPs to accomplish partial sequence specificity functioning around structural properties of DNA. Exploring the structure-function relationships of the existing zinc finger-DNA complexes at the indirect recognition level can aid in predicting the probable zinc fingers that could bind to any target DNA. Deformation energy, which defines the energy required to bend DNA from its native shape to its shape when bound to the ZFP, is an effect of indirect recognition mechanism. Water is treated as a co-reactant for unfurling the affinity studies in ZFP-DNA binding equilibria that takes into account the unavoidable change in hydration that occurs when these two solvated surfaces come into contact. Results Aspects like desolvation and DNA deformation have been theoretically investigated based on simulations and free energy perturbation data revealing a consensus in correlating affinity and specificity as well as stability for ZFP-DNA interactions. Greater loss of water at the interaction interface of the DNA calls for binding with higher affinity, eventually distorting the DNA to a greater extent accounted by the change in major groove width and DNA tilt, stretch and rise. Conclusion Most prediction algorithms for ZFPs do not account for water loss at the

  5. Dielectric approach to investigation of erythrocyte aggregation. II. Kinetics of erythrocyte aggregation-disaggregation in quiescent and flowing blood.

    PubMed

    Pribush, A; Meiselman, H J; Meyerstein, D; Meyerstein, N

    2000-01-01

    A method based on dielectric properties of dispersed systems was applied to investigate the kinetics of RBC aggregation and the break-up of the aggregates. Experimentally, this method consists of measuring the capacitance at a frequency in the beginning of the beta-dispersion. Two experimental protocols were used to investigate the aggregation process. In the first case, blood samples were fully dispersed and then the flow was decreased or stopped to promote RBC aggregation. It was found that the initial phases of RBC aggregation are not affected by the shear rate. This finding indicates that RBC aggregation is a slow coagulation process. In the second case, RBCs aggregated under flow conditions at different shear rates and after the capacitance reached plateau levels, the flow was ceased. The steady-state capacitance of the quiescent blood and the kinetics of RBC aggregation after stoppage of shearing depend on the prior shear rate. To clarify the reasons for this effect, the kinetics of the disaggregation process was studied. In these experiments, time courses of the capacitance were recorded under different flow conditions and then a higher shear stress was applied to break up RBC aggregates. It was found that the kinetics of the disaggregation process depend on both the prior and current shear stresses. Results obtained in this study and their analysis show that the kinetics of RBC aggregation in stasis consists of two consecutive phases: At the onset, red blood cells interact face-to-face to form linear aggregates and then, after an accumulation of an appropriate concentration of these aggregates, branched rouleaux are formed via reactions of ends of the linear rouleaux with sides of other rouleaux (face-to-side interactions). Branching points are broken by low shear stresses whereas dispersion of the linear rouleaux requires significantly higher energy.

  6. Crystallization kinetics of rapidly quenched Cu50Zr50 and Cu46Zr46Al8 glass-forming alloys

    NASA Astrophysics Data System (ADS)

    Kulikova, T. V.; Ryltseva, A. A.; Bykov, V. A.; Estemirova, S. Kh; Shuhyaev, K. Yu

    2017-01-01

    We studied the crystallization processes, the structure and thermal properties of amorphous alloys Cu50Zr50 and Cu46Zr46Al8 in a wide temperature range. Comparative study of the crystallization kinetics of these amorphous alloys was carried out for the first time using multivariate non-linear regression. It was found that mechanisms of the crystallization of studied metallic glasses are substantially different. The binary alloy is crystallized by branched reaction complex in four steps. For the ternary system was proposed two-step kinetic model of the crystallization process with consecutive reactions. The values of the total energy of activation for each crystallization stage reach to Cu50Zr50: E1 (345.2 kJ/mol); E2 (307.9 kJ/mol), E3 (281.1 kJ/mol), E4 (259.51 kJ/mol) and Cu46Zr46Al8: E1 (350.7 kJ/mol); E2 (150.4 kJ/mol).

  7. Three-stage autoignition of gasoline in an HCCI engine: An experimental and chemical kinetic modeling investigation

    SciTech Connect

    Machrafi, Hatim; Cavadias, Simeon

    2008-12-15

    The alternative HCCI combustion mode presents a possible means for decreasing the pollution with respect to conventional gasoline or diesel engines, while maintaining the efficiency of a diesel engine or even increasing it. This paper investigates the possibility of using gasoline in an HCCI engine and analyzes the autoignition of gasoline in such an engine. The compression ratio that has been used is 13.5, keeping the inlet temperature at 70 C, varying the equivalence ratio from 0.3 to 0.54, and the EGR (represented by N{sub 2}) ratio from 0 to 37 vol%. For comparison, a PRF95 and a surrogate containing 11 vol% n-heptane, 59 vol% iso-octane, and 30 vol% toluene are used. A previously validated kinetic surrogate mechanism is used to analyze the experiments and to yield possible explanations to kinetic phenomena. From this work, it seems quite possible to use the high octane-rated gasoline for autoignition purposes, even under lean inlet conditions. Furthermore, it appeared that gasoline and its surrogate, unlike PRF95, show a three-stage autoignition. Since the PRF95 does not contain toluene, it is suggested by the kinetic mechanism that the benzyl radical, issued from toluene, causes this so-defined ''obstructed preignition'' and delaying thereby the final ignition for gasoline and its surrogate. The results of the kinetic mechanism supporting this explanation are shown in this paper. (author)

  8. Study on biodegradation of Mazut by newly isolated strain Enterobacter cloacae BBRC10061: improving and kinetic investigation

    PubMed Central

    2013-01-01

    Mazut as a source content of various hydrocarbons is hard to be degraded and its cracking could turn mazut into useful materials. Nevertheless degradation of mazut by routine methods is too expensive but application of indigenous microorganisms as biocatalysts could be effective and important to lower the costs and expand its consumption. Mazut biodegradation can be improved using various strategies; Therefore in this study newly isolated strain Enterobacter cloacae BBRC 10061 was used in a method of gradual addition of mazut into medium and its results were compared with simple addition method. To investigate degradation of mazut by BBRC 10061, influence of increase of mazut concentration was assayed based on gradual addition method. Also different kinetic models were used to evaluate kinetics of the process. Results showed that gradual addition method has been a beneficial technique for improvement of mazut degradation because bacterial induction to produce biosurfactant and essential enzymes for cracking mazut was higher during process. Although addition of more mazut increased the rate of biodegradation but percentage of degradation decreased. pH of medium decreased during biodegradation period while electric potential increased. Also the biodegradation kinetics was not fitted with the biokinetic models; therefore kinetics of biodegradation of mazut has to be studied by new models. PMID:23369455

  9. Geometrical investigation of the kinetic evolution of the magnetic field in a periodic flux rope

    SciTech Connect

    Restante, A. L.; Lapenta, G.; Markidis, S.; Intrator, T.

    2013-08-15

    Flux ropes are bundles of magnetic field wrapped around an axis. Many laboratory, space, and astrophysics processes can be represented using this idealized concept. Here, a massively parallel 3D kinetic simulation of a periodic flux rope undergoing the kink instability is studied. The focus is on the topology of the magnetic field and its geometric structures. The analysis considers various techniques such as Poincaré maps and the quasi-separatrix layer (QSL). These are used to highlight regions with expansion or compression and changes in the connectivity of magnetic field lines and consequently to outline regions where heating and current may be generated due to magnetic reconnection. The present study is, to our knowledge, the first QSL analysis of a fully kinetic 3D particle in cell simulation and focuses the existing QSL method of analysis to periodic systems.

  10. Magnetic reconnection in multispecies plasmas investigated by a kinetic fluid code

    NASA Astrophysics Data System (ADS)

    Dong, Chuanfei; Wang, Liang; Bhattacharjee, Amitava; Hakim, Ammar; Huang, Yi-Min; Germaschewski, Kai

    2016-10-01

    We first study the reconnection process in multispecies plasmas by using Gkeyll, which is a kinetic fluid code solving the continuity, momentum and energy equations of each species, and the full Maxwell equations. Thus, there is no assumption by solving the generalized ohm's law in Gkeyll. We studied the reconnection processes in the plasma consisting of electrons, protons and oxygen ions. If time allows, we also plan to show some preliminary results of magnetic reconnection in dusty plasmas with negatively charged dust.

  11. Rapid renaturation of complementary DNA strands mediated by cationic detergents: a role for high-probability binding domains in enhancing the kinetics of molecular assembly processes.

    PubMed Central

    Pontius, B W; Berg, P

    1991-01-01

    The rate of renaturation for complementary DNA strands can be enhanced greater than 10(4)-fold by the addition of simple cationic detergents, and the reaction is qualitatively and quantitatively very similar to that found with purified heterogeneous nuclear ribonucleoprotein A1 protein. Under optimal conditions, renaturation rates are greater than 2000-fold faster than reactions run in 1 M NaCl at 68 degrees C. The reaction is second-order with respect to DNA concentration, and reaction rates approach or equal the rate with which complementary strands are expected to encounter each other in solution. Renaturation can even be observed well above the expected melting temperature of the duplex DNA, demonstrating that some cationic detergents have DNA double-helix-stabilizing properties. The reaction is also extremely rapid in the presence of up to a 10(6)-fold excess of noncomplementary sequences, establishing that renaturation is specific and relatively independent of heterologous DNA. This finding also implies that up to several thousand potential target sequences can be sampled per strand per second. Such reagents may be useful for procedures that require rapid nucleic acid renaturation, and these results suggest ways to identify and design other compounds that increase the kinetics of association reactions. Moreover, this work provides further support for a model relating the existence of flexible, weakly interacting, repeating domains to their function in rapid molecular assembly processes in vitro and in vivo. PMID:1896475

  12. Wide-dynamic-range kinetic investigations of deep proton tunnelling in proteins

    NASA Astrophysics Data System (ADS)

    Salna, Bridget; Benabbas, Abdelkrim; Sage, J. Timothy; van Thor, Jasper; Champion, Paul M.

    2016-09-01

    Directional proton transport along ‘wires’ that feed biochemical reactions in proteins is poorly understood. Amino-acid residues with high pKa are seldom considered as active transport elements in such wires because of their large classical barrier for proton dissociation. Here, we use the light-triggered proton wire of the green fluorescent protein to study its ground-electronic-state proton-transport kinetics, revealing a large temperature-dependent kinetic isotope effect. We show that ‘deep’ proton tunnelling between hydrogen-bonded oxygen atoms with a typical donor-acceptor distance of 2.7-2.8 Å fully accounts for the rates at all temperatures, including the unexpectedly large value (2.5 × 109 s-1) found at room temperature. The rate-limiting step in green fluorescent protein is assigned to tunnelling of the ionization-resistant serine hydroxyl proton. This suggests how high-pKa residues within a proton wire can act as a ‘tunnel diode’ to kinetically trap protons and control the direction of proton flow.

  13. A Pilot Study Investigating the Potential of High-Intensity Focused Ultrasound to Treat Tumours Rapidly

    NASA Astrophysics Data System (ADS)

    Cranston, Jonathan M.; Rivens, Ian; ter Haar, Gail; Kennedy, James

    2007-05-01

    The aim of this project was to investigate the possibility of rapid tumour destruction by a novel method of treating the periphery of a tumour and inducing ischemia by impeding the blood supply. Ex vivo experiments were initially carried out in bovine liver to determine the optimum conditions for focal depth, gantry transducer speed circle diameter and intensity of the ultrasound beam. In vivo experiments were then performed in PGV rat livers implanted with a HSN fibrosarcoma cell line. The tumours were treated by novel technique of creating an annular lesion around the perimeter of the tumour. Macroscopic and microscopic examination of the lesion at post mortem was performed. In addition histological examination of the untreated tumour which was within the annular circle of treatment was examined. This showed evidence of karyolytic nuclei a week after treatment suggesting death by infarction within this area. There was also some evidence of endothelial damage in the blood vessels with fragmented nuclei visible in the lumen. The work presented here adds to our understanding of how high intensity focused ultrasound may be used to treat tumours in as faster and more efficient way. Further work in this area will facilitate the design of future therapeutic interventions in the medical and veterinary world.

  14. Investigation of the effect of rapidly solidified braze ribbons on the microstructure of brazed joints

    NASA Astrophysics Data System (ADS)

    Bobzin, K.; Öte, M.; Wiesner, S.; Rochala, P.; Mayer, J.; Aretz, A.; Iskandar, R.; Schwedt, A.

    2017-03-01

    Shrinkage and warpage due to melting and solidification are crucial for the geometric precision of related components. In order to assure a high geometric precision, the formation of the microstructure in the joint during brazing must be taken into consideration. An extensive interaction can occur between liquid melt and base material, resulting in the formation of distinctive phases. This interaction depends on the parameters of the brazing process. However, the consequences of the interaction between phase formation and process parameters in terms of geometric precision cannot be estimated yet. Insufficient quality of the joint can be a result. In this study, investigations focus on the process of solidification in terms of time dependent diffusion behavior of elements. Therefore, microcrystalline and amorphous braze ribbons based on Ti are produced by rapid solidification and are used for joining. The microstructure of the braze ribbons as well as the melting behavior and phase formation during brazing are considered to be of particular importance for the mechanical properties of the brazed components.

  15. Ozone-surface interactions: Investigations of mechanisms, kinetics, mass transport, and implications for indoor air quality

    SciTech Connect

    Morrison, Glenn Charles

    1999-12-01

    In this dissertation, results are presented of laboratory investigations and mathematical modeling efforts designed to better understand the interactions of ozone with surfaces. In the laboratory, carpet and duct materials were exposed to ozone and measured ozone uptake kinetics and the ozone induced emissions of volatile organic compounds. To understand the results of the experiments, mathematical methods were developed to describe dynamic indoor aldehyde concentrations, mass transport of reactive species to smooth surfaces, the equivalent reaction probability of whole carpet due to the surface reactivity of fibers and carpet backing, and ozone aging of surfaces. Carpets, separated carpet fibers, and separated carpet backing all tended to release aldehydes when exposed to ozone. Secondary emissions were mostly n-nonanal and several other smaller aldehydes. The pattern of emissions suggested that vegetable oils may be precursors for these oxidized emissions. Several possible precursors and experiments in which linseed and tung oils were tested for their secondary emission potential were discussed. Dynamic emission rates of 2-nonenal from a residential carpet may indicate that intermediate species in the oxidation of conjugated olefins can significantly delay aldehyde emissions and act as reservoir for these compounds. The ozone induced emission rate of 2-nonenal, a very odorous compound, can result in odorous indoor concentrations for several years. Surface ozone reactivity is a key parameter in determining the flux of ozone to a surface, is parameterized by the reaction probability, which is simply the probability that an ozone molecule will be irreversibly consumed when it strikes a surface. In laboratory studies of two residential and two commercial carpets, the ozone reaction probability for carpet fibers, carpet backing and the equivalent reaction probability for whole carpet were determined. Typically reaction probability values for these materials were 10

  16. Kinetic anharmonic coupling in the trihalomethanes: A mechanism for rapid intramolecular redistribution of CH stretch vibrational energy

    SciTech Connect

    Green, W.H. Jr.; Lawrance, W.D.; Moore, C.B.

    1987-06-01

    The coupling of CH stretching and CH bending vibrations in trisubstituted methanes is analyzed. Improved spectroscopic constants, especially the cubic anharmonic stretch--bend coupling constants, are extracted from Fermi resonances in the overtone spectra of HCF/sub 3/ and HCCl/sub 3/. Both harmonic oscillator and Morse oscillator basis functions are used in the analysis and the results compared. That part of the coupling which arises from the kinetic energy as expressed in curvilinear coordinates is calculated and compared to the coupling calculated using the more conventional rectilinear treatment. Use of curvilinear coordinates is found to provide significant advantages. The formalism for curvilinear normal coordinates is clarified and generalized. From these calculations and the spectral analysis, one of the cubic anharmonic constants of the potential energy surface is extracted for comparison with ab initio calculations. The curvilinear model of the CH stretch--bend interaction tested for these isolated CH chromophores is expected to be useful in understanding CH bonds and vibrational energy flow in larger hydrocarbons.

  17. Rapid and direct spectrophotometric method for kinetics studies and routine assay of peroxidase based on aniline diazo substrates.

    PubMed

    Mirazizi, Fatemeh; Bahrami, Azita; Haghbeen, Kamahldin; Shahbani Zahiri, Hossein; Bakavoli, Mehdi; Legge, Raymond L

    2016-12-01

    Peroxidases are ubiquitous enzymes that play an important role in living organisms. Current spectrophotometrically based peroxidase assay methods are based on the production of chromophoric substances at the end of the enzymatic reaction. The ambiguity regarding the formation and identity of the final chromophoric product and its possible reactions with other molecules have raised concerns about the accuracy of these methods. This can be of serious concern in inhibition studies. A novel spectrophotometric assay for peroxidase, based on direct measurement of a soluble aniline diazo substrate, is introduced. In addition to the routine assays, this method can be used in comprehensive kinetics studies. 4-[(4-Sulfophenyl)azo]aniline (λmax = 390 nm, ɛ = 32 880 M(-1) cm(-1) at pH 4.5 to 9) was introduced for routine assay of peroxidase. This compound is commercially available and is indexed as a food dye. Using this method, a detection limit of 0.05 nmol mL(-1) was achieved for peroxidase.

  18. Rapid hydrolysis of model phosphate diesters by alkaline-earth cations in aqueous DMSO: speciation and kinetics.

    PubMed

    Taran, Olga; Medrano, Felipe; Yatsimirsky, Anatoly K

    2008-12-14

    Kinetics of the cleavage of two phosphate diesters, bis(4-nitrophenyl) phosphate and 2-hydroxypropyl 4-nitrophenyl phosphate and a triester, 4-nitrophenyl diphenyl phosphate, in the presence of Mg(II), Ca(II) and Sr(II) were studied in 90% vol. DMSO at 37 degrees C. The alkaline hydrolysis of the triester was inhibited by all cations, but with both phosphodiesters strong catalytic effects were observed. Potentiometric titrations of metal perchlorates by Bu4N(OH) revealed formation of M2(OH)3+, M(OH)+, M(OH)2 and M2(OH)5- species. Rate constants for phosphodiester cleavage by individual species were obtained from analysis of rate-concentration profiles. Observed first-order rate constants in the presence of 1-2 mM Mg(II) or Ca(II) in neutral and weakly basic solutions were 10(8)-10(11) times higher than those for background hydrolysis at the same pH while in water additions of up to 50 mM metal produced <100-fold accelerations. Possible structures of DMSO solvated catalyst-substrate complexes were modeled by DFT calculations with Mg(II). The increased catalytic activity in 90% DMSO is attributed to stronger association of hydroxide ions and anionic phosphodiesters with metal ions and to preferable solvation of cations by DMSO, which creates favorable for reaction anhydrous microenvironment in the coordination sphere of the catalyst.

  19. An investigation of the kinetics of the mesophase transformations in petroleum pitch by the ESR method

    SciTech Connect

    Samoilov, V.M.; Frolov, V.I.; Kotosonov, A.S.; Ostronov, B.G.; Rumyantsev, S.M.

    1983-01-01

    The amount of ..cap alpha../sub 1/ fraction, the concentration of paramagnetic centers, and the width of the line of the ESR signal have been determined for samples of mesophase pitches obtained by treating an initial petroleum pitch at 400-440/sup 0/C. The applicability of the ESR method for studying the kinetics and mechanism of the process of mesophase transformations has been shown. From the change in the parameters studied the rate constants and activation energies of the processes of the formation and growth of the aromatic regions of polyconjugation and of the accumulation of mesophase have been calculated.

  20. Kinetic model for conventional flotation of coal. Report of investigations/1995

    SciTech Connect

    Susko, F.J.; Stanley, D.A.

    1995-12-31

    The U.S. Bureau of Mines has developed a computer model to describe a flotation process. Coal data from conventional flotation has been converted to a simple two-parameter kinetic model developed by Reuter and van Deventer. Each set of coal data was represented by two constants, alpha and beta, and an average flotation rate. The success of the model was demonstrated when the calculated and experimental recoveries showed good correlation. The two-parameter model allows complex data to be defined much more efficiently than traditional knowledge-based models.

  1. Dosimetric and kinetic investigations of γ-irradiated sodium tartrate dihydrate.

    PubMed

    Tuner, H; Kayikçi, M A

    2012-03-01

    Effects of gamma radiation on solid sodium tartrate dihydrate (NaTA) were studied using electron spin resonance (ESR) spectroscopy. One main singlet located at g = 2.0034 and many weak lines located at low and high magnetic field sides were found in the irradiated samples. Dosimetric and kinetic features of the radical species responsible for the experimental ESR spectra were explored through the variations in the signal intensities with respect to applied microwave power, temperature and storage time. Activation energies of the involved radical species were also determined using data derived from annealing studies.

  2. PFD: a database for the investigation of protein folding kinetics and stability.

    PubMed

    Fulton, Kate F; Devlin, Glyn L; Jodun, Rachel A; Silvestri, Linda; Bottomley, Stephen P; Fersht, Alan R; Buckle, Ashley M

    2005-01-01

    We have developed a new database that collects all protein folding data into a single, easily accessible public resource. The Protein Folding Database (PFD) contains annotated structural, methodological, kinetic and thermodynamic data for more than 50 proteins, from 39 families. A user-friendly web interface has been developed that allows powerful searching, browsing and information retrieval, whilst providing links to other protein databases. The database structure allows visualization of folding data in a useful and novel way, with a long-term aim of facilitating data mining and bioinformatics approaches. PFD can be accessed freely at http://pfd.med.monash.edu.au.

  3. Kinetic investigation of catalytic disproportionation of superoxide ions in the non-aqueous electrolyte used in Li–air batteries

    DOE PAGES

    Wang, Qiang; Zheng, Dong; McKinnon, Meaghan E.; ...

    2014-10-28

    Superoxide reacts with carbonate solvents in Li–air batteries. Tris(pentafluorophenyl)borane is found to catalyze a more rapid superoxide (O2-) disproportionation reaction than the reaction between superoxide and propylene carbonate (PC). With this catalysis, the negative impact of the reaction between the electrolyte and O2-produced by the O2 reduction can be minimized. A simple kinetic study using ESR spectroscopy was reported to determine reaction orders and rate constants for the reaction between PC and superoxide, and the disproportionation of superoxide catalyzed by Tris(pentafluorophenyl)borane and Li ions. As a result, the reactions are found to be first order and the rate constants aremore » 0.033 s-1 M-1, 0.020 s-1 M-1and 0.67 s-1M-1 for reactions with PC, Li ion and Tris(pentafluorophenyl)borane, respectively.« less

  4. Rapid Whole-Genome Sequencing for Investigation of a Neonatal MRSA Outbreak

    PubMed Central

    Köser, Claudio U.; Holden, Matthew T.G.; Ellington, Matthew J.; Cartwright, Edward J.P.; Brown, Nicholas M.; Ogilvy-Stuart, Amanda L.; Hsu, Li Yang; Chewapreecha, Claire; Croucher, Nicholas J.; Harris, Simon R.; Sanders, Mandy; Enright, Mark C.; Dougan, Gordon; Bentley, Stephen D.; Parkhill, Julian; Fraser, Louise J.; Betley, Jason R.; Schulz-Trieglaff, Ole B.; Smith, Geoffrey P.; Peacock, Sharon J.

    2013-01-01

    Background Isolates of methicillin-resistant Staphylococcus aureus (MRSA) belonging to a single lineage are often indistinguishable by means of current typing techniques. Whole-genome sequencing may provide improved resolution to define transmission pathways and characterize outbreaks. Methods We investigated a putative MRSA outbreak in a neonatal intensive care unit. By using rapid high-throughput sequencing technology with a clinically relevant turnaround time, we retrospectively sequenced the DNA from seven isolates associated with the outbreak and another seven MRSA isolates associated with carriage of MRSA or bacteremia in the same hospital. Results We constructed a phylogenetic tree by comparing single-nucleotide polymorphisms (SNPs) in the core genome to a reference genome (an epidemic MRSA clone, EMRSA-15 [sequence type 22]). This revealed a distinct cluster of outbreak isolates and clear separation between these and the nonoutbreak isolates. A previously missed transmission event was detected between two patients with bacteremia who were not part of the outbreak. We created an artificial “resistome” of antibiotic-resistance genes and demonstrated concordance between it and the results of phenotypic susceptibility testing; we also created a “toxome” consisting of toxin genes. One outbreak isolate had a hypermutator phenotype with a higher number of SNPs than the other outbreak isolates, highlighting the difficulty of imposing a simple threshold for the number of SNPs between isolates to decide whether they are part of a recent transmission chain. Conclusions Whole-genome sequencing can provide clinically relevant data within a time frame that can influence patient care. The need for automated data interpretation and the provision of clinically meaningful reports represent hurdles to clinical implementation. (Funded by the U.K. Clinical Research Collaboration Translational Infection Research Initiative and others.) PMID:22693998

  5. Kinetic Roughening and Energetics of Tetragonal Lysozyme Crystal Growth: A Preliminary Atomic Force Microscopy Investigation

    NASA Technical Reports Server (NTRS)

    Gorti, Sridhar; Forsythe, Elizabeth L.; Pusey, Marc L.

    2004-01-01

    We examined particulars of crystal growth from measurements obtained at both microscopic and molecular levels. The crystal growth measurements performed at the microscopic level are well characterized by a model that balances the flux of macromolecules towards the crystal surface with the flux of the crystal surface. Numerical evaluation of model with measurements of crystal growth, in time, provided accurate estimates for the average growth velocities. Growth velocities thus obtained were also interpreted using well-established phenomenological theories. Moreover, we find that microscopic measurements of growth velocity measurements obtained as a function of temperature best characterizes changes in crystal growth modes, when present. We also examined the possibility of detecting a change in crystal growth modes at the molecular level using atomic force microscopy, AFM. From preliminary AFM measurements performed at various supersaturations, we find that magnitude of surface height fluctuations, h(x), increases with supersaturation. Further examination of surface height fluctuations using methods established for fluctuation spectroscopy also enabled the discovery of the existence of a characteristic length, c, which may possibly determine the mode of crystal growth. Although the results are preliminary, we establish the non- critical divergence of 5 and the root-mean-square (rms) magnitude of height-height fluctuations as the kinetic roughening transition temperatures are approached. Moreover, we also examine approximate models for interpreting the non-critical behavior of both 6 and rms magnitude of height-height fluctuations, as the solution supersaturation is increased towards the kinetic roughening supersaturation.

  6. Advanced kinetic plasma model implementation for new large-scale investigations

    NASA Astrophysics Data System (ADS)

    Reddell, Noah; Shumlak, Uri

    2013-10-01

    A kinetic plasma model for of one or more particle species described by the Vlasov equation and coupled to fully dynamic electromagnetic forces is presented. The model is implemented as evolving continuous PDF (probability density function) in particle phase space (position-velocity) as opposed to particle-in-cell (PIC) methods which discretely sample the PDF. A new boundary condition for the truncated velocity-space edge, motivated by physical properties of the PDF tail, is introduced. The hyperbolic model is evolved using the discontinuous Galerkin numerical method, conserving system mass, momentum, and energy - an advantage compared to PIC. Simulations of two- to six-dimensional phase space are computationally expensive. To maximize performance and scaling to large simulations, a new framework, WARPM, has been developed for many-core (e.g. GPU) computing architectures. WARPM supports both multi-fluid and continuum kinetic plasma models as coupled hyperbolic systems with nearest neighbor predictable communication. Exemplary physics results and computational performance are presented.

  7. A novel bench-scale column assay to investigate site-specific nitrification biokinetics in biological rapid sand filters.

    PubMed

    Tatari, K; Smets, B F; Albrechtsen, H-J

    2013-10-15

    A bench-scale assay was developed to obtain site-specific nitrification biokinetic information from biological rapid sand filters employed in groundwater treatment. The experimental set-up uses granular material subsampled from a full-scale filter, packed in a column, and operated with controlled and continuous hydraulic and ammonium loading. Flowrates and flow recirculation around the column are chosen to mimic full-scale hydrodynamic conditions, and minimize axial gradients. A reference ammonium loading rate is calculated based on the average loading experienced in the active zone of the full-scale filter. Effluent concentrations of ammonium are analyzed when the bench-scale column is subject to reference loading, from which removal rates are calculated. Subsequently, removal rates above the reference loading are measured by imposing short-term loading variations. A critical loading rate corresponding to the maximum removal rate can be inferred. The assay was successfully applied to characterize biokinetic behavior from a test rapid sand filter; removal rates at reference loading matched those observed from full-scale observations, while a maximum removal capacity of 6.9 g NH4(+)-N/m(3) packed sand/h could easily be determined at 7.5 g NH4(+)-N/m(3) packed sand/h. This assay, with conditions reflecting full-scale observations, and where the biological activity is subject to minimal physical disturbance, provides a simple and fast, yet powerful tool to gain insight in nitrification kinetics in rapid sand filters.

  8. Confocal-based method for quantification of diffusion kinetics in microwell plates and its application for identifying a rapid mixing method for high-content/throughput screening.

    PubMed

    Song, Ok Ryul; Kim, Tae-Hee; Perrodon, Xavier; Lee, Changbok; Jeon, Hee Kyoung; Seghiri, Zahir; Kwon, Ho Jeong; Cechetto, Jonathan; Christophe, Thierry

    2010-02-01

    Rapid mixing in microplates is still an underappreciated challenge in screening assay development, particularly with the use of noncontact nanoliter liquid handlers. In high-content/throughput screening (HC/TS), fast and efficient mixing between compounds and cell culture medium is even more critical as biological kinetics dictates speed of mixing, usually within a few minutes. Moreover, mixing in HC/TS should be gentle enough to avoid any negative disruption in cell layer. Here the authors introduce a method to accurately quantify drop diffusion into a microplate well, independently of buffer, liquid handler, or dispensing protocol. This method was used to determine the effect of various mixing methods on the diffusion of a nanoliter drop of pure DMSO in aqueous buffer in 384-well plates. Rapid plate shaking and additional buffer addition were shown to be the most efficient and effective mixing methods for HC/TS. However, efficient mixing by plate shaking is limited by assay volume. Bulk addition shows fast and efficient mixing, without negative effects on cells. Moreover, this simple, fast, and inexpensive method can be easily adapted on any platform.

  9. Insights into the mechanism of Pseudomonas dacunhae aspartate beta-decarboxylase from rapid-scanning stopped-flow kinetics.

    PubMed

    Phillips, Robert S; Lima, Santiago; Khristoforov, Roman; Sudararaju, Bakthavatsalam

    2010-06-22

    The mechanism of wild-type and R37A mutant Pseudomonas dacunhae aspartate beta-decarboxylase (ABDC) was studied by rapid-scanning stopped-flow spectrophotometry. Mixing wild-type ABDC with 50 mM disodium l-Asp resulted in the formation of a 325 nm absorption peak within the dead time of the stopped-flow instrument, likely the ketimine of pyridoxamine 5'-phosphate and oxaloacetate or pyruvate. After consumption of the l-Asp, the 360 nm feature of the resting enzyme was restored. Thus, the 325 nm species is a catalytically competent intermediate. In contrast, mixing wild-type ABDC with the disodium salt of either threo- or erythro-beta-hydroxy-dl-Asp at 50 mM resulted in a much slower formation of the 325 nm complex, with an apparent rate constant of approximately 1 or 0.006 s(-1), respectively. When wild-type ABDC is mixed with disodium succinate, a nonreactive analogue of l-Asp, formation of a new peak at 425 nm is observed. The apparent rate constant for formation of the 425 nm band exhibits a hyperbolic dependence on succinate concentration, showing that there is a rapid binding equilibrium, followed by a slower reaction in which the internal aldimine is protonated on the Schiff base N. Hydrostatic pressure shifts the spectrum from the 425 nm form to the 360 nm form, consistent with a conformational change. It is likely that the binding of substrate or analogues induces a conformational change that releases strain in the Lys pyridoxal 5'-phosphate Schiff base and increases the pK(a), resulting in protonation of the Schiff base to initiate transaldimination. Mixing of R37A mutant ABDC with 50 mM l-Asp also results in the formation of the 325 nm complex, but with an apparent rate constant of 0.2 s(-1), at least 5000-fold slower than the rate of wild-type ABDC. In contrast to wild-type ABDC, R37A ABDC shows no change in the cofactor spectrum when mixed with disodium succinate. These results suggest that Arg-37, a conserved active site residue in ABDC, plays a role

  10. Kinetic investigation of sulfidizing annealing of scorodite in processing of refractory oxidized gold-containing ores

    NASA Astrophysics Data System (ADS)

    Boboev, I. R.; Strizhko, L. S.; Bobozoda, Sh.; Gorbunov, E. P.

    2016-03-01

    The results of kinetic studies on the removal of arsenic from scorodite using sulfidizing annealing are presented. The reaction order with respect to the reactant and the activation energy are established from the experimental data. The rate-determining step of the sulfidizing annealing process is determined. The main reactions that occur during the sulfidizing of arsenic in scorodite are proposed on the basis of the obtained results and confirmed by thermodynamic calculations and chemical analyses. The major results of testing this technology, as applied to the refractory oxidized ores in which arsenic is mainly concentrated in scorodite, are presented. Arsenic removal from this ore is confirmed by chemical and quantitative X-ray diffraction analyses and by qualitative phase analysis. Industrial use of this technology provides safe and efficient processing of refractory gold-containing ores, where arsenic is mainly concentrated in scorodite.

  11. NO binding kinetics in myoglobin investigated by picosecond Fe K-edge absorption spectroscopy

    PubMed Central

    Silatani, Mahsa; Lima, Frederico A.; Penfold, Thomas J.; Rittmann, Jochen; Reinhard, Marco E.; Rittmann-Frank, Hannelore M.; Borca, Camelia; Grolimund, Daniel; Milne, Christopher J.; Chergui, Majed

    2015-01-01

    Diatomic ligands in hemoproteins and the way they bind to the active center are central to the protein’s function. Using picosecond Fe K-edge X-ray absorption spectroscopy, we probe the NO-heme recombination kinetics with direct sensitivity to the Fe-NO binding after 532-nm photoexcitation of nitrosylmyoglobin (MbNO) in physiological solutions. The transients at 70 and 300 ps are identical, but they deviate from the difference between the static spectra of deoxymyoglobin and MbNO, showing the formation of an intermediate species. We propose the latter to be a six-coordinated domed species that is populated on a timescale of ∼200 ps by recombination with NO ligands. This work shows the feasibility of ultrafast pump–probe X-ray spectroscopic studies of proteins in physiological media, delivering insight into the electronic and geometric structure of the active center. PMID:26438842

  12. NO binding kinetics in myoglobin investigated by picosecond Fe K-edge absorption spectroscopy.

    PubMed

    Silatani, Mahsa; Lima, Frederico A; Penfold, Thomas J; Rittmann, Jochen; Reinhard, Marco E; Rittmann-Frank, Hannelore M; Borca, Camelia; Grolimund, Daniel; Milne, Christopher J; Chergui, Majed

    2015-10-20

    Diatomic ligands in hemoproteins and the way they bind to the active center are central to the protein's function. Using picosecond Fe K-edge X-ray absorption spectroscopy, we probe the NO-heme recombination kinetics with direct sensitivity to the Fe-NO binding after 532-nm photoexcitation of nitrosylmyoglobin (MbNO) in physiological solutions. The transients at 70 and 300 ps are identical, but they deviate from the difference between the static spectra of deoxymyoglobin and MbNO, showing the formation of an intermediate species. We propose the latter to be a six-coordinated domed species that is populated on a timescale of ∼ 200 ps by recombination with NO ligands. This work shows the feasibility of ultrafast pump-probe X-ray spectroscopic studies of proteins in physiological media, delivering insight into the electronic and geometric structure of the active center.

  13. Theoretical investigation of the mechanism and kinetics for HCO + HCN ⇄ HCHO + CN

    NASA Astrophysics Data System (ADS)

    Wen, Lin Feng; Yan, Wang; Shao, Wen Zhang; Xian, Yong Pang

    1997-02-01

    The mechanism and kinetics for HCO + HCN ⇄ HCNO + CN have been studied theoretically. The potential energy profile along the intrinsic reaction coordinate (IRC) has been obtained at ab initio QCISD/6-31G ∗∗//UHF/6-31G ∗∗ and CCSD/6-31G ∗∗//UHF/6-31G ∗∗ levels. The forward activation barriers are about 136.45 adn 140.94 kJ mol -1 at these levels, respectively, and the reverse barriers are 2.71 and 1.26 kJ mol -1, respectively. The canonical rate constants for the forward and reverse reactions have been calculated by using statistical theory.

  14. Nantenine as an acetylcholinesterase inhibitor: SAR, enzyme kinetics and molecular modeling investigations

    PubMed Central

    Pecic, Stevan; McAnuff, Marie A.; Harding, Wayne W.

    2015-01-01

    Nantenine, as well as a number of flexible analogs, were evaluated for acetylcholinesterase (AChE) inhibitory activity in microplate spectrophotometric assays based on Ellman’s method. It was found that the rigid aporphine core of nantenine is an important structural requirement for its anticholinesterase activity. Nantenine showed mixed inhibition kinetics in enzyme assays. Molecular docking experiments suggest that nantenine binds preferentially to the catalytic site of AChE but is also capable of interacting with the peripheral anionic site (PAS) of the enzyme, thus accounting for its mixed inhibition profile. The aporphine core of nantenine may thus be a useful template for the design of novel PAS or dual-site AChE inhibitors. Inhibiting the PAS is desirable for prevention of aggregation of the amyloid peptide Aβ, a major causative factor in the progression of Alzheimer’s disease (AD). PMID:20583856

  15. Wetting of biopolymer coatings: contact angle kinetics and image analysis investigation.

    PubMed

    Farris, Stefano; Introzzi, Laura; Biagioni, Paolo; Holz, Torsten; Schiraldi, Alberto; Piergiovanni, Luciano

    2011-06-21

    The surface wetting of five biopolymers, used as coating materials for a plastic film, was monitored over a span of 8 min by means of the optical contact angle technique. Because most of the total variation was observed to occur during the first 60 s, we decided to focus on this curtailed temporal window. Initial contact angle values (θ(0)) ranged from ∼91° for chitosan to ∼30° for pullulan. However, the water drop profile began to change immediately following drop deposition for all biocoatings, confirming that the concept of water contact angle equilibrium is not applicable to most biopolymers. First, a three-parameter decay equation [θ(t) = θ(0) exp(kt(n))] was fit to the experimental contact angle data to describe the kinetics of the contact angle change for each biocoating. Interestingly, the k constant correlated well with the contact angle evolution rate and the n exponent seemed to be somehow linked to the physicochemical phenomena underlying the overall kinetics process. Second, to achieve a reliable description of droplet evolution, the contact angle (CA) analysis was coupled with image analysis (IA) through a combined geometric/trigonometric approach. Absorption and spreading were the key factors governing the overall mechanism of surface wetting during the 60 s analysis, although the individual quantification of both phenomena demonstrated that spreading provided the largest contribution for all biopolymers, with the only exception of gelatin, which showed two quasi-equivalent and counterbalancing effects. The possible correlation between these two phenomena and the topography of the biopolymer surfaces are then discussed on the basis of atomic force microscopy analyses.

  16. An Initial Ultraviolet Investigation of Rapidly Evolving Short Period Eclipsing Binaries

    NASA Astrophysics Data System (ADS)

    Shaw, J. Scott

    A new class of short period, strongly interacting eclipsing binary systems undergoing rapid mass exchange and/or mass loss has been recently identified by one of us (JSS). This group of close binary systems is akin to W UMa-type systems but has somewhat longer orbital periods and components of very dissimilar temperatures. The systems SW Lyn, V1010 Oph, and RT Scl are the best known members of this class of binaries. These Systems appear to be in an early stage of case A binary evolution prior to becoming contact systems in which the more massive hotter (A to F) component is close to or at its Roche limiting surface. Analyses of their asymmetric light curves and period changes indicate substantial mass exchange and/or mass loss. Present groundbased spectra show variable asymmetric line profiles. The photometric studies indicate that the observed asymmetries in the light curves can be explained by the presence of a bright shock region ("hot spot") produced on the receding hemisphere of the cooler component, by the impact of a gas stream from the more massive component. In this initial UV study we propose to observe a small, but representative sample of these stars with the IUE satellite in the wavelength region 1175-3200 using the SWP and LWR cameras. Low dispersion SWP and LWR spectra will be taken during eclipses and at elongations to allow us to identify and map out gas flows and the interacting plasmas using resonance lines of Fe II and Mg II h and k in the near UV and lines such as CIII, CIV, NIV, NV, and SiIII and SiIV in the far UV. High dispersion UV spectra of the brightest member of the class, V1010 Oph, will be obtained for a detailed investigation of the velocities of the expected gas streaming as well as the thermal and mass flow properties of the interacting plasmas. We plan to obtain ground-based spectroscopic and photometric observations of V1010 Oph at or near the time the UV observations are made.

  17. Long-Term Follow-up Investigation of Isolated Rapid Eye Movement Sleep Without Atonia Without Rapid Eye Movement Sleep Behavior Disorder: A Pilot Study

    PubMed Central

    Stefani, Ambra; Gabelia, David; Högl, Birgit; Mitterling, Thomas; Mahlknecht, Philipp; Stockner, Heike; Poewe, Werner; Frauscher, Birgit

    2015-01-01

    Study Objectives: Idiopathic rapid eye movement (REM) sleep behavior disorder (RBD) is a harbinger of synuclein-mediated neurodegenerative diseases. It is unknown if this also applies to isolated REM sleep without atonia (RWA). We performed a long-term follow-up investigation of subjects with isolated RWA. Methods: Participants were recruited from 50 subjects with isolated RWA who were identified at the sleep laboratory of the Department of Neurology at the Medical University of Innsbruck between 2003 and 2005. Eligible subjects underwent follow-up clinical examination, polysomnography, and assessment of neurodegenerative biomarkers (cognitive impairment, finger speed deficit, impaired color vision, olfactory dysfunction, orthostatic hypotension, and substantia nigra hyperechogenicity). Results: After a mean of 8.6 ± 0.9 y, 1 of 14 participating subjects (7.3%) progressed to RBD. Ten of 14 RWA subjects (71.4%) were positive for at least one neurodegenerative biomarker. Substantia nigra hyperechogenicity and presence of mild cognitive impairment were both present in 4 of 14 subjects with isolated RWA. Electromyographic activity measures increased significantly from baseline to follow-up polysomnography (“any” mentalis and both anterior tibialis muscles: 32.5 ± 9.4 versus 52.2 ± 16.6%; p = 0.004). Conclusion: This study provides first evidence that isolated RWA is an early biomarker of synuclein-mediated neurodegeneration. These results will have to be replicated in larger studies with longer observational periods. If confirmed, these disease findings have implications for defining at-risk cohorts for Parkinson disease. Citation: Stefani A, Gabelia D, Högl B, Mitterling T, Mahlknecht P, Stockner H, Poewe W, Frauscher B. Long-term follow-up investigation of isolated rapid eye movement sleep without atonia without rapid eye movement sleep behavior disorder: a pilot study. J Clin Sleep Med 2015;11(11):1273–1279. PMID:26156949

  18. Structural investigation of oxovanadium(IV) Schiff base complexes: X-ray crystallography, electrochemistry and kinetic of thermal decomposition

    NASA Astrophysics Data System (ADS)

    Asadi, Mozaffar; Asadi, Zahra; Savaripoor, Nooshin; Dusek, Michal; Eigner, Vaclav; Shorkaei, Mohammad Ranjkesh; Sedaghat, Moslem

    2015-02-01

    A series of new VO(IV) complexes of tetradentate N2O2 Schiff base ligands (L1-L4), were synthesized and characterized by FT-IR, UV-vis and elemental analysis. The structure of the complex VOL1ṡDMF was also investigated by X-ray crystallography which revealed a vanadyl center with distorted octahedral coordination where the 2-aza and 2-oxo coordinating sites of the ligand were perpendicular to the "-yl" oxygen. The electrochemical properties of the vanadyl complexes were investigated by cyclic voltammetry. A good correlation was observed between the oxidation potentials and the electron withdrawing character of the substituents on the Schiff base ligands, showing the following trend: MeO < H < Br < Cl. We also studied the thermodynamics of formation of the complexes and kinetic aspects of their thermal decomposition. The formation constants with various substituents on the aldehyde ring follow the trend 5-OMe > 5-H > 5-Br > 5-Cl. Furthermore, the kinetic parameters of thermal decomposition were calculated by using the Coats-Redfern equation. According to the Coats-Redfern plots the kinetics of thermal decomposition of studied complexes is of the first-order in all stages, the free energy of activation for each following stage is larger than the previous one and the complexes have good thermal stability. The preparation of VOL1ṡDMF yielded also another compound, one kind of vanadium oxide [VO]X, with different habitus of crystals, (platelet instead of prisma) and without L1 ligand, consisting of a V10O28 cage, diaminium moiety and dimethylamonium as a counter ions. Because its crystal structure was also new, we reported it along with the targeted complex.

  19. Time resolved spectroscopic investigation of SiD2 + D2: kinetic study

    NASA Astrophysics Data System (ADS)

    Al-Rubaiey, Najem A.; Walsh, Robin

    2017-03-01

    Silylenes (silanediyls) have made an important impact on organosilicon chemistry even if it is of more recent foundation than carbenes in organic chemistry and much less complete. These species are highly reactive intermediates. They play a central role in the chemical vapour deposition (CVD) of various silicon-containing thin films which have a technological importance in microelectronics as well as in the dry etching processes of silicon wafers. Spectroscopic methods have been developed to observe these species, a necessary pre-requisite to their direct monitoring. In this work, deuterated phenylsilane precursor, PhSiD3 was chosen for SiD2 because its analogue phenylsilane, PhSiH3 proved to be a good precursor for SiH2 and the high quality decay signals observed revealed that SiD2 be readily detected from PhSiD3 and that if other decomposition pathways (e.g. PhSiD + D2) are occurring, they do not effect measurements of the rate constants for SiD2. The absorption spectrum of SiD2 formed from the flash photolysis of a mixture of PhSiD3 and SF6 at 193nm were found in the region 17384-17391 cm-1 with strong band at 17387.07 cm-1. This single rotational line of pQ1 was chosen to monitor SiD2 removal. Time-resolved studies of SiD2 have been carried out to obtain rate constants for its bimolecular reactions with D2. The reactions were studied over the pressure range 5-100 Torr (in SF6 bath gas) at four temperatures in the range 298-498K. Single decay from 10 photolysis laser shots were averaged and found to give reasonable first-order kinetics fits. Second order kinetics were obtained by pressure dependence of the pseudo first order decay constants and substance D2 pressures within experimental error. The reaction was found to be weakly pressure dependent at all temperatures, consistent with a third-body mediated association process. In addition, SiH2+ H2 reaction is approximately ca. 60% faster than SiD2+D2 reaction. Theoretical extrapolations (using Lindemann

  20. The Investigation of Demand for a Rapid Document Delivery Service for the University of Pittsburgh Library System. Final Report.

    ERIC Educational Resources Information Center

    Montgomery, K. Leon; And Others

    A joint project of the University of Pittsburgh Library System and the School of Library and Information Science investigated the need for a rapid document delivery service within the University Library System (ULS). Two instruments were designed to answer questions about library patrons' uses of bibliographic citations retrieved in online…

  1. Rapid kinetics of insertion and accessibility of spin-labeled phospholipid analogs in lipid membranes: a stopped-flow electron paramagnetic resonance approach.

    PubMed Central

    Marx, U; Lassmann, G; Wimalasena, K; Müller, P; Herrmann, A

    1997-01-01

    Spin-labeled phospholipid analogs have been employed to probe the transbilayer distribution of endogenous phospholipids in various membrane systems. To determine the transmembrane distribution of the spin-labeled analogs, the analogs are usually inserted into the membrane of interest and subsequently the amount of analog in the outer membrane leaflet is determined either by chemical reduction with ascorbate or by back-exchange to bovine serum albumin (BSA). For accurate determination of the transbilayer distribution of analogs, both the kinetics of incorporation and those of accessibility of analogs to ascorbate or BSA have to be fast in comparison to their transbilayer movement. By means of stopped-flow electron paramagnetic resonance (EPR) spectroscopy, we have studied the kinetics of incorporation of the spin-labeled phosphatidylcholine (PC) analog 1-palmitoyl-2-(4-doxylpentanoyl)-sn-glycero-3-phosphocholine (SL-PC) and of its accessibility to chemical reduction and to back-exchange at room temperature. Incorporation of SL-PC into the outer leaflet of egg phosphatidylcholine (EPC) and red cell ghost membranes was essentially completed within 5 s. Ninety percent of the SL-PC molecules located in the outer membrane leaflet of those membranes were extracted by BSA within 15 s. All exterior-facing SL-PC molecules were reduced by ascorbate in a pseudo-first-order reaction within 60 s in EPC membranes and within 90 s in red cell ghost membranes. The rate of the reduction process could be enhanced by approximately 30-fold when 6-O-phenyl-ascorbic acid was used instead of ascorbate as the reducing agent. The results are discussed in light of assaying rapid transbilayer movement of spin-labeled analogs in biological membranes. PMID:9284331

  2. Human enteropeptidase light chain: bioengineering of recombinants and kinetic investigations of structure and function.

    PubMed

    Smith, Eliot T; Johnson, David A

    2013-05-01

    The serine protease enteropeptidase exhibits a high level of substrate specificity for the cleavage sequence DDDDK∼ X, making this enzyme a useful tool for the separation of recombinant protein fusion domains. In an effort to improve the utility of enteropeptidase for processing fusion proteins and to better understand its structure and function, two substitution variants of human enteropeptidase, designated R96Q and Y174R, were created and produced as active (>92%) enzymes secreted by Pichia pastoris with yields in excess of 1.7 mg/Liter. The Y174R variant showed improved specificities for substrates containing the sequences DDDDK (kcat /KM = 6.83 × 10⁶ M⁻¹ sec⁻¹) and DDDDR (kcat /KM = 1.89 × 10⁷ M⁻¹ sec⁻¹) relative to all other enteropeptidase variants reported to date. BPTI inhibition of Y174R was significantly decreased. Kinetic data demonstrate the important contribution of the positively charged residue 96 to extended substrate specificity in human enteropeptidase. Modeling shows the importance of the charge-charge interactions in the extended substrate binding pocket.

  3. Towards in situ fluorescence spectroscopy and microscopy investigations of asphaltene precipitation kinetics.

    PubMed

    Franco, Juliana C; Gonçalves, Grasiele; Souza, Monique S; Rosa, Samantha B C; Thiegue, Larissa M; Atvars, Teresa D Z; Rosa, Paulo T V; Nome, René A

    2013-12-16

    We perform a spectroscopic analysis of asphaltene in solution and in crude oil with the goal of designing an optical probe of asphaltene precipitation inside high-pressure cells. Quantitative analysis of steady-state spectroscopic data is employed to identify fluorescence and Raman contributions to the observed signals. Time-resolved fluorescence spectroscopy indicates that fluorescence lifetime can be used as a spectroscopic probe of asphaltene in crude oil. Quantitative confocal laser-scanning microscopy studies of asphaltene in n-heptane are used to calculate particle-size distributions as a function of time, both at the sample surface and asphaltene interior. The resulting precipitation kinetics is well described by stochastic numerical simulations of diffusion-limited aggregation. Based on these results, we present the design and construction of an apparatus to optically probe the in situ precipitation of asphaltene suitable for studies inside high pressure cells. Design considerations include the use of a spatial light modulator for aberration correction in microscopy measurements, together with the design of epi-fluorescence spectrometer, both fiber-based and for remote sensing fluorescence spectroscopy.

  4. A methyl methacrylate-HEMA-CL(n) copolymerization investigation: from kinetics to bioapplications.

    PubMed

    Ferrari, Raffaele; Rooney, Thomas R; Lupi, Monica; Ubezio, Paolo; Hutchinson, Robin A; Moscatelli, Davide

    2013-10-01

    The radical copolymerization kinetics of methyl methacrylate (MMA) and poly-ϵ-caprolactone macromonomer functionalized with a vinyl end group (HEMA-CL(n)) is studied using a pulsed-laser technique. The reactivity ratios for this system are near unity, while a linear relationship between k(p,cop), the copolymer-averaged propagation rate coefficient, and the composition of macromonomer in the feed (0-80 wt% range) is determined. At 50 wt% macromonomer in the feed, a 1.67 ± 0.02 and 1.64 ± 0.06 increase in k(p,cop)/k(p,MMA) is determined for HEMA-CL3 and HEMA-CL2, respectively. These macromonomers are adopted to synthesize nanoparticles (NPs) in the range of 100-150 nm through batch emulsion free radical polymerization (BEP) to produce partially degradable drug delivery carriers. The produced NPs are tested in 4T1 cell line and show excellent characteristics as carriers: they do not affect cell proliferation, and a relevant number of NPs, thousands per cell, are internalized.

  5. Investigating the nitrification and denitrification kinetics under aerobic and anaerobic conditions by Paracoccus denitrificans ISTOD1.

    PubMed

    Medhi, Kristina; Singhal, Anjali; Chauhan, D K; Thakur, Indu Shekhar

    2017-03-16

    Municipal wastewater contains multiple nitrogen contaminants such as ammonia, nitrate and nitrite. Two heterotrophic nitrifier and aerobic denitrifiers, bacterial isolates ISTOD1 and ISTVD1 were isolated from domestic wastewater. On the basis of removal efficiency of ammonia, nitrate and nitrite under both aerobic and anaerobic conditions, ISTOD1 was selected and identified as Paracoccus denitrificans. Aerobically, NH4(+)-N had maximum specific nitrogen removal rate (Rxi) of 7.6g/gDCW/h and anaerobically, NO3(-)N showed Rxi of 2.5*10(-1)g/g DCW/h. Monod equation described the bioprocess kinetic coefficients, µmax and Ks, obtained by regression. Error functions were calculated to validate the Monod equation experimental data. Aerobic NO3(-)N showed the highest YW of 0.372mg DCW/mg NO3(-)N among the five conditions. ISTOD1 serves as a potential candidate for treating nitrogen rich wastewater using simultaneous nitrification and aerobic denitrification. It can be used in bioaugmentation studies under varied condition.

  6. Mechanisms and Kinetics of Amyloid Aggregation Investigated by a Phenomenological Coarse-Grained Model

    NASA Astrophysics Data System (ADS)

    Magno, Andrea; Pellarin, Riccardo; Caflisch, Amedeo

    Amyloid fibrils are ordered polypeptide aggregates that have been implicated in several neurodegenerative pathologies, such as Alzheimer's, Parkinson's, Huntington's, and prion diseases, [1, 2] and, more recently, also in biological functionalities. [3, 4, 5] These findings have paved the way for a wide range of experimental and computational studies aimed at understanding the details of the fibril-formation mechanism. Computer simulations using low-resolution models, which employ a simplified representation of protein geometry and energetics, have provided insights into the basic physical principles underlying protein aggregation in general [6, 7, 8] and ordered amyloid aggregation. [9, 10, 11, 12, 13, 14, 15] For example, Dokholyan and coworkers have used the Discrete Molecular Dynamics method [16, 17] to shed light on the mechanisms of protein oligomerization [18] and the conformational changes that take place in proteins before the aggregation onset. [19, 20] One challenging observation, which is difficult to observe by computer simulations, is the wide range of aggregation scenarios emerging from a variety of biophysical measurements. [21, 22] Atomistic models have been employed to study the conformational space of amyloidogenic polypeptides in the monomeric state, [23, 24, 25] the very initial steps of amyloid formation, [26, 27, 28, 29, 30, 31, 32] and the structural stability of fibril models. [33, 34, 35) However, all-atom simulations of the kinetics of fibril formation are beyond what can be done with modern computers.

  7. Thermodynamic and kinetic investigations of PO3-4 adsorption on blast furnace slag.

    PubMed

    Oguz, Ensar

    2005-01-01

    The kinetics of adsorption of PO(3-)(4) by blast furnace slag were found to be fast, reaching equilibrium in 20 min and following a pseudo-second-order rate equation. The adsorption behavior of PO(3-)(4) on blast furnace slag has been studied as a function of the solution agitation speed, pH, and temperature. Results have been analyzed by Freundlich, Langmuir, BET, and Dubinin-Radushkevich (D-R) adsorption isotherms. The mean energy of adsorption, 10.31 kJ mol(-1), was calculated from the D-R adsorption isotherm. The rate constants were calculated for 293, 298, 303, and 308 K using a pseudo-second-order rate equation and the activation energy (E(a)) was derived using the Arrhenius equation. Thermodynamic parameters such as DeltaH(0), DeltaS(0), and DeltaG(0) were calculated from the slope and intercept of linear plot of lnK(D) against 1/T. The DeltaH(0) and DeltaG(0) values of PO(3-)(4) adsorption on the blast furnace slag show endothermic heat of adsorption. But there is a negative free energy value, indicating that the process of PO(3-)(4) adsorption is favored at high temperatures.

  8. Nitrite dismutase reaction mechanism: kinetic and spectroscopic investigation of the interaction between nitrophorin and nitrite.

    PubMed

    He, Chunmao; Howes, Barry D; Smulevich, Giulietta; Rumpel, Sigrun; Reijerse, Edward J; Lubitz, Wolfgang; Cox, Nicholas; Knipp, Markus

    2015-04-01

    Nitrite is an important metabolite in the physiological pathways of NO and other nitrogen oxides in both enzymatic and nonenzymatic reactions. The ferric heme b protein nitrophorin 4 (NP4) is capable of catalyzing nitrite disproportionation at neutral pH, producing NO. Here we attempt to resolve its disproportionation mechanism. Isothermal titration calorimetry of a gallium(III) derivative of NP4 demonstrates that the heme iron coordinates the first substrate nitrite. Contrary to previous low-temperature EPR measurements, which assigned the NP4-nitrite complex electronic configuration solely to a low-spin (S = 1/2) species, electronic absorption and resonance Raman spectroscopy presented here demonstrate that the NP4-NO2(-) cofactor exists in a high-spin/low-spin equilibrium of 7:3 which is in fast exchange in solution. Spin-state interchange is taken as evidence for dynamic NO2(-) coordination, with the high-spin configuration (S = 5/2) representing the reactive species. Subsequent kinetic measurements reveal that the dismutation reaction proceeds in two discrete steps and identify an {FeNO}(7) intermediate species. The first reaction step, generating the {FeNO}(7) intermediate, represents an oxygen atom transfer from the iron bound nitrite to a second nitrite molecule in the protein pocket. In the second step this intermediate reduces a third nitrite substrate yielding two NO molecules. A nearby aspartic acid residue side-chain transiently stores protons required for the reaction, which is crucial for NPs' function as nitrite dismutase.

  9. Curing behavior and reaction kinetics of binder resins for 3D-printing investigated by dielectric analysis (DEA)

    NASA Astrophysics Data System (ADS)

    Möginger, B.; Kehret, L.; Hausnerova, B.; Steinhaus, J.

    2016-05-01

    3D-Printing is an efficient method in the field of additive manufacturing. In order to optimize the properties of manufactured parts it is essential to adapt the curing behavior of the resin systems with respect to the requirements. Thus, effects of resin composition, e.g. due to different additives such as thickener and curing agents, on the curing behavior have to be known. As the resin transfers from a liquid to a solid glass the time dependent ion viscosity was measured using DEA with flat IDEX sensors. This allows for a sensitive measurement of resin changes as the ion viscosity changes two to four decades. The investigated resin systems are based on the monomers styrene and HEMA. To account for the effects of copolymerization in the calculation of the reaction kinetics it was assumed that the reaction can be considered as a homo-polymerization having a reaction order n≠1. Then the measured ion viscosity curves are fitted with the solution of the reactions kinetics - the time dependent degree of conversion (DC-function) - for times exceeding the initiation phase representing the primary curing. The measured ion viscosity curves can nicely be fitted with the DC-function and the determined fit parameters distinguish distinctly between the investigated resin compositions.

  10. Investigating Rapid Uplift and Subsidence Near Norris, Yellowstone, During 2013-2014

    NASA Astrophysics Data System (ADS)

    Stovall, W. K.; Cervelli, P. F.; Shelly, D. R.

    2014-12-01

    Although Yellowstone's last magmatic eruption occurred about 70,000 years ago, hydrothermal explosions, earthquakes, and ground deformation still occur as testament to ongoing volcanic and tectonic processes. Since the late 1990s, a network of continuously recording Global Positioning System (GPS) receivers has recorded uplift and subsidence of the caldera and northwest caldera margin near Norris Geyser Basin. Previous deformation episodes have shown opposing vertical motion at the two sites, which has been attributed to temporal variations in magmatic fluid flux from the caldera laterally through the Norris-Mammoth fault corridor that intersects the caldera's northwest margin (Dzurisin et al., 2012; Wicks et al., 2006). These episodes have exhibited gradual changes, transitioning from uplift to subsidence (and vice versa) over weeks to months. Large earthquake swarms accompanied transitions from caldera uplift to subsidence in 1985 and 2010. Recent deformation in Yellowstone differs from previously observed episodes. In the latter half of 2013, uplift began around Norris, and by January of 2014 it reached rates of over 15 cm/yr. Also at the start of 2014, caldera deformation shifted from approximately 4 years of slow subsidence to slow uplift. On March 30, 2014, a M4.8 earthquake, the largest in Yellowstone since 1980, occurred northwest of Norris Geyser Basin near the center of uplift. Shortly after the event, deformation near Norris abruptly reversed to rapid subsidence (over 20 cm/yr). Caldera uplift began to accelerate around the same time. Thus, uplift can occur simultaneously in both the caldera and the Norris area, and dramatic reversals from rapid uplift to rapid subsidence can occur within a matter of days. While the complexity of the deformation defies a simple explanation, we hypothesize that the rapid transition from uplift to subsidence at Norris may indicate that the M4.8 earthquake opened a pathway for fluid migration away from Norris and allowed an

  11. Freeze concentration effects on ice (photo) chemical kinetics investigated by UV-Vis spectroscopy

    NASA Astrophysics Data System (ADS)

    Newberg, J. T.; Arble, C.; Zhang, J.

    2013-12-01

    We will describe the setup of a fiber coupled UV-Vis spectrometer to investigate the chemistry and photochemistry of aqueous solutions before and after freezing. The photochemical degradation of pyranine at the isosbestic point was investigated. Direct photochemical degradation was minor compared to indirect degradation through hydroxyl radical (OH) attack at room temperature. At -10 C indirect OH degradation was increased relative to room temperature studies, and has been attributed to the freeze concentration effect. The reaction of bromate with bromide in the presence of acid to form molecular bromine was investigated. Upon freezing the formation rate of bromine significantly increases, which we attribute to the freeze concentration effect.

  12. Investigation of the first-order phase transition kinetics using the method of pulsed photothermal surface deformation: radial measurements

    NASA Astrophysics Data System (ADS)

    Vintzentz, S. V.; Sandomirsky, V. B.

    1992-09-01

    An extension of the photothermal surface deformation (PTSD) method to study the macroscopic kinetics of the first-order phase transition (PTr) is given. The movement of the phase interface (PI) over a surface with a PTr locally induced in the subsurface volume by a focused laser pulse is investigated for the first time using radial measurements of the PTSD kinetics. For the known metal-to-semiconductor PTr in VO 2 (a good model system) a procedure is suggested for measuring the maximum size rsm of the "hot" (metal) phase on the surface (a parameter most difficult to determine) as well as for estimating the velocity of the PI movement over the surface, vs, and in the bulk, vb. Besides, it is shown that the PTSD method may be used to determine the "local" threshold energy E0 needed for the laser-induced PTr and the "local" latent heat L of the PTr. This demonstrates the feasibility of scanning surface E0- and L-microscopy.

  13. Irradiation deformation near different atomic grain boundaries in α-Zr: An investigation of thermodynamics and kinetics of point defects

    PubMed Central

    Arjhangmehr, A.; Feghhi, S. A. H.

    2016-01-01

    Understanding radiation performance of nanocrystalline Zr-based alloys is essential to develop internal components and external cladding materials with self-healing capabilities for longer and safer life cycles in harsh reactor environments. However, the precise role of interfaces in modifying defect production and evolution in α-Zr is not yet determined. Using atomistic simulation methods, we investigate the influence of different atomic grain boundaries (GBs) in thermodynamic and kinetic properties of defects on short timescales. We observe that the sink efficiency and sink strength of interfaces vary significantly with the boundary structures, with a preference to absorb interstitials (vacancies) when the GBs are semi-parallel (semi-perpendicular) relative to the basal planes. Further, we identify three distinct primary cascade geometries, and find that the residual defect clustering in grain interiors depends on how the atomic GBs modify the spatial distribution of defects within the crystal structure. Finally, we explain and discuss the dynamic results in terms of energetic and kinetic behaviors of defects near the pristine and damaged boundaries. Eventually, these will provide a microscopic reference for further improving the radiation response of Zr by using fine grains or by introducing a high density of dispersoids in material metallurgy. PMID:27004606

  14. Kinetics and mechanism of the degradation of methyl parathion in aqueous hydrogen sulfide solution: investigation of natural organic matter effects.

    PubMed

    Guo, Xiaofen; Jans, Urs

    2006-02-01

    The kinetics of the transformation of methyl parathion have been investigated in aqueous solution containing reduced sulfur species and small concentrations of natural organic matter (NOM) from different sources such as soil, river, and peat. It was shown that NOM mediates the degradation of methyl parathion in aqueous solutions containing hydrogen sulfide. After evaluating and quantifying the effect of the NOM concentration on the degradation kinetics of methyl parathion in the presence of hydrogen sulfide, it was found that the observed pseudo-first-order reaction rate constants (k(obs)) were proportional to NOM concentrations. The influence of pH on the degradation of methyl parathion in the aqueous solutions containing hydrogen sulfide and NOM has been studied. The rate of degradation of methyl parathion was strongly pH dependent. The results indicate k(obs) with a commercially available humic acid has a maximum value at approximately pH 8.3. Two main reaction mechanisms are identified to dominate the degradation of methyl parathion in aqueous solution containing hydrogen sulfide and NOM based on the products aminomethyl parathion and desmethyl methyl parathion. The two mechanisms are nitro-group reduction and nucleophilic attack at the methoxy-carbon. The reduction of the nitro-group is only observed in the presence of NOM. The results of this study form an important base for the evaluation and interpretation of transformation processes of methyl parathion in the environment.

  15. Irradiation deformation near different atomic grain boundaries in α-Zr: An investigation of thermodynamics and kinetics of point defects.

    PubMed

    Arjhangmehr, A; Feghhi, S A H

    2016-03-23

    Understanding radiation performance of nanocrystalline Zr-based alloys is essential to develop internal components and external cladding materials with self-healing capabilities for longer and safer life cycles in harsh reactor environments. However, the precise role of interfaces in modifying defect production and evolution in α-Zr is not yet determined. Using atomistic simulation methods, we investigate the influence of different atomic grain boundaries (GBs) in thermodynamic and kinetic properties of defects on short timescales. We observe that the sink efficiency and sink strength of interfaces vary significantly with the boundary structures, with a preference to absorb interstitials (vacancies) when the GBs are semi-parallel (semi-perpendicular) relative to the basal planes. Further, we identify three distinct primary cascade geometries, and find that the residual defect clustering in grain interiors depends on how the atomic GBs modify the spatial distribution of defects within the crystal structure. Finally, we explain and discuss the dynamic results in terms of energetic and kinetic behaviors of defects near the pristine and damaged boundaries. Eventually, these will provide a microscopic reference for further improving the radiation response of Zr by using fine grains or by introducing a high density of dispersoids in material metallurgy.

  16. Frijolito Watershed: Integrated investigations of a rapidly eroding pinyon-juniper hillslope

    SciTech Connect

    Wilcox, B.P.; Pitlick, J.; Allen, C.D.

    1995-12-31

    The dramatic acceleration of erosion associated with the expansion of pinyon-juniper woodlands over the past 100 years has been widely recognized, but few process-based studies of this phenomenon have been undertaken. In an attempt to identify the underlying causes, and the factors that affect erosion processes, we have initiated an interdisciplinary study of a rapidly eroding pinyon-juniper woodland in northern New Mexico. Since July 1993, we have collected data on runoff, erosion, and weather conditions from a 1-ha catchment study area and have conducted surveys of topography, soils, and vegetation. Our preliminary results indicate that although runoff makes up less than 10% of the annual water budget, runoff events - which are frequent in the summer - are capable of moving large amounts of sediment. We estimate that between July 1993 and October 1994, between 25,000 and 50,000 kg of sediment has eroded and been transported from the catchment. The information gained from such studies is essential to our ability to formulate effective strategies for managing these rapidly eroding woodlands.

  17. Preliminary Investigations of the Kinetics of Nitrogen Transformation and Nitrosamine Formation in Land Treatment of Wastewater.

    DTIC Science & Technology

    1979-03-01

    including: Acetomonas, Alcaligenes, Bacillus , , Corynebacterium, Flavobacterium, 5 Ilalobacterium, Listeria, Paracoccus, Pseudomonas and...On the other hand, denitrifying members of the genus Bacillus have also been found in high numbers (60). Another researcher (91) has found a...preponderance of Bacillus types at low nitrate levels in soil, and after the soil was enriched with nitrate and incubated anaerobibally, this investigator

  18. Kinetic investigation of catalytic disproportionation of superoxide ions in the non-aqueous electrolyte used in Li–air batteries

    SciTech Connect

    Wang, Qiang; Zheng, Dong; McKinnon, Meaghan E.; Yang, Xiao -Qing; Qu, Deyang

    2014-10-28

    Superoxide reacts with carbonate solvents in Li–air batteries. Tris(pentafluorophenyl)borane is found to catalyze a more rapid superoxide (O2-) disproportionation reaction than the reaction between superoxide and propylene carbonate (PC). With this catalysis, the negative impact of the reaction between the electrolyte and O2-produced by the O2 reduction can be minimized. A simple kinetic study using ESR spectroscopy was reported to determine reaction orders and rate constants for the reaction between PC and superoxide, and the disproportionation of superoxide catalyzed by Tris(pentafluorophenyl)borane and Li ions. As a result, the reactions are found to be first order and the rate constants are 0.033 s-1 M-1, 0.020 s-1 M-1and 0.67 s-1M-1 for reactions with PC, Li ion and Tris(pentafluorophenyl)borane, respectively.

  19. Microstructural investigation to the controlled release kinetics of monolith osmotic pump tablets via synchrotron radiation X-ray microtomography.

    PubMed

    Li, Haiyan; Yin, Xianzhen; Ji, Junqiu; Sun, Lixin; Shao, Qun; York, Peter; Xiao, Tiqiao; He, You; Zhang, Jiwen

    2012-05-10

    Tomographic imaging techniques are attractive tools for the visualization of the internal structural characteristics of pharmaceutical solid dosage forms. In this paper, the internal structure of the tablet core for a monolith osmotic drug delivery system, felodipine sustained-release tablet, was visualized via synchrotron radiation X-ray computed microtomography during the drug release process. The surface areas and three dimensional parameters of the tablet core were calculated based on the three dimensional reconstruction of the images. At different stages of the drug release process, the surface morphology, the hydration, the swelling, and the structure changing of the tablet, were visualized from the two dimensional monochrome X-ray images. The three dimensional volumes of the remaining tablet core correlated well with the percentages of felodipine (R=0.9988). Also, the three dimensional surface area almost unchanged during the drug release process, which clearly demonstrated the intrinsic drug release mechanism of the osmotic drug delivery system. In conclusion, the synchrotron radiation X-ray computed microtomography, with rapid acquisition, high intensity and micro-scale spatial resolution, was found to be a useful tool for the quantitative elucidation of the intrinsic drug release kinetics and the three dimensional parameters such as surface areas of the remained core obtained by the synchrotron radiation. Thus, X-ray computed microtomography can be considered as a new and complimentary analytical tool to standard compendial pharmaceutical tests for quality control of osmotic drug delivery systems.

  20. Investigation of the aluminum phthalocyanine nanoparticles colloidal solutions pH-dependent photoluminescence kinetics in pico- and nanosecond time range

    NASA Astrophysics Data System (ADS)

    Bystrov, F. G.; Makarov, V. I.; Loschenov, V. B.

    2016-08-01

    In this study, the fluorescence intensity decay of aluminum phthalocyanine nanoparticles colloidal solutions at different pH was investigated. Hamamatsu Streak-Camera (C10627 - 13 Hamamatsu Photonics) with picosecond temporal resolution (15 ps) was used to carry out the measurements. For excitation we used Hamamatsu Picosecond Light Pulser PLP - 10 with 637 nm wavelength and 65 ps pulse duration. The changes in fluorescence decay kinetics were found during the experiment. The number of fluorescence lifetime components and duration of lifetimes depends on pH. At pH 2 the presence of two fluorescence lifetimes was recorded: the first one was 5 ns, which corresponded to the molecular form in solution, and 1.5 ns, which corresponded to bound state of phthalocyanine molecules. This work is a preparatory step towards a model which describes the interaction of aluminum phthalocyanine nanoparticles with environment in biological tissue.

  1. An Investigation of the Effect of Surface Impurities on the Adsorption Kinetics of Hydrogen Chemisorbed onto Iron

    NASA Technical Reports Server (NTRS)

    Shanabarger, R. M.

    1997-01-01

    The original goal of this program was to investigate the effect surface impurities have on the heterogeneous kinetic processes of those molecular species which produce gaseous hydrogen degradation of the mechanical properties of metallic structural materials. However, shortly after the initiation of the original program, the program's NASA Technical Monitor, Dr. Howard Nelson, requested that the effort supported by this Co-operative Agreement be redirected to study more pressing materials issues associated to the development of the National Aero-Space Plane (NASP). The results of these efforts are outlined in this report. Detailed discussions of specific work, including experimental techniques and procedures, will be found in the publications listed with the subsection discussing that specific work as well and in Section 5. No inventions were generated or disclosed within this Agreement.

  2. Cyanide inhibition of cytochrome c oxidase. A rapid-freeze e.p.r. investigation.

    PubMed Central

    Jensen, P; Wilson, M T; Aasa, R; Malmström, B G

    1984-01-01

    The inhibition of cytochrome c oxidase by cyanide, starting either with the resting or the pulsed enzyme, was studied by rapid-freeze quenching followed by quantitative e.p.r. It is found that a partial reduction of cytochrome oxidase by transfer of 2 electron equivalents from ferrocytochrome c to cytochrome a and CuA will induce a transition from a closed to an open enzyme conformation, rendering the cytochrome a3-CuB site accessible for cyanide binding, possibly as a bridging ligand. A heterogeneity in the enzyme is observed in that an e.p.r. signal from the cytochrome a3 3+-HCN complex is only found in 20% of the molecules, whereas the remaining cyanide-bound a3-CuB sites are e.p.r.-silent. PMID:6098268

  3. An experimental and theoretical investigation of the rapid consolidation of continuously reinforced, metal-matrix composites

    SciTech Connect

    Nicolaou, P.D.; Semiatin, S.L.; Goetz, R.L.

    1996-06-01

    The feasibility of the rapid consolidation of Ti-14Al-21Nb/SCS-6 foil/fiber/foil composites using a forging approach was established as an alternative to slower and more expensive processes such as those based on hot isostatic pressing (HIP) or vacuum hot pressing (VHP). A firm basis for the technique was developed through theoretical analyses of temperature transients, forging pressures, and fiber fracture. These analyses demonstrated that there exists an optimal forging speed at which the consolidation stresses are a minimum. It was also shown that the flow stress of the encapsulation material relative to that of the densifying layup is an important consideration in achieving full consolidation during forging. Specifically, the difference in flow stress between the two materials influences the magnitude and sign of the in-plane (secondary) stresses that are developed during forging and therefore the rate of pore closure during the latter stages of the process. With regard to fiber fracture, analyses were performed to estimate the axial and tangential stresses during rapid consolidation. The theoretical work was validated by experimental trials using the Ti-14Al-21Nb matrix/silicon carbide fiber system. Measured forging pressures were in good agreement wit h predictions. Fiber fracture observations indicated that tangential tensile stresses developed in the fiber control failure; a forging window to avoid such failures was thus developed. Finally, it was demonstrated that matrix microstructures and mechanical properties similar to those of conventionally consolidated Ti-14Al-21Nb/silicon carbide composites can be achieved by the forge-consolidation technique.

  4. An experimental and theoretical investigation of the rapid consolidation of continuously reinforced, metal-matrix Composites

    NASA Astrophysics Data System (ADS)

    Nicolaou, P. D.; Semiatin, S. L.; Goetz, R. L.

    1996-06-01

    The feasibility of the rapid consolidation of T-14Al-21Nb/SCS-6 foil/fiber/foil composites using a forging approach was established as an alternative to slower and more expensive processes such as those based on hot isostatic pressing (HIP) or vacuum hot pressing (VHP). A firm basis for the technique was developed through theoretical analyses of temperature transients, forging pressures, and fiber fracture. These analyses demonstrated that there exists an optimal forging speed at which the consolidation stresses are a minimum. It was also shown that the flow stress of the encapsulation material relative to that of the densifying layup is an important consideration in achieving full consolidation during forging. Specifically, the difference in flow stress between the two materials influences the magnitude and sign of the in-plane (secondary) stresses that are developed during forging and therefore the rate of pore closure during the latter stages of the process. With regard to fiber fracture, analyses were performed to estimate the axial and tangential stresses during rapid consolidation. The theoretical work was validated by experimental trials using the Ti-14Al-21Nb matrix/silicon carbide fiber system. Measured forging pressures were in good agreement with predictions. Fiber fracture observations indicated that tangential tensile stresses developed in the fiber control failure; a forging window to avoid such failures was thus developed. Finally, it was demonstrated that matrix microstructures and mechanical properties similar to those of conventionally consolidated Ti-14Al-21Nb/silicon carbide composites can be achieved by the forge-consolidation technique.

  5. Pharmaceutical solid-state kinetic stability investigation by using moisture-modified Arrhenius equation and JMP statistical software.

    PubMed

    Fu, Mingkun; Perlman, Michael; Lu, Qing; Varga, Csanad

    2015-03-25

    An accelerated stress approach utilizing the moisture-modified Arrhenius equation and JMP statistical software was utilized to quantitatively assess the solid state stability of an investigational oncology drug MLNA under the influence of temperature (1/T) and humidity (%RH). Physical stability of MLNA under stress conditions was evaluated by using XRPD, DSC, TGA, and DVS, while chemical stability was evaluated by using HPLC. The major chemical degradation product was identified as a hydrolysis product of MLNA drug substance, and was subsequently subjected to an investigation of kinetics based on the isoconversion concept. A mathematical model (ln k=-11,991×(1/T)+0.0298×(%RH)+29.8823) based on the initial linear kinetics observed for the formation of this degradant at all seven stress conditions was built by using the moisture-modified Arrhenius equation and JMP statistical software. Comparison of the predicted versus experimental lnk values gave a mean deviation value of 5.8%, an R(2) value of 0.94, a p-value of 0.0038, and a coefficient of variation of the root mean square error CV(RMSE) of 7.9%. These statistics all indicated a good fit to the model for the stress data of MLNA. Both temperature and humidity were shown to have a statistically significant impact on stability by using effect leverage plots (p-value<0.05 for both 1/T and %RH). Inclusion of a term representing the interaction of relative humidity and temperature (%RH×1/T) was shown not to be justified by using Analysis of Covariance (ANCOVA), which supported the use of the moisture-corrected Arrhenius equation modeling theory. The model was found to be of value to aid setting of specifications and retest period, and storage condition selection. A model was also generated using only four conditions, as an example from a resource saving perspective, which was found to provide a good fit to the entire set of data.

  6. Experimental investigation of convective drying kinetics of kiwi under different conditions

    NASA Astrophysics Data System (ADS)

    Darıcı, Selçuk; Şen, Soner

    2015-08-01

    The effects of air temperature, velocity and humidity on drying characteristics of kiwi are experimentally investigated for the temperatures in the range of 50-80 °C, of the velocities 0.5-2.0 m/s, of the relative humidity values of 5-20 % and for two slice thicknesses. It is observed that there is a very close agreement between the model of Midilli et al. (Dry Technol 20:1503-1513, 2002) and the present study with coefficients of correlation R2 of 0.9949-0.9996.

  7. Investigation of rapid degradation in GaN-based blue laser diodes

    NASA Astrophysics Data System (ADS)

    Wen, Pengyan; Zhang, Shuming; Li, Deyao; Liu, Jianping; Zhang, Liqun; Shi, Dong; Zhou, Kun; Tian, Aiqin; Feng, Shiwei; Yang, Hui

    2016-11-01

    Investigation of the degradation modes in GaN-based blue laser diodes grown by metal organic chemical vapor deposition (MOCVD) is carried out. Early failure of the LDs happened at the initial stage of the aging. After analysis of the electrical and thermal characteristics, local degradation of the active region is observed. Further investigation on the microstructures of the local regions shows that the early failure of the LDs is due to the local structure damage with the formation of gallium metal.

  8. Investigating synergies of data fusion and image segmentation in earth observation based rapid mapping workflows

    NASA Astrophysics Data System (ADS)

    Witharana, C.

    2013-12-01

    In humanitarian emergencies, the timeliness of data provision and the short time-window available for dispatching value-added information pose major challenges to the mapping community. We have been engaged with a continuous research effort to explore novel ways to catalyze the EO-based humanitarian crisis information retrieval chain. This paper is an exploratory study, which aimed to discover the synergies of data fusion and image segmentation in the context of EO-based rapid mapping workflows. Our approach pillared on the geographic object-based image analysis (GEOBIA) focusing on multiscale, internally-displaced persons' (IDP) camp information extraction from very high spatial resolution (VHSR) images. We applied twelve pansharpening algorithms to two subsets of a GeoEye-1 image scene that was taken over a former war-induced ephemeral settlement in Sri Lanka. A multidimensional assessment was employed to benchmark pansharpening algorithms with respect to their spectral and spatial fidelity. The multiresolution segmentation (MRS) algorithm of the eCognition Developer software served as the key algorithm in the segmentation process. The first study site was used for comparing segmentation results produced from the twelve fused products at a series of scale, shape, and compactness settings of the MRS algorithm. The segmentation quality and optimum parameter settings of the MRS algorithm were estimated by using empirical discrepancy measures. Non-parametric statistical tests were used to compare the quality of image object candidates, which were derived from the twelve pansharpened products. A wall-to-wall classification was performed based on a support vector machine (SVM) classifier to classify image objects candidates of the fused images. The second site simulated a more realistic crisis information extraction scenario where the domain expertise is crucial in segmentation and classification. We compared segmentation and classification results of the original

  9. Investigating the fluid dynamics of rapid processes within microfluidic devices using bright-field microscopy.

    PubMed

    Pirbodaghi, Tohid; Vigolo, Daniele; Akbari, Samin; deMello, Andrew

    2015-05-07

    The widespread application of microfluidic devices in the biological and chemical sciences requires the implementation of complex designs and geometries, which in turn leads to atypical fluid dynamic phenomena. Accordingly, a complete understanding of fluid dynamics in such systems is key in the facile engineering of novel and efficient analytical tools. Herein, we present an accurate approach for studying the fluid dynamics of rapid processes within microfluidic devices using bright-field microscopy with white light illumination and a standard high-speed camera. Specifically, we combine Ghost Particle Velocimetry and the detection of moving objects in automated video surveillance to track submicron size tracing particles via cross correlation between the speckle patterns of successive images. The efficacy of the presented technique is demonstrated by measuring the flow field over a square pillar (80 μm × 80 μm) in a 200 μm wide microchannel at high volumetric flow rates. Experimental results are in excellent agreement with those obtained via computational fluid dynamics simulations. The method is subsequently used to study the dynamics of droplet generation at a flow focusing microfluidic geometry. A unique feature of the presented technique is the ability to perform velocimetry analysis of high-speed phenomena, which is not possible using micron-resolution particle image velocimetry (μPIV) approaches based on confocal or fluorescence microscopy.

  10. Is rapid growth in Internet usage environmentally sustainable for Australia? An empirical investigation.

    PubMed

    Salahuddin, Mohammad; Alam, Khorshed; Ozturk, Ilhan

    2016-03-01

    This study estimates the short- and long-run effects of Internet usage and economic growth on carbon dioxide (CO2) emissions using annual time series macro data for Australia for the period 1985-2012. Autoregressive distributive lag (ARDL) bounds and Gregory-Hansen structural break cointegration tests are applied. ARDL estimates indicate no significant long-run relationship between Internet usage and CO2 emissions, which implies that the rapid growth in Internet usage is still not an environmental threat for Australia. The study further indicates that higher level of economic growth is associated with lower level of CO2 emissions; however, Internet usage and economic growth have no significant short-run relationship with CO2 emissions. Financial development has both short-run and long-run significant positive association with CO2 emissions. The findings offer support in favor of energy efficiency gains and a reduction in energy intensity in Australia. However, impulse response and variance decomposition analysis suggest that Internet usage, economic growth and financial development will continue to impact CO2 emissions in the future, and as such, this study recommends that in addition to the existing measures to combat CO2 emissions, Australia needs to exploit the potential of the Internet not only to reduce its own carbon footprint but also to utilize information and communication technology (ICT)-enabled emissions abatement potential to reduce emissions in various other sectors across the economy, such as, power, renewable energy especially in solar and wind energy, agriculture, transport and service.

  11. Effect of morin on pharmacokinetics of piracetam in rats, in vitro enzyme kinetics and metabolic stability assay using rapid UPLC method.

    PubMed

    Sahu, Kapendra; Shaharyar, Mohammad; Siddiqui, Anees A

    2013-07-01

    The aim of this study was to investigate the effect of Morin on the pharmacokinetics of Piracetam in rats, in vitro enzyme kinetics and metabolic stability (high throughput) studies using human liver microsomes in UPLC. For pharmacokinetics studies, male Wistar rats were pretreated with Morin (10 mg/kg) for one week and on the last day, a single dose of Piracetam (50 mg/kg) was given orally. In another group, both Morin and Piracetam were co-administered to evaluate the acute effect of Morin on Piracetam. The control group received oral distilled water for one week and administered with Piracetam on the last day. As Morin is an inhibitor of P- Glycoprotein (P-gp) and CYP 3A, it was anticipated to improve the bioavailability of Piracetam. Amazingly, relative to control, the areas under the concentration time curve and peak plasma concentration of Piracetam were 1.50- and 1.45-fold, respectively, greater in the Morin-pretreated group. However, co-administration of Morin had no significant effect on these parameters. Apart from the aforementioned merits, the results of this study are further confirmed by clinical trials; Piracetam dosages should be adjusted to avoid potential drug interaction when Piracetam is used clinically in combination with Morin and Morin-containing dietary supplements. The in vitro enzyme kinetics were performed to determined km, Vmax & CLins . The in vitro metabolic stability executed for the estimation of metabolic rate constant and half-life of Piracetam. These studies also extrapolate to in vivo intrinsic hepatic clearance (Clint, in vivo ) from in vitro intrinsic hepatic clearance (CLint, in vitro ).

  12. What is the true enzyme kinetics in the biological system? An investigation of macromolecular crowding effect upon enzyme kinetics of glucose-6-phosphate dehydrogenase.

    PubMed

    Norris, Matthew G S; Malys, Naglis

    2011-02-18

    Enzyme kinetic parameters for rate equations are vital in metabolic network simulation, a major part of systems biology research efforts. Measurements of Michaelis-Menten kinetic parameters Km and Kcat have been performed for enzymes glucose-6-phosphate dehydrogenase (G6P DH) under crowded conditions using molecular crowding agents bovine serum albumin (BSA) and polyethylene glycol (PEG) of 8000 Da molecular weight. An increase in Kcat was observed at very low concentrations of crowding agent, and also at high crowder concentrations when the experiment was performed at 45 °C with PEG. The observed pattern in Kcat for G6P DH at high crowder concentrations has been explained via modelling using excluded volume theory. An increase in rate was observed at 45 °C for G6P DH versus 30 °C; this has been modelled via the Arrhenius equation.

  13. Application of SPECT/CT imaging system and radiochemical analysis for investigation of blood kinetics and tissue distribution of radiolabeled plumbagin in healthy and Plasmodium berghei-infected mice.

    PubMed

    Sumsakul, W; Karbwang, J; Na-Bangchang, K

    2016-02-01

    Plumbagin is a derivative of napthoquinone which is isolated from the roots of plants in several families. These compound exhibits a wide range of biological and pharmacological activities including antimalarial, antibacterial, antifungal, and anticancer activities. The aim of the study was to investigate blood kinetics and tissue distribution of plumbagin in healthy and Plasmodium berghei-infected mice using Single-Photon Emission Computed Tomography/Computed Tomography (SPECT/CT) and radiochemical analysis by gamma counter. Plumbagin was labeled with (99m)technetium and the reducing agent stannous chloride dihydrate (50 μg/ml) at pH 6.5. Blood kinetics and tissue distribution of the radiolabeled plumbagin were investigated in healthy and P. berghei-infected mice (2 males and 2 females for each experimental group). In vitro and in vivo stability of plumbagin complex suggested satisfactory stability profiles of (99m)Tc-plumbagin complex in plasma and normal saline (92.21-95.47%) within 24 h. Significant difference in blood kinetics parameters (Cmax, AUC, t1/2, MRT, Vd, and CL) were observed between P. berghei-infected and healthy mice. The labeled complex distributed to all organs of both healthy and infected mice but with high intensity in liver, followed by lung, stomach, large intestine and kidney. Accumulation in spleen was markedly noticeable in the infected mice. Plumbagin-labeled complex was rapidly cleared from blood and major routes of excretion were hepatobiliary and pulmonary routes. In P. berghei-infected mice, t1/2 was significantly decreased, while Vd and CL were increased compared with healthy mice. Result suggests that malaria disease state influenced the pharmacokinetics and disposition of plumbagin. SPECT/CT imaging with radiolabeled (99m)Tc is a viable non-invasive technique that can be applied for investigation of kinetics and biodistribution of plumbagin in animal models.

  14. Rapid equilibrium kinetic analysis of arsenite methylation catalyzed by recombinant human arsenic (+3 oxidation state) methyltransferase (hAS3MT).

    PubMed

    Wang, Shuping; Li, Xiangli; Song, Xiaoli; Geng, Zhirong; Hu, Xin; Wang, Zhilin

    2012-11-09

    In the human body, arsenic is metabolized by methylation. Understanding this process is important and provides insight into the relationship between arsenic and its related diseases. We used the rapid equilibrium kinetic model to study the reaction sequence of arsenite methylation. The results suggest that the mechanism for arsenite methylation is a completely ordered mechanism that is also of general interest in reaction systems with different reductants, such as tris(2-carboxyethyl)phosphine, cysteine, and glutathione. In the reaction, cysteine residues of recombinant human arsenic (+3 oxidation state) methyltransferase (hAS3MT) coordinate with arsenicals and involve the methyl transfer step. S-Adenosyl-l-methionine (AdoMet) is the first-order reactant, which modulates the conformation of hAS3MT to a best matched state by hydrophobic interaction. As the second-order reactant, reductant reduces the disulfide bond, most likely between Cys-250 and another cysteine residue of hAS3MT, and exposes the active site cysteine residues for binding trivalent inorganic arsenic (iAs(3+)) to give monomethylarsonic dicysteine (MADC(3+)). In addition, the reaction can be extended to further methylate MADC(3+) to dimethylarsinic cysteine (DAMC(3+)). In the methylation reaction, the β-pleated sheet content of hAS3MT is increased, and the hydrophobicity of the microenvironment around the active sites is decreased. Similarly, we confirm that both the high β-pleated sheet content of hAS3MT and the high dissociation ability of the enzyme-AdoMet-reductant improve the yield of dimethylated arsenicals.

  15. Investigation of CaO-CO₂ reaction kinetics by in-situ XRD using synchrotron radiation

    SciTech Connect

    Biasin, A.; Segre, C. U.; Salviulo, G.; Zorzi, F.; Strumendo, M.

    2015-02-05

    In this work, in-situ synchrotron radiation x-ray powder diffraction (SR-XRPD), performed at the Advanced Photon Source (APS) facilities of the Argonne National Laboratory, was applied to investigate the CaO–CO2 reaction. A set of CO2 absorption experiments were conducted in a high temperature reaction capillary with a controlled atmosphere (CO2 partial pressure of 1 bar), in the temperature range between 450 °C and 750 °C using CaO based sorbents obtained by calcination of commercial calcium carbonate. The evolution of the crystalline phases during CO2 uptake by the CaO solid sorbents was monitored for a carbonation time of 20 min as a function of the carbonation temperature and of the calcination conditions. The Rietveld refinement method was applied to estimate the calcium oxide conversion during the reaction progress and the average size of the initial (at the beginning of carbonation) calcium oxide crystallites. The measured average initial carbonation rate (in terms of conversion time derivative) of 0.280 s-1 (±13.2% standard deviation) is significantly higher than the values obtained by thermo-gravimetric analysis and reported thus far in the literature. Additionally, a dependence of the conversion versus time curves on the initial calcium oxide crystallite size was observed and a linear relationship between the initial CaO crystallite size and the calcium oxide final conversion was identified.

  16. Investigation of H2 Concentration and Combustion Instability Effects on the Kinetics of Strained Syngas Flames

    SciTech Connect

    Ahsan R. Choudhuri

    2006-08-07

    The flame extinction limits of syngas (H{sub 2}-CO) flames were measured using a twin-flame-counter-flow burner. Plots of Extinction limits vs. global stretch rates were generated at different mixture compositions and an extrapolation method was used to calculate the flame extinction limit corresponding to an experimentally unattainable zero-stretch condition. The zero-stretch extinction limit of H{sub 2}-CO mixtures decreases (from rich to lean) with the increase in H{sub 2} concentration in the mixture. The average difference between the measured flame extinction limit and the Le Chatelier's calculation is around {approx} 7%. The measured OH{sup -} chemiluminescent data indicates that regardless of mixture compositions the OH radical concentration reduces (within the experimental uncertainties) to an extinction value prior to the flame extinction. Flame extinction limits of H{sub 2}-CO mixtures measured in a flat-flame burner configuration also show a similar relation. Additionally, the measured laminar flame velocity close to the extinction indicates that regardless of fuel composition the premixed flame of hydrogen fuel blends extinguishes when the mixture laminar flame velocity falls below a critical value. The critical laminar flame velocity at extinction for H{sub 2}-CO premixed flames (measured in the flat flame burner configuration) is found to be 3.77({+-}0.38) cm/s. An externally perturbed H{sub 2}-CO twin flame was not experimentally achievable for the mixture conditions used in the present investigation. A slightest perturbation in the flow-field distorts the H{sub 2}-CO twin-flame. The flame becomes highly unstable with the introduction of an externally excited flow oscillation.

  17. Results of paleoflood investigations for Spring, Rapid, Boxedler, and Elk Creeks, Black Hills, western South Dakota

    USGS Publications Warehouse

    Driscoll, Daniel G.; O'Connor, James E.; Harden, Tessa M.

    2012-01-01

    Flood-frequency analyses for the Black Hills area are especially important because of severe flooding of June 9–10, 1972, that was caused by a large mesoscale convective system and resulted in at least 238 deaths. This paper summarizes results of paleoflood investigations for six study reaches in the central Black Hills. Stratigraphic records and resulting long-term flood chronologies, locally extending more than 2,000 years, were combined with observed and historical flood information to derive flood-frequency estimates. Results indicate that floods as large as and even substantially larger than 1972 have affected most of the study reaches. Results of the paleoflood investigations provide better physically based information on low-probability floods than has been previously available, substantially improving estimates of the magnitude and frequency of large floods in the central Black Hills and reducing associated uncertainties. Collectively, the results provide insights regarding regional flood-generation processes and their spatial controls, enable approaches for extrapolation of results for hazard assessment beyond specific study reaches, and provide a millennial-scale perspective on the 1972 flooding.

  18. Adsorption of di-l-alanine on Cu(110) investigated with scanning tunneling microscopy [rapid communication

    NASA Astrophysics Data System (ADS)

    Stensgaard, I.

    2003-11-01

    Sub-monolayer growth of a small chiral peptide, di- L-alanine, on Cu(1 1 0) was investigated by variable temperature scanning tunneling microscopy (STM). At low coverage and for temperatures above ≈-220 K the molecules nucleate along the [ 3¯ 3 2] direction to form short, mainly one-dimensional islands. An increase in coverage leads to the formation of [ 3¯ 3 2]-directed, elongated islands. Images with sub-molecular resolution reveal that the orientation of the molecules within one particular island depends on the deposition temperature. At higher coverage, up to one monolayer, the islands coalesce, giving rise to phase boundaries between domains of opposite orientation. An atomic-scale model for di- L-alanine on Cu(1 1 0) is presented.

  19. Investigation of fluorescence methods for rapid detection of municipal wastewater impact on drinking water sources

    NASA Astrophysics Data System (ADS)

    Peleato, Nicolas M.; Legge, Raymond L.; Andrews, Robert C.

    2017-01-01

    Fluorescence spectroscopy as a means to detect low levels of treated wastewater impact on two source waters was investigated using effluents from five wastewater facilities. To identify how best to interpret the fluorescence excitation-emission matrices (EEMs) for detecting the presence of wastewater, several feature selection and classification methods were compared. An expert supervised regional integration approach was used based on previously identified features which distinguish biologically processed organic matter including protein-like fluorescence and the ratio of protein to humic-like fluorescence. Use of nicotinamide adenine dinucleotide-like (NADH) fluorescence was found to result in higher linear correlations for low levels of wastewater presence. Parallel factors analysis (PARAFAC) was also applied to contrast an unsupervised multiway approach to identify underlying fluorescing components. A humic-like component attributed to reduced semiquinone-like structures was found to best correlate with wastewater presence. These fluorescent features were used to classify, by volume, low (0.1-0.5%), medium (1-2%), and high (5-15%) levels by applying support vector machines (SVMs) and logistic regression. The ability of SVMs to utilize high-dimensional input data without prior feature selection was demonstrated through their performance when considering full unprocessed EEMs (66.7% accuracy). The observed high classification accuracies are encouraging when considering implementation of fluorescence spectroscopy as a water quality monitoring tool. Furthermore, the use of SVMs for classification of fluorescence data presents itself as a promising novel approach by directly utilizing the high-dimensional EEMs.

  20. Rapid adsorption of copper(II) and lead(II) by rice straw/Fe₃O₄ nanocomposite: optimization, equilibrium isotherms, and adsorption kinetics study.

    PubMed

    Khandanlou, Roshanak; Ahmad, Mansor B; Fard Masoumi, Hamid Reza; Shameli, Kamyar; Basri, Mahiran; Kalantari, Katayoon

    2015-01-01

    Rice straw/magnetic nanocomposites (RS/Fe3O4-NCs) were prepared via co-precipitation method for removal of Pb(II) and Cu(II) from aqueous solutions. Response surface methodology (RSM) was utilized to find the optimum conditions for removal of ions. The effects of three independent variables including initial ion concentration, removal time, and adsorbent dosage were investigated on the maximum adsorption of Pb (II) and Cu (II). The optimum conditions for the adsorption of Pb(II) and Cu(II) were obtained (100 and 60 mg/L) of initial ion concentration, (41.96 and 59.35 s) of removal time and 0.13 g of adsorbent for both ions, respectively. The maximum removal efficiencies of Pb(II) and Cu(II) were obtained 96.25% and 75.54%, respectively. In the equilibrium isotherm study, the adsorption data fitted well with the Langmuir isotherm model. The adsorption kinetics was best depicted by the pseudo-second order model. Desorption experiments showed adsorbent can be reused successfully for three adsorption-desorption cycles.

  1. Rapid Adsorption of Copper(II) and Lead(II) by Rice Straw/Fe3O4 Nanocomposite: Optimization, Equilibrium Isotherms, and Adsorption Kinetics Study

    PubMed Central

    Khandanlou, Roshanak; Ahmad, Mansor B.; Fard Masoumi, Hamid Reza; Shameli, Kamyar; Basri, Mahiran; Kalantari, Katayoon

    2015-01-01

    Rice straw/magnetic nanocomposites (RS/Fe3O4-NCs) were prepared via co-precipitation method for removal of Pb(II) and Cu(II) from aqueous solutions. Response surface methodology (RSM) was utilized to find the optimum conditions for removal of ions. The effects of three independent variables including initial ion concentration, removal time, and adsorbent dosage were investigated on the maximum adsorption of Pb (II) and Cu (II). The optimum conditions for the adsorption of Pb(II) and Cu(II) were obtained (100 and 60 mg/L) of initial ion concentration, (41.96 and 59.35 s) of removal time and 0.13 g of adsorbent for both ions, respectively. The maximum removal efficiencies of Pb(II) and Cu(II) were obtained 96.25% and 75.54%, respectively. In the equilibrium isotherm study, the adsorption data fitted well with the Langmuir isotherm model. The adsorption kinetics was best depicted by the pseudo-second order model. Desorption experiments showed adsorbent can be reused successfully for three adsorption-desorption cycles. PMID:25815470

  2. The solution, solid state stability and kinetic investigation in degradation studies of lercanidipine: study of excipients compatibility of lercanidipine.

    PubMed

    Parmar, Nitin; Amin, Saima; Singla, Neelam; Kohli, Kanchan

    2012-01-01

    The objectives of this research were to evaluate the stability of lercanidipine in solution state and solid state and explore the compatibility of drug with oils, surfactants and cosurfactants as excipients. The effect of pH on the degradation in solution state was studied through pH-rate profile of lercanidipine in constant ionic strength buffer solutions in pH range 1-8 which gives the pH of maximum stability. Powdered lercanidipine was stored under 40°C/0%~75% relative humidities (RH) or 0% RH/5~50°C to study the influence of RH and temperature on the stability of lercanidipine in solid state. Binary mixtures of lercanidipine and different excipients were stored at 40°C/75% RH, 40°C and at room temperature for excipient compatibility evaluation. The degradation of lercanidipine at different pH appears to fit a typical first-order reaction, but in solid state, it does not fit any obvious reaction model. Moisture content and temperature both play important roles affecting the degradation rate. Lercanidipine exhibits good compatibility with surfactants, cosurfactants and oils as excipients under stressed conditions of different storage temperature in a 3-week screening study. Moreover, the proposed high-performance liquid chromatography method was utilized to investigate the kinetics of the acidic and alkaline degradation processes of lercanidipine at different temperatures.

  3. Analytical chemical kinetic investigation of the effects of oxygen, hydrogen, and hydroxyl radicals on hydrogen-air combustion

    NASA Technical Reports Server (NTRS)

    Carson, G. T., Jr.

    1974-01-01

    Quantitative values were computed which show the effects of the presence of small amounts of oxygen, hydrogen, and hydroxyl radicals on the finite-rate chemical kinetics of premixed hydrogen-air mixtures undergoing isobaric autoignition and combustion. The free radicals were considered to be initially present in hydrogen-air mixtures at equivalence ratios of 0.2, 0.6, 1.0, and 1.2. Initial mixture temperatures were 1100 K, 1200 K, and 1500 K, and pressures were 0.5, 1.0, 2.0, and 4.0 atm. Of the radicals investigated, atomic oxygen was found to be the most effective for reducing induction time, defined as the time to 5 percent of the total combustion temperature rise. The reaction time, the time between 5 percent and 95 percent of the temperature rise, is not decreased by the presence of free radicals in the initial hydrogen-air mixture. Fuel additives which yield free radicals might be used to effect a compact supersonic combustor design for efficient operation in an otherwise reaction-limited combustion regime.

  4. Photodegradation of the azole fungicide fluconazole in aqueous solution under UV-254: kinetics, mechanistic investigations and toxicity evaluation.

    PubMed

    Chen, Zhi-Feng; Ying, Guang-Guo; Jiang, Yu-Xia; Yang, Bin; Lai, Hua-Jie; Liu, You-Sheng; Pan, Chang-Gui; Peng, Fu-Qiang

    2014-04-01

    The azole fungicide fluconazole has been reported to be persistent in conventional wastewater treatment plants. This study investigated the photodegradation of fluconazole under UV-254 in aqueous solutions. The results revealed that the photodegradation of fluconazole was pH-dependent (2.0-12.0) following the pseudo-first-order kinetics with quantum yield values ranging from 0.023 to 0.090 mol einstein(-1), and it underwent a direct and self-sensitized mechanism involving (1)O2. The main photodegradation by-products were identified and semi-quantitated. The proposed photodegradation pathway included hydroxylative defluorination reaction. The 72 h-NOEC and 72 h-LOEC values for fluconazole using a freshwater unicellular green alga Pseudokirchneriella subcapitata were 10 μM and 15 μM. Overall, the photodegradation of fluconazole produced a significant decrease in algal toxicity. It also proved that the photodegradation by-products will not present extra toxicity to this alga than fluconazole itself.

  5. The effect of pressure on the kinetics of γ-anhydrite crystallization investigated by diamond anvil cell

    NASA Astrophysics Data System (ADS)

    Liu, Chuanjiang; Zheng, Haifei; Du, Jianguo; Wang, Duojun

    2015-01-01

    The crystallization kinetics of γ-anhydrite was investigated in the temperature and pressure ranges of 373-473 K and 1094-1903 MPa using a hydrothermal diamond anvil cell (HDAC) and Raman spectroscopy. A calcium sulfate solution was formed by dissolving gypsum in water at high pressure, and γ-anhydrite crystallized due to the increasing temperature. The relationship among the reaction rate, k, the temperature, T, and the pressure, P was established as k=-1.75×10-3+1.83×10-6P+3.57×10-7T, with an R2 value of 0.943, of which the applicable range is 373 K≤T≤473 K and 1196 MPa≤P≤1903 MPa. An elevation of T or P will accelerate the crystallization rate of γ-anhydrite. The time exponent n obtained between 0.96 and 1.29 indicates that the process of crystallization should be controlled by instant nucleation on the grain boundary and diffusion controlled growth. In the process of crystallization, the volume is reduced because of the decrease of pressure, and the volume change ΔV is equal to -6.05×10-6 m3/mol. The calculated activation energy Ea is 10.7 kJ/mol, and the pre-exponential factor A is 2.27×10-2 s-1.

  6. A new real-time method for investigation of affinity properties and binding kinetics of magnetic nanoparticles

    NASA Astrophysics Data System (ADS)

    Orlov, Alexey V.; Nikitin, Maxim P.; Bragina, Vera A.; Znoyko, Sergey L.; Zaikina, Marina N.; Ksenevich, Tatiana I.; Gorshkov, Boris G.; Nikitin, Petr I.

    2015-04-01

    A method for quantitative investigation of affinity constants of receptors immobilized on magnetic nanoparticles (MP) is developed based on spectral correlation interferometry (SCI). The SCI records with a picometer resolution the thickness changes of a layer of molecules or nanoparticles due to a biochemical reaction on a cover slip, averaged over the sensing area. The method is compatible with other types of sensing surfaces employed in biosensing. The measured values of kinetic association constants of magnetic nanoparticles are 4 orders of magnitude higher than those of molecular antibody association with antigen. The developed method also suggests highly sensitive detection of antigens in a wide dynamic range. The limit of detection of 92 pg/ml has been demonstrated for prostate-specific antigen (PSA) with 50-nm MP employed as labels, which produce 3-order amplification of the SCI signals. The calibration curve features high sensitivity (slope) of 3-fold signal raise per 10-fold increase of PSA concentration within 4-order dynamic range, which is an attractive compromise for precise quantitative and highly sensitive immunoassay. The proposed biosensing technique offers inexpensive disposable sensor chips of cover slips and represents an economically sound alternative to traditional immunoassays for disease diagnostics, detection of pathogens in food and environmental monitoring.

  7. Mechanistic investigations of the hydrolysis of amides, oxoesters and thioesters via kinetic isotope effects and positional isotope exchange.

    PubMed

    Robins, Lori I; Fogle, Emily J; Marlier, John F

    2015-11-01

    The hydrolysis of amides, oxoesters and thioesters is an important reaction in both organic chemistry and biochemistry. Kinetic isotope effects (KIEs) are one of the most important physical organic methods for determining the most likely transition state structure and rate-determining step of these reaction mechanisms. This method induces a very small change in reaction rates, which, in turn, results in a minimum disturbance of the natural mechanism. KIE studies were carried out on both the non-enzymatic and the enzyme-catalyzed reactions in an effort to compare both types of mechanisms. In these studies the amides and esters of formic acid were chosen because this molecular structure allowed development of methodology to determine heavy-atom solvent (nucleophile) KIEs. This type of isotope effect is difficult to measure, but is rich in mechanistic information. Results of these investigations point to transition states with varying degrees of tetrahedral character that fit a classical stepwise mechanism. This article is part of a special issue entitled: Enzyme Transition States from Theory and Experiment.

  8. Investigation into solar drying of potato: effect of sample geometry on drying kinetics and CO2 emissions mitigation.

    PubMed

    Tripathy, P P

    2015-03-01

    Drying experiments have been performed with potato cylinders and slices using a laboratory scale designed natural convection mixed-mode solar dryer. The drying data were fitted to eight different mathematical models to predict the drying kinetics, and the validity of these models were evaluated statistically through coefficient of determination (R(2)), root mean square error (RMSE) and reduced chi-square (χ (2)). The present investigation showed that amongst all the mathematical models studied, the Modified Page model was in good agreement with the experimental drying data for both potato cylinders and slices. A mathematical framework has been proposed to estimate the performance of the food dryer in terms of net CO2 emissions mitigation potential along with unit cost of CO2 mitigation arising because of replacement of different fossil fuels by renewable solar energy. For each fossil fuel replaced, the gross annual amount of CO2 as well as net amount of annual CO2 emissions mitigation potential considering CO2 emissions embodied in the manufacture of mixed-mode solar dryer has been estimated. The CO2 mitigation potential and amount of fossil fuels saved while drying potato samples were found to be the maximum for coal followed by light diesel oil and natural gas. It was inferred from the present study that by the year 2020, 23 % of CO2 emissions can be mitigated by the use of mixed-mode solar dryer for drying of agricultural products.

  9. Purification and investigation of some kinetic properties of glucose-6-phosphate dehydrogenase from parsley (Petroselinum hortense) leaves.

    PubMed

    Coban, T Abdül Kadir; Ciftçi, Mehmet; Küfrevioğlu, O Irfan

    2002-05-01

    In this study, glucose-6-phosphate dehydrogenase (D-glucose-6-phosphate: NADP+ oxidoreductase, EC 1.1.1.49; G6PD) was purified from parsley (Petroselinum hortense) leaves, and analysis of the kinetic behavior and some properties of the enzyme were investigated. The purification consisted of three steps: preparation of homogenate, ammonium sulfate fractionation, and DEAE-Sephadex A50 ion exchange chromatography. The enzyme was obtained with a yield of 8.79% and had a specific activity of 2.146 U (mg protein)(-1). The overall purification was about 58-fold. Temperature of +4 degrees C was maintained during the purification process. Enzyme activity was spectrophotometrically measured according to the Beutler method, at 340 nm. In order to control the purification of enzyme, SDS-polyacrylamide gel electrophoresis was carried out in 4% and 10% acrylamide for stacking and running gel, respectively. SDS-polyacrylamide gel electrophoresis showed a single band for enzyme. The molecular weight was found to be 77.6 kDa by Sephadex G-150 gel filtration chromatography. A protein band corresponding to a molecular weight of 79.3 kDa was obtained on SDS-polyacrylamide gel electrophoresis. For the enzymes, the stable pH, optimum pH, and optimum temperature were found to be 6.0, 8.0, and 60 degrees C, respectively. Moreover, KM and Vmax values for NADP+ and G6-P at optimum pH and 25 degrees C were determined by means of Lineweaver-Burk graphs. Additionally, effects of streptomycin sulfate and tetracycline antibiotics were investigated for the enzyme activity of glucose-6-phosphate dehydrogenase in vitro.

  10. A mechanistic investigation of the kinetic resolution of secondary aromatic alcohols using a ferrocene-based planar chiral 4-(dimethylamino)pyridine catalyst.

    PubMed

    Mesas-Sánchez, Laura; Dinér, Peter

    2015-03-27

    A detailed computational and kinetic analysis of the acetylation of 1-phenylethanol with acetic anhydride catalyzed by planar chiral 4-(dimethylamino)pyridine (DMAP) catalyst (-)-1 is presented. The study includes a computational investigation of the potential-energy surface including the acylation and stereoselective transition states at the DFT level of theory. Experimentally, the kinetic study shows that the reaction proceeds in a first-order manner in catalyst, whereas both substrates, acetic anhydride and 1-phenylethanol, show fractional order, which is in accordance with steady-state conditions. The fractional order depends on an equilibrium between the free catalyst and the acetylated catalyst.

  11. Investigating chemical changes during shelf-life of thermal and high-pressure high-temperature sterilised carrot purees: A 'fingerprinting kinetics' approach.

    PubMed

    Kebede, Biniam T; Grauwet, Tara; Palmers, Stijn; Michiels, Chris; Hendrickx, Marc; Van Loey, Ann

    2015-10-15

    This work investigates chemical changes during shelf-life of thermally and high pressure high temperature (HPHT) sterilised carrot purees using a 'fingerprinting kinetics' approach. Fingerprinting enabled selection of Strecker aldehydes, terpenes, phenylpropanoids, fatty acid derivatives and carotenoid degradation products as volatiles clearly changing during shelf-life. Next, kinetic modelling of these volatiles was performed to compare their reaction kinetics during storage in differently sterilised samples. Immediately after processing, the Strecker aldehydes were detected at higher levels in thermally sterilised samples. During storage, the compounds increased at a comparable rate in thermally and HPHT processed samples. In contrast, immediately after processing, most of the naturally occurring terpenes and phenylpropanoids were better preserved in HPHT treated samples. Nevertheless, by the end of storage, the concentration of these compounds decreased to almost the same level in both thermal and HPHT samples (with a higher degradation rate in HPHT samples).

  12. Glutathione reductase: Comparison of steady-state and rapid reaction primary kinetic isotope effects exhibited by the yeast, spinach, and Escherichia coli enzymes

    SciTech Connect

    Vanoni, M.A.; Wong, K.K.; Ballou, D.P.; Blanchard, J.S. )

    1990-06-19

    Kinetic parameters for NADPH and NADH have been determined at pH 8.1 for spinach, yeast, and E. coli glutathione reductases. NADPH exhibited low Km values for all enzymes (3-6 microM), while the Km values for NADH were 100 times higher (approximately 400 microM). Under our experimental conditions, the percentage of maximal velocities with NADH versus those measured with NADPH were 18.4, 3.7, and 0.13% for the spinach, yeast, and E. coli enzymes, respectively. Primary deuterium kinetic isotope effects were independent of GSSG concentration between Km and 15Km levels, supporting a ping-pong kinetic mechanism. For each of the three enzymes, NADPH yielded primary deuterium kinetic isotope effects on Vmax only, while NADH exhibited primary deuterium kinetic isotope effects on both V and V/K. The magnitude of DV/KNADH at pH 8.1 is 4.3 for the spinach enzyme, 2.7 for the yeast enzyme, and 1.6 for the E. coli glutathione reductase. The experimentally determined values of TV/KNADH of 7.4, 4.2, and 2.2 for the spinach, yeast, and E. coli glutathione reductases agree well with those calculated from the corresponding DV/KNADH using the Swain-Schaad expression. This suggests that the intrinsic primary kinetic isotope effect on NADH oxidation is fully expressed. In order to confirm this conclusion, single-turnover experiments have been performed. The measured primary deuterium kinetic isotope effects on the enzyme reduction half-reaction using NADH match those measured in the steady state for each of the three glutathione reductases.

  13. Rapid Prototyping for In Vitro Knee Rig Investigations of Prosthetized Knee Biomechanics: Comparison with Cobalt-Chromium Alloy Implant Material

    PubMed Central

    Schröder, Christian; Steinbrück, Arnd; Müller, Tatjana; Woiczinski, Matthias; Chevalier, Yan; Müller, Peter E.; Jansson, Volkmar

    2015-01-01

    Retropatellar complications after total knee arthroplasty (TKA) such as anterior knee pain and subluxations might be related to altered patellofemoral biomechanics, in particular to trochlear design and femorotibial joint positioning. A method was developed to test femorotibial and patellofemoral joint modifications separately with 3D-rapid prototyped components for in vitro tests, but material differences may further influence results. This pilot study aims at validating the use of prostheses made of photopolymerized rapid prototype material (RPM) by measuring the sliding friction with a ring-on-disc setup as well as knee kinematics and retropatellar pressure on a knee rig. Cobalt-chromium alloy (standard prosthesis material, SPM) prostheses served as validation standard. Friction coefficients between these materials and polytetrafluoroethylene (PTFE) were additionally tested as this latter material is commonly used to protect pressure sensors in experiments. No statistical differences were found between friction coefficients of both materials to PTFE. UHMWPE shows higher friction coefficient at low axial loads for RPM, a difference that disappears at higher load. No measurable statistical differences were found in knee kinematics and retropatellar pressure distribution. This suggests that using polymer prototypes may be a valid alternative to original components for in vitro TKA studies and future investigations on knee biomechanics. PMID:25879019

  14. Decoding the Formation of New Semantics: MVPA Investigation of Rapid Neocortical Plasticity during Associative Encoding through Fast Mapping

    PubMed Central

    Atir-Sharon, Tali; Gilboa, Asaf; Hazan, Hananel; Koilis, Ester; Manevitz, Larry M.

    2015-01-01

    Neocortical structures typically only support slow acquisition of declarative memory; however, learning through fast mapping may facilitate rapid learning-induced cortical plasticity and hippocampal-independent integration of novel associations into existing semantic networks. During fast mapping the meaning of new words and concepts is inferred, and durable novel associations are incidentally formed, a process thought to support early childhood's exuberant learning. The anterior temporal lobe, a cortical semantic memory hub, may critically support such learning. We investigated encoding of semantic associations through fast mapping using fMRI and multivoxel pattern analysis. Subsequent memory performance following fast mapping was more efficiently predicted using anterior temporal lobe than hippocampal voxels, while standard explicit encoding was best predicted by hippocampal activity. Searchlight algorithms revealed additional activity patterns that predicted successful fast mapping semantic learning located in lateral occipitotemporal and parietotemporal neocortex and ventrolateral prefrontal cortex. By contrast, successful explicit encoding could be classified by activity in medial and dorsolateral prefrontal and parahippocampal cortices. We propose that fast mapping promotes incidental rapid integration of new associations into existing neocortical semantic networks by activating related, nonoverlapping conceptual knowledge. In healthy adults, this is better captured by unique anterior and lateral temporal lobe activity patterns, while hippocampal involvement is less predictive of this kind of learning. PMID:26257961

  15. Rapid prototyping for in vitro knee rig investigations of prosthetized knee biomechanics: comparison with cobalt-chromium alloy implant material.

    PubMed

    Schröder, Christian; Steinbrück, Arnd; Müller, Tatjana; Woiczinski, Matthias; Chevalier, Yan; Weber, Patrick; Müller, Peter E; Jansson, Volkmar

    2015-01-01

    Retropatellar complications after total knee arthroplasty (TKA) such as anterior knee pain and subluxations might be related to altered patellofemoral biomechanics, in particular to trochlear design and femorotibial joint positioning. A method was developed to test femorotibial and patellofemoral joint modifications separately with 3D-rapid prototyped components for in vitro tests, but material differences may further influence results. This pilot study aims at validating the use of prostheses made of photopolymerized rapid prototype material (RPM) by measuring the sliding friction with a ring-on-disc setup as well as knee kinematics and retropatellar pressure on a knee rig. Cobalt-chromium alloy (standard prosthesis material, SPM) prostheses served as validation standard. Friction coefficients between these materials and polytetrafluoroethylene (PTFE) were additionally tested as this latter material is commonly used to protect pressure sensors in experiments. No statistical differences were found between friction coefficients of both materials to PTFE. UHMWPE shows higher friction coefficient at low axial loads for RPM, a difference that disappears at higher load. No measurable statistical differences were found in knee kinematics and retropatellar pressure distribution. This suggests that using polymer prototypes may be a valid alternative to original components for in vitro TKA studies and future investigations on knee biomechanics.

  16. Stabilities of neutral and basic esters of bendamustine in plasma compared to the parent compound: kinetic investigations by HPLC.

    PubMed

    Huber, S; Antoni, F; Schickaneder, C; Schickaneder, H; Bernhardt, G; Buschauer, A

    2015-02-01

    Esters of the cytostatic bendamustine (1), previously demonstrated to be much more potent than the parent compound as antiproliferative agents in vitro, were investigated for stability in buffer and plasma, as well as against porcine liver esterase in the presence of different amounts of albumin using a validated RP-HPLC method with fluorescence detection. The hydrolysis of the nitrogen mustard moiety was retarded (for 1: approximately 130 vs. 11 min) in the presence of plasma proteins. For the derivatives, both cleavage of ester and nitrogen mustard moieties were analyzed. Enzymatic hydrolysis was very fast in the case of 2-pyrrolidino-, 2-piperidino- and 2-(4-methylpiperazino)-ethyl esters, whereas methyl, ethyl, morpholinoethyl and branched 2-pyrrolidinoethyl esters were considerably more stable (half-lives between 41 and 116 min, compared to <5 min). Inhibition by physostigmine indicated unspecific cholinesterases to be involved in the rapid ester cleavage. Due to lower protein content and higher enzymatic activity in murine compared to human plasma, reduced stability of all investigated esters in mouse plasma (t½<2 min) has to be taken into account with respect to the design of animal studies.

  17. An investigation into the crystallization tendency/kinetics of amorphous active pharmaceutical ingredients: A case study with dipyridamole and cinnarizine.

    PubMed

    Baghel, Shrawan; Cathcart, Helen; Redington, Wynette; O'Reilly, Niall J

    2016-07-01

    Amorphous drug formulations have great potential to enhance solubility and thus bioavailability of BCS class II drugs. However, the higher free energy and molecular mobility of the amorphous form drive them towards the crystalline state which makes them unstable. Accurate determination of the crystallization tendency/kinetics is the key to the successful design and development of such systems. In this study, dipyridamole (DPM) and cinnarizine (CNZ) have been selected as model compounds. Thermodynamic fragility (mT) was measured from the heat capacity change at the glass transition temperature (Tg) whereas dynamic fragility (mD) was evaluated using methods based on extrapolation of configurational entropy to zero [Formula: see text] , and heating rate dependence of Tg [Formula: see text] . The mean relaxation time of amorphous drugs was calculated from the Vogel-Tammann-Fulcher (VTF) equation. Furthermore, the correlation between fragility and glass forming ability (GFA) of the model drugs has been established and the relevance of these parameters to crystallization of amorphous drugs is also assessed. Moreover, the crystallization kinetics of model drugs under isothermal conditions has been studied using Johnson-Mehl-Avrami (JMA) approach to determine the Avrami constant 'n' which provides an insight into the mechanism of crystallization. To further probe into the crystallization mechanism, the non-isothermal crystallization kinetics of model systems were also analysed by statistically fitting the crystallization data to 15 different kinetic models and the relevance of model-free kinetic approach has been established. The crystallization mechanism for DPM and CNZ at each extent of transformation has been predicted. The calculated fragility, glass forming ability (GFA) and crystallization kinetics are found to be in good correlation with the stability prediction of amorphous solid dispersions. Thus, this research work involves a multidisciplinary approach to

  18. An investigation of the reliability of Rapid Upper Limb Assessment (RULA) as a method of assessment of children's computing posture.

    PubMed

    Dockrell, Sara; O'Grady, Eleanor; Bennett, Kathleen; Mullarkey, Clare; Mc Connell, Rachel; Ruddy, Rachel; Twomey, Seamus; Flannery, Colleen

    2012-05-01

    Rapid Upper Limb Assessment (RULA) is a quick observation method of posture analysis. RULA has been used to assess children's computer-related posture, but the reliability of RULA on a paediatric population has not been established. The purpose of this study was to investigate the inter-rater and intra-rater reliability of the use of RULA with children. Video recordings of 24 school children were independently viewed by six trained raters who assessed their postures using RULA, on two separate occasions. RULA demonstrated higher intra-rater reliability than inter-rater reliability although both were moderate to good. RULA was more reliable when used for assessing the older children (8-12 years) than with the younger children (4-7 years). RULA may prove useful as part of an ergonomic assessment, but its level of reliability warrants caution for its sole use when assessing children, and in particular, younger children.

  19. Strain induced directional coarsening in nickel based superalloys: Investigation on kinetics using the small angle neutron scattering (SANS) technique

    SciTech Connect

    Veron, M.; Bastie, P.

    1997-08-01

    Using the small angle neutron scattering technique, the authors have observed rafting in nickel based single crystal superalloys. Kinetics of morphological evolution of the precipitates have been studied in situ. Therefore the authors used a special furnace designed for the ageing of prestrained specimens under a neutron beam. The evolution of both the precipitate aspect ratio and the distance between precipitates confirms the importance of strain in the directional coarsening process. Results are presented and discussed regarding kinetics and microstructural aspects. In such conditions, rafts seem to be different from those obtained after a creep test.

  20. An investigation of the effect of surface impurities on the adsorption kinetics of hydrogen chemisorbed onto iron

    NASA Technical Reports Server (NTRS)

    Shanabarger, Mickey R.

    1993-01-01

    The goal of this program was to develop an understanding of heterogeneous kinetic processes for those molecular species which produce gaseous hydrogen degradation of the mechanical properties of metallic structural materials. Although hydrogen degradation of metallic materials is believed to result from dissolved protonic hydrogen, the heterogeneous hydrogen interface transport processes often dominate the kinetics of degradation. The initial step in the interface transport process is the dissociative chemisorption of the molecular species at the metal surface followed by hydrogen absorption into and transport through the bulk. The interaction of hydrogen with the surfaces of alpha-2(Ti3Al) titanium aluminide, gamma(TiAl) titanium aluminide, and beryllium were studied.

  1. Charge translocation by the Na+/K+-ATPase investigated on solid supported membranes: rapid solution exchange with a new technique.

    PubMed Central

    Pintschovius, J; Fendler, K

    1999-01-01

    Adsorption of Na+/K+-ATPase containing membrane fragments from pig kidney to lipid membranes allows the detection of electrogenic events during the Na+/K+-ATPase reaction cycle with high sensitivity and time resolution. High stability preparations can be obtained using solid supported membranes (SSM) as carrier electrodes for the membrane fragments. The SSMs are prepared using an alkanethiol monolayer covalently linked to a gold surface on a glass substrate. The hydrophobic surface is covered with a lipid monolayer (SAM, self-assembled monolayer) to obtain a double layer system having electrical properties similar to those of unsupported bilayer membranes (BLM). As we have previously shown (, Biophys. J. 64:384-391), the Na+/K+-ATPase on a SSM can be activated by photolytic release of ATP from caged ATP. In this publication we show the first results of a new technique which allows rapid solution exchange at the membrane surface making use of the high mechanical stability of SSM preparations. Especially for substrates, which are not available as a caged substance-such as Na+ and K+-this technique is shown to be capable of yielding new results. The Na+/K+-ATPase was activated by rapid concentration jumps of ATP and Na+ (in the presence of ATP). A time resolution of up to 10 ms was obtained in these experiments. The aim of this paper is to present the new technique together with the first results obtained from the investigation of the Na+/K+-ATPase. A comparison with data taken from the literature shows considerable agreement with our experiments. PMID:9929483

  2. Investigating the Mechanism of Heteroaromatic Decarboxylation Using Solvent Kinetic Isotope Effects and Eyring Transition-State Theory

    ERIC Educational Resources Information Center

    Mundle, Scott O. C.; Opinska, Liliana Guevara; Kluger, Ronald; Dicks, Andrew P.

    2011-01-01

    An upper-level mechanistic organic experiment is outlined where undergraduates measure kinetic rate constants for decarboxylation of pyrrole-2-carboxylic acid by the initial-rates method. UV spectroscopy is used to monitor reactant disappearance in both hydrochloric acid and deuterium chloride at different temperatures. Individual data are pooled…

  3. Investigations on the pharmacokinetics of trofosfamide and its metabolites-first report of 4-hydroxy-trofosfamide kinetics in humans.

    PubMed

    Preiss, Rainer; Baumann, Frank; Stefanovic, Dragan; Niemeyer, Ulf; Pönisch, Wolfgang; Niederwieser, Dietger

    2004-06-01

    Trofosfamide (TRO), like cyclophosphamide (CYCLO) and ifosfamide (IFO), is a prodrug oxazaphosphorine derivative that requires hepatic biotransformation to form the cytotoxically active 4-hydroxy derivative (4-hydroxy-TRO). Individual 4-hydroxyoxazaphosphorines and 4-hydroxy-TRO itself have not been demonstrated in humans up to now. For investigation of the principal pharmacokinetics of TRO and its metabolites, six tumour patients (49-65 years of age, Karnofsky index >70%) with normal liver and renal function were given a single oral dose of 600 mg/m(2) TRO. Plasma was sampled using a bedside technique. Individual 4-hydroxyoxazaphosphorines and TRO together with further metabolites were determined by a specially developed HPLC-UV method and a HPLC-MS method, respectively. With a short apparent half-life (1.2 h) and high apparent clearance (Cl/F 4.0 l/min), TRO was very quickly eliminated from plasma and highly converted to its metabolites, mainly 4-hydroxy-TRO and IFO. In relation to the AUC values of TRO (1.0) the following molar quotients were calculated: 1.59 (4-hydroxy-TRO), 0.40 (4-hydroxy-IFO), 6.90 (IFO) and 0.74 (CYCLO). C(max) values were in the range 10-13 micromol/l for TRO, 4-hydroxy-TRO and IFO and in the range 1.5-4.0 micromol/l for CYCLO, 2- and 3-dechloroethyl-IFO and 4-hydroxy-IFO. Kinetic data indicate that 4-hydroxy-IFO is formed by both hydroxylation of TRO and exocyclic N-dechloroethylation of 4-hydroxy-TRO. 4-hydroxy-CYCLO was not detected above the quantification limit of the method. Only mild haemodepressive side effects were observed after oral administration of 600 mg/m(2) TRO. In relation to known data for IFO, TRO is much more 4-hydroxylated than IFO. The high 4-hydroxy-TRO/TRO ratio found suggests that TRO is a promising tumourstatic agent.

  4. Demonstration of Ion Kinetic Effects in Inertial Confinement Fusion Implosions and Investigation of Magnetic Reconnection Using Laser-Produced Plasmas

    NASA Astrophysics Data System (ADS)

    Rosenberg, M. J.

    2016-10-01

    Shock-driven laser inertial confinement fusion (ICF) implosions have demonstrated the presence of ion kinetic effects in ICF implosions and also have been used as a proton source to probe the strongly driven reconnection of MG magnetic fields in laser-generated plasmas. Ion kinetic effects arise during the shock-convergence phase of ICF implosions when the mean free path for ion-ion collisions (λii) approaches the size of the hot-fuel region (Rfuel) and may impact hot-spot formation and the possibility of ignition. To isolate and study ion kinetic effects, the ratio of N - K =λii /Rfuel was varied in D3He-filled, shock-driven implosions at the Omega Laser Facility and the National Ignition Facility, from hydrodynamic-like conditions (NK 0.01) to strongly kinetic conditions (NK 10). A strong trend of decreasing fusion yields relative to the predictions of hydrodynamic models is observed as NK increases from 0.1 to 10. Hydrodynamics simulations that include basic models of the kinetic effects that are likely to be present in these experiments-namely, ion diffusion and Knudsen-layer reduction of the fusion reactivity-are better able to capture the experimental results. This type of implosion has also been used as a source of monoenergetic 15-MeV protons to image magnetic fields driven to reconnect in laser-produced plasmas at conditions similar to those encountered at the Earth's magnetopause. These experiments demonstrate that for both symmetric and asymmetric magnetic-reconnection configurations, when plasma flows are much stronger than the nominal Alfvén speed, the rate of magnetic-flux annihilation is determined by the flow velocity and is largely insensitive to initial plasma conditions. This work was supported by the Department of Energy Grant Number DENA0001857.

  5. Tolrestat kinetics

    SciTech Connect

    Hicks, D.R.; Kraml, M.; Cayen, M.N.; Dubuc, J.; Ryder, S.; Dvornik, D.

    1984-10-01

    The kinetics of tolrestat, a potent inhibitor of aldose reductase, were examined. Serum concentrations of tolrestat and of total /sup 14/C were measured after dosing normal subjects and subjects with diabetes with /sup 14/C-labeled tolrestat. In normal subjects, tolrestat was rapidly absorbed and disappearance from serum was biphasic. Distribution and elimination t 1/2s were approximately 2 and 10 to 12 hr, respectively, after single and multiple doses. Unchanged tolrestat accounted for the major portion of /sup 14/C in serum. Radioactivity was rapidly and completely excreted in urine and feces in an approximate ratio of 2:1. Findings were much the same in subjects with diabetes. In normal subjects, the kinetics of oral tolrestat were independent of dose in the 10 to 800 mg range. Repetitive dosing did not result in unexpected cumulation. Tolrestat was more than 99% bound to serum protein; it did not compete with warfarin for binding sites but was displaced to some extent by high concentrations of tolbutamide or salicylate.

  6. A novel photochemical system of ferrous sulfite complex: kinetics and mechanisms of rapid decolorization of Acid Orange 7 in aqueous solutions.

    PubMed

    Zhou, Danna; Chen, Long; Zhang, Changbo; Yu, Yingtan; Zhang, Li; Wu, Feng

    2014-06-15

    We previously reported the decolorization of the azo dye Acid Orange 7 (AO7) by sulfate radical (SO4(-)) in the presence of iron(II) sulfite complex and oxygen under UV-vis irradiation (photo-iron(II) sulfite system). This system, however, achieves very limited mineralization of AO7 (in terms of total organic carbon (TOC) removal), which is not in accordance with literature reports on the oxidation of organic contaminants by SO4(-). In the present work, kinetics and products under irradiation of xenon lamp (350 W) were analyzed to reveal the reaction pathway of decolorization of AO7. Steady-state approximation (SSA) of SO4(-) radicals and apparent kinetics of AO7 were examined. The reaction between AO7 and SO4(-) was found to proceed in two steps, namely, electron transfer and SO4(-) addition. The second-order rate constant for the reaction between AO7 and SO4(-) was found to be 8.07 ± 1.07 × 10(9) M(-1) s(-1) by SSA and 6.80 ± 0.68 × 10(9) M(-1) s(-1) by competition kinetics method. The apparent kinetics of the decolorization of AO7 under irradiation closely fits the mechanism of radical chain reactions of various reactive sulfur species. By liquid chromatography coupled with mass spectrometry, we identified the sulfate adduct AO7-SO4 and confirmed the two-step reaction between AO7 and SO4(-). This stable sulfate adduct provides a good explanation of the poor TOC removal during decolorization of AO7 by the photo-iron(II) sulfite system.

  7. Investigations of rapid thermal annealing induced structural evolution of ZnO: Ge nanocomposite thin films via GISAXS

    NASA Astrophysics Data System (ADS)

    Ceylan, Abdullah; Ozcan, Yusuf; Orujalipoor, Ilghar; Huang, Yen-Chih; Jeng, U.-Ser; Ide, Semra

    2016-06-01

    In this work, we present in depth structural investigations of nanocomposite ZnO: Ge thin films by utilizing a state of the art grazing incidence small angle x-ray spectroscopy (GISAXS) technique. The samples have been deposited by sequential r.f. and d.c. sputtering of ZnO and Ge thin film layers, respectively, on single crystal Si(100) substrates. Transformation of Ge layers into Ge nanoparticles (Ge-np) has been initiated by ex-situ rapid thermal annealing of asprepared thin film samples at 600 °C for 30, 60, and 90 s under forming gas atmosphere. A special attention has been paid on the effects of reactive and nonreactive growth of ZnO layers on the structural evolution of Ge-np. GISAXS analyses have been performed via cylindrical and spherical form factor calculations for different nanostructure types. Variations of the size, shape, and distributions of both ZnO and Ge nanostructures have been determined. It has been realized that GISAXS results are not only remarkably consistent with the electron microscopy observations but also provide additional information on the large scale size and shape distribution of the nanostructured components.

  8. Depth investigation of rapid sand filters for drinking water production reveals strong stratification in nitrification biokinetic behavior.

    PubMed

    Tatari, K; Smets, B F; Albrechtsen, H-J

    2016-09-15

    The biokinetic behavior of NH4(+) removal was investigated at different depths of a rapid sand filter treating groundwater for drinking water preparation. Filter materials from the top, middle and bottom layers of a full-scale filter were exposed to various controlled NH4(+) loadings in a continuous-flow lab-scale assay. NH4(+) removal capacity, estimated from short term loading up-shifts, was at least 10 times higher in the top than in the middle and bottom filter layers, consistent with the stratification of Ammonium Oxidizing Bacteria (AOB). AOB density increased consistently with the NH4(+) removal rate, indicating their primarily role in nitrification under the imposed experimental conditions. The maximum AOB cell specific NH4(+) removal rate observed at the bottom was at least 3 times lower compared to the top and middle layers. Additionally, a significant up-shift capacity (4.6 and 3.5 times) was displayed from the top and middle layers, but not from the bottom layer at increased loading conditions. Hence, AOB with different physiological responses were active at the different depths. The biokinetic analysis predicted that despite the low NH4(+) removal capacity at the bottom layer, the entire filter is able to cope with a 4-fold instantaneous loading increase without compromising the effluent NH4(+). Ultimately, this filter up-shift capacity was limited by the density of AOB and their biokinetic behavior, both of which were strongly stratified.

  9. Effects of partial sleep deprivation on slow waves during non-rapid eye movement sleep: a high density EEG investigation

    PubMed Central

    Plante, David T.; Goldstein, Michael R.; Cook, Jesse D.; Smith, Richard; Riedner, Brady A.; Rumble, Meredith E.; Jelenchick, Lauren; Roth, Andrea; Tononi, Giulio; Benca, Ruth M.; Peterson, Michael J.

    2015-01-01

    Objective Changes in slow waves during non-rapid eye movement (NREM) sleep in response to acute total sleep deprivation are well-established measures of sleep homeostasis. This investigation utilized high-density electroencephalography (hdEEG) to examine topographic changes in slow waves during repeated partial sleep deprivation. Methods Twenty-four participants underwent a 6-day sleep restriction protocol. Spectral and period-amplitude analyses of sleep hdEEG data were used to examine changes in slow wave energy, count, amplitude, and slope relative to baseline. Results Changes in slow wave energy were dependent on the quantity of NREM sleep utilized for analysis, with widespread increases during sleep restriction and recovery when comparing data from the first portion of the sleep period, but restricted to recovery sleep if the entire sleep episode was considered. Period-amplitude analysis was less dependent on the quantity of NREM sleep utilized, and demonstrated topographic changes in the count, amplitude, and distribution of slow waves, with frontal increases in slow wave amplitude, numbers of high-amplitude waves, and amplitude/slopes of low amplitude waves resulting from partial sleep deprivation. Conclusions Topographic changes in slow waves occur across the course of partial sleep restriction and recovery. Significance These results demonstrate a homeostatic response to partial sleep loss in humans. PMID:26596212

  10. Flood-frequency analyses from paleoflood investigations for Spring, Rapid, Boxelder, and Elk Creeks, Black Hills, western South Dakota

    USGS Publications Warehouse

    Harden, Tessa M.; O'Connor, Jim E.; Driscoll, Daniel G.; Stamm, John F.

    2011-01-01

    Flood-frequency analyses for the Black Hills area are important because of severe flooding of June 9-10, 1972, that was caused by a large mesoscale convective system and caused at least 238 deaths. Many 1972 peak flows are high outliers (by factors of 10 or more) in observed records that date to the early 1900s. An efficient means of reducing uncertainties for flood recurrence is to augment gaged records by using paleohydrologic techniques to determine ages and magnitudes of prior large floods (paleofloods). This report summarizes results of paleoflood investigations for Spring Creek, Rapid Creek (two reaches), Boxelder Creek (two subreaches), and Elk Creek. Stratigraphic records and resulting long-term flood chronologies, locally extending more than 2,000 years, were combined with observed and adjusted peak-flow values (gaged records) and historical flood information to derive flood-frequency estimates for the six study reaches. Results indicate that (1) floods as large as and even substantially larger than 1972 have affected most of the study reaches, and (2) incorporation of the paleohydrologic information substantially reduced uncertainties in estimating flood recurrence. Canyons within outcrops of Paleozoic rocks along the eastern flanks of the Black Hills provided excellent environments for (1) deposition and preservation of stratigraphic sequences of late-Holocene flood deposits, primarily in protected slack-water settings flanking the streams; and (2) hydraulic analyses for determination of associated flow magnitudes. The bedrock canyons ensure long-term stability of channel and valley geometry, thereby increasing confidence in hydraulic computations of ancient floods from modern channel geometry. Stratigraphic records of flood sequences, in combination with deposit dating by radiocarbon, optically stimulated luminescence, and cesium-137, provided paleoflood chronologies for 29 individual study sites. Flow magnitudes were estimated from elevations of flood

  11. Sorption potential of rice husk for the removal of 2,4-dichlorophenol from aqueous solutions: kinetic and thermodynamic investigations.

    PubMed

    Akhtar, Mubeena; Bhanger, M I; Iqbal, Shahid; Hasany, S Moosa

    2006-01-16

    The sorption potential of chemically and thermally treated rice husk (RHT) for the removal of 2,4-dichlorophenol (DCP) from aqueous solutions has been investigated. Sorption of DCP by rice husk was observed over a wide pH range of 1-10. The effect of contact time between liquid and solid phases, sorbent dose, pH, concentration of sorbate and temperature on the sorption of DCP onto rice husk has been studied. The pore area and average pore diameter of RHT by BET method are calculated to be 17+/-0.6 m2g-1 and 51.3+/-1.5 nm, respectively. Maximum sorption (98+/-1.2%) was achieved for RHT from 6.1x10(-5) moldm(-3) of sorbate solution using 0.1g of rice husk for 10 min agitation time at pH 6 and 303K, which is comparable to activated carbon commercial (ACC) 96.6+/-1.2%, but significantly higher than chemically treated rice husk (RHCT) 65+/-1.6% and rice husk untreated (RHUT) 41+/-2.3%. The sorption data obtained at optimized conditions was subjected to Freundlich, Langmuir and Dubinin-Radushkevich (D-R) isotherms. Sorption intensity 1/n (0.31+/-0.01) and sorption capacity multilayer C(m) (12.0+/-1.6 mmolg(-1)) have been evaluated using Freundlich sorption isotherm, whereas the values of sorption capacity monolayer Q (0.96+/-0.03 mmolg(-1)) and binding energy, b, (4.5+/-1.0)x10(4)dm(3)mol(-1) have been estimated by Langmuir isotherm. The Langmuir constant, b, was also used to calculate the dimensionless factor, R(L), in the concentration range (0.6-6.1)x10(-4) moldm(-3), suggesting greater sorption at low concentration. D-R sorption isotherm was employed to calculate sorption capacity X(m) (2.5+/-0.07 mmolg(-1)) and sorption energy E (14.7+/-0.13 kJmol(-1)). Lagergren and Morris-Weber equations were employed to study kinetics of sorption process using 0.2g of RHT, 25 cm(3) of 0.61x10(-4)moldm(-3) sorbate concentration at pH 6, giving values of first-order rate constant, k, and rate constant of intraparticle transport, R(id), (0.48+/-0.04 min(-1) and 6.8+/-0.8 nmolg(-1

  12. Global investigation of potential energy surfaces for the pyrolysis of C(1)-C(3) hydrocarbons: toward the development of detailed kinetic models from first principles.

    PubMed

    Ryazantsev, Mikhail N; Jamal, Adeel; Maeda, Satoshi; Morokuma, Keiji

    2015-11-07

    Detailed kinetic models (DKMs) are the most fundamental "bottom-up" approaches to computational investigation of the pyrolysis and oxidation of fuels. The weakest points of existing DKMs are incomplete information about the reaction types that can be involved in the potential energy surfaces (PESs) in pyrolysis and oxidation processes. Also, the computational thermodynamic parameters available in the literature vary widely with the level of theory employed. More sophisticated models require improvement both in our knowledge of the type of the reactions involved and the consistency of thermodynamic and kinetic parameters. In this paper, we aim to address these issues by developing ab initio models that can be used to describe early stages of pyrolysis of C1-C3 hydrocarbons. We applied a recently developed global reaction route mapping (GRRM) strategy to systematically investigate the PES of the pyrolysis of C1-C3 hydrocarbons at a consistent level of theory. The reactions are classified into 14 reaction types. The critical points on the PES for all reactions in the network are calculated at the highly accurate UCCSD(T)-F12b/cc-pVTZ//UM06-2X/cc-pVTZ level of theory. The data reported in this paper can be used for first principle calculations of kinetic constants and for a subsequent study on modeling the evolution of the species from the reaction network of the pyrolysis and oxidation of C1-C3 hydrocarbons.

  13. Parametric Investigation of the Isothermal Kinetics of Growth of Graphene on a Nickel Catalyst in the Process of Chemical Vapor Deposition of Hydrocarbons

    NASA Astrophysics Data System (ADS)

    Futko, S. I.; Shulitskii, B. G.; Labunov, V. A.; Ermolaeva, E. M.

    2016-11-01

    A kinetic model of isothermal synthesis of multilayer graphene on the surface of a nickel foil in the process of chemical vapor deposition, on it, of hydrocarbons supplied in the pulsed regime is considered. The dependences of the number of graphene layers formed and the time of their growth on the temperature of the process, the concentration of acetylene, and the thickness of the nickel foil were calculated. The regime parameters of the process of chemical vapor deposition, at which single-layer graphene and bi-layer graphene are formed, were determined. The dynamics of growth of graphene domains at chemical-vapor-deposition parameters changing in wide ranges was investigated. It is shown that the time dependences of the rates of growth of single-layer graphene and bi-layer graphene are nonlinear in character and that they are determined by the kinetics of nucleation and growth of graphene and the diffusion flow of carbon atoms in the nickel foil.

  14. An automated image-based method of 3D subject-specific body segment parameter estimation for kinetic analyses of rapid movements.

    PubMed

    Sheets, Alison L; Corazza, Stefano; Andriacchi, Thomas P

    2010-01-01

    Accurate subject-specific body segment parameters (BSPs) are necessary to perform kinetic analyses of human movements with large accelerations, or no external contact forces or moments. A new automated topographical image-based method of estimating segment mass, center of mass (CM) position, and moments of inertia is presented. Body geometry and volume were measured using a laser scanner, then an automated pose and shape registration algorithm segmented the scanned body surface, and identified joint center (JC) positions. Assuming the constant segment densities of Dempster, thigh and shank masses, CM locations, and moments of inertia were estimated for four male subjects with body mass indexes (BMIs) of 19.7-38.2. The subject-specific BSP were compared with those determined using Dempster and Clauser regression equations. The influence of BSP and BMI differences on knee and hip net forces and moments during a running swing phase were quantified for the subjects with the smallest and largest BMIs. Subject-specific BSP for 15 body segments were quickly calculated using the image-based method, and total subject masses were overestimated by 1.7-2.9%.When compared with the Dempster and Clauser methods, image-based and regression estimated thigh BSP varied more than the shank parameters. Thigh masses and hip JC to thigh CM distances were consistently larger, and each transverse moment of inertia was smaller using the image-based method. Because the shank had larger linear and angular accelerations than the thigh during the running swing phase, shank BSP differences had a larger effect on calculated intersegmental forces and moments at the knee joint than thigh BSP differences did at the hip. It was the net knee kinetic differences caused by the shank BSP differences that were the largest contributors to the hip variations. Finally, BSP differences produced larger kinetic differences for the subject with larger segment masses, suggesting that parameter accuracy is more

  15. Origins of sequence selectivity in homologous genetic recombination: insights from rapid kinetic probing of RecA-mediated DNA strand exchange.

    PubMed

    Lee, Andrew M; Xiao, Jie; Singleton, Scott F

    2006-07-07

    Despite intense effort over the past 30 years, the molecular determinants of sequence selectivity in RecA-mediated homologous recombination have remained elusive. Here, we describe when and how sequence homology is recognized between DNA strands during recombination in the context of a kinetic model for RecA-mediated DNA strand exchange. We characterized the transient intermediates of the reaction using pre-steady-state kinetic analysis of strand exchange using oligonucleotide substrates containing a single fluorescent G analog. We observed that the reaction system was sensitive to heterology between the DNA substrates; however, such a "heterology effect" was not manifest when functional groups were added to or removed from the edges of the base-pairs facing the minor groove of the substrate duplex. Hence, RecA-mediated recombination must occur without the involvement of a triple helix, even as a transient intermediate in the process. The fastest detectable reaction phase was accelerated when the structure or stability of the substrate duplex was perturbed by internal mismatches or the replacement of G.C by I.C base-pairs. These findings indicate that the sequence specificity in recombination is achieved by Watson-Crick pairing in the context of base-pair dynamics inherent to the extended DNA structure bound by RecA during strand exchange.

  16. Reaction condition optimization and kinetic investigation of roasting zinc oxide ore using (NH4)2SO4

    NASA Astrophysics Data System (ADS)

    Shao, Hong-mei; Shen, Xiao-yi; Sun, Yi; Liu, Yan; Zhai, Yu-chun

    2016-10-01

    An orthogonal test was used to optimize the reaction conditions of roasting zinc oxide ore using (NH4)2SO4. The optimized reaction conditions are defined as an (NH4)2SO4/zinc molar ratio of 1.4:1, a roasting temperature of 440°C, and a thermostatic time of 60 min. The molar ratio of (NH4)2SO4/zinc is the most predominant factor and the roasting temperature is the second significant factor that governs the zinc extraction. Thermogravimetric-differential thermal analysis was used for (NH4)2SO4 and zinc mixed in a molar ratio of 1.4:1 at the heating rates of 5, 10, 15, and 20 K·min-1. Two strong endothermic peaks indicate that the complex chemical reactions occur at approximately 290°C and 400°C. XRD analysis was employed to examine the transformations of mineral phases during roasting process. Kinetic parameters, including reaction apparent activation energy, reaction order, and frequency factor, were calculated by the Doyle-Ozawa and Kissinger methods. Corresponding to the two endothermic peaks, the kinetic equations were obtained.

  17. Low density lipoprotein detection based on antibody immobilized self-assembled monolayer: investigations of kinetic and thermodynamic properties.

    PubMed

    Matharu, Zimple; Bandodkar, Amay Jairaj; Sumana, G; Solanki, Pratima R; Ekanayake, E M I Mala; Kaneto, Keiichi; Gupta, Vinay; Malhotra, B D

    2009-10-29

    Human plasma low density lipoprotein (LDL) immunosensor based on surface plasmon resonance (SPR) and quartz crystal microbalance (QCM) was fabricated by immobilizing antiapolipoprotein B (AAB) onto self-assembled monolayer (SAM) of 4-aminothiophenol (ATP). The AAB/ATP/Au immunosensor can detect LDL up to 0.252 microM (84 mg/dL) and 0.360 microM (120 mg/dL) with QCM and SPR, respectively. The SPR and QCM measurements were further utilized to study the reaction kinetics of the AAB-LDL interaction. The adsorption process involved was explored using Langmuir adsorption isotherm and Freundlich adsorption models. The thermodynamic parameters such as change in Gibb's free energy (DeltaG(ads)), change in enthalpy (DeltaH(ads)), and change in entropy (DeltaS(ads)) determined at 283, 298, and 308 K revealed that the AAB-LDL interaction is endothermic in nature and is governed by entropy. Kinetic, thermodynamic, and sticking probability studies disclosed that desorption of the water molecules from the active sites of AAB and LDL plays a key role in the interaction process and increase in temperature favors binding of LDL with the AAB/ATP/Au immunosensor. Thus, the studies were utilized to unravel the most important subprocess involved in the adsorption of LDL onto AAB-modified ATP/Au surface that may help in the fabrication of LDL immunosensors with better efficiency.

  18. Investigation of nonlinear kinetic effects induced by weak turbulencein Vlasov-Maxwell simulations of Backward Stimulated Raman Scattering

    NASA Astrophysics Data System (ADS)

    Ghizzo, A.; Albrecht-Marc, M.; Johnston, T. W.; Reveille, T.; Bertrand, P.; Afeyan, B.

    2006-04-01

    We report here our recent results from semi-lagrangian Vlasov-Maxwell simulations which have been performed for homogeneous or inhomogeneous (parabolic) profiles over a long time. A major role is played by the conventional Backward Stimulated Raman Scattering (B-SRS) for only a short time, after what trapping effects induce a new kinetic regime dominated by self-organized and self-sustained phase space holes induced by EPW vortex merging and similar to Bernstein-Greene-Kruskal (BGK) equilibria. Optical mixing was considered in simulations that means the start of the instability (B-SRS) was controlled by the injection of a low-amplitude electromagnetic probe allowing by the noiseless character of the Vlasov code. A new parametric interaction mechanism was observed involving the scattering off of the probe light by BGK-like structures. These results shows also that the fluid-like behavior at early times of simulation becomes afterwards fully kinetic, invalidating a fluid approach based on a usual three-wave model in this regime.

  19. Characterization and scanning electron microscopic investigation of crosslinked freeze dried gelatin matrices for study of drug diffusivity and release kinetics.

    PubMed

    Thakur, Goutam; Mitra, Analava; Basak, Amit; Sheet, Debdoot

    2012-02-01

    Drug delivery is a promising technique to enhance the therapeutic efficacy of the drug. However, properties of carrier materials require intense improvement for effective transport of drug molecules. In the current study, attempts have been made to develop freeze dried gelatin matrices cross linked with genipin at various temperatures (5°C, 15°C and 25°C) prior to freeze-drying (-80°C). The freeze dried matrices thus obtained at the said temperatures are characterized for crosslinking density, compression strength, swelling behaviors. The matrix crosslinked at 25°C showed highest Flory-Rehner crosslinking density (467 ± 46) (p<0.05), highest compressive strength (12.36 ± 0.12) (p<0.05) and lowest equilibrium water content. In this context, scanning electron microscopy (SEM) was performed to study the surface morphology (size and shape of pores) of the crosslinked matrices. These images were further processed for quantitative analysis of morphological features, viz., areas, radius, ferret diameter, length of major and minor axis and eccentricity using MATLAB toolboxes. These quantitative analyses correlate transport and the release kinetics of model anti-inflammatory drug (indomethacin) from crosslinked matrices in vitro to tune as a controllable delivery system. The diffusional exponent (n) for all constructs ranging from 0.61 to 0.69 (p<0.05) (0.45kinetics.

  20. A joint experimental and theoretical investigation of kinetics and mechanistic study in a synthesis reaction between triphenylphosphine and dialkyl acetylenedicarboxylates in the presence of benzhydrazide.

    PubMed

    Kazemian, Mohammad Amin; Habibi-Khorassani, Sayyed Mostafa; Ebrahimi, Ali; Maghsoodlou, Malek Taher; Jahani, Peyman Mohammadzadeh; Ghahramaninezhad, Mahbobeh

    2012-12-01

    Stable crystalline phosphorus ylides were obtained in excellent yields from the 1:1:1 addition reaction between triphenylphosphine (TPP) and dialkyl acetylenedicarboxylates, in the presence of NH-acids, such as benzhydrazide. To determine the kinetic parameters of the reactions, they were monitored by UV spectrophotometery. The second order fits were automatically drawn and the values of the second order rate constant (k(2)) were calculated using standard equations within the program. At the temperature range studied the dependence of the second order rate constant (Ln k(2)) on reciprocal temperature was compatible with Arrhenius equation. This provided the relevant plots to calculate the activation energy of all reactions. Furthermore, useful information were obtained from studies of the effect of solvent, structure of reactants (different alkyl groups within the dialkyl acetylenedicarboxylates) and also concentration of reactants on the rate of reactions. On the basis of experimental data the proposed mechanism was confirmed according to the obtained results and a steady state approximation and the first step (k(2)) and third (k(3)) steps of the reactions were recognized as the rate determining steps, respectively. In addition, three speculative proposed mechanisms were theoretically investigated using quantum mechanical calculation. The results, arising from the second and third speculative mechanisms, were far from the experimental data. Nevertheless, there was a good agreement between the theoretical kinetic data, emerge from the first speculative mechanism, and experimental kinetic data of proposed mechanism.

  1. Kinetics of α-(2,6-Dimethylphenl)vinyllithium: How To Control Errors Caused by Inefficient Mixing with Pairs of Rapidly Competing Ketones.

    PubMed

    Knorr, Rudolf; Knittl, Monika; Behringer, Claudia; Ruhdorfer, Jakob; Böhrer, Petra

    2017-03-17

    Kinetic studies are a suitable tool to disclose the role of tiny reagent fractions. The title compound 2 reacted in a kinetic reaction order of 0.5 (square root of its concentration) with an excess of the electrophiles ClSiMe3, 1-bromobutane (n-BuBr), or 1-iodobutane (n-BuI) at 32 °C in Et2O or in hydrocarbon solvents. This revealed that the tiny (NMR-invisible) amount of a deaggregated equilibrium component (presumably monomeric 2) was the reactive species, whereas the disolvated dimer 2 was only indirectly involved as a supply depot. Selectivity data (relative rate constants κobs) were collected from competition experiments with the faster reactions of 2 in THF and the addition reactions of 2 to carbonyl compounds. This provided the rate sequences of Et2C═O > dicyclopropyl ketone > t-Bu-C(═O)-Ph > diisopropyl ketone ≫ t-Bu2C═O > ClSiMe3 > n-BuI > n-BuBr ≈ (bromomethyl)cyclopropane (but t-Bu2C═O < ClSiMe3 in THF only) and also of cyclopropanecarbaldehyde > acetone ≥ t-Bu-CH═O. It is suggested that a deceivingly depressed selectivity (1 < κobs < kA/kB), caused by inefficient microscopic mixing of a reagent X with two competing substrates A and B, may become evident toward zero deviation from the correlation line of the usual inverse (1/T) linear temperature dependence of ln κobs.

  2. Temperature dependence of the electrode kinetics of oxygen reduction at the platinum/Nafion interface - A microelectrode investigation

    NASA Technical Reports Server (NTRS)

    Parthasarathy, Arvind; Srinivasan, Supramanian; Appleby, A. J.; Martin, Charles R.

    1992-01-01

    Results of a study of the temperature dependence of the oxygen reduction kinetics at the Pt/Nafion interface are presented. This study was carried out in the temperature range of 30-80 C and at 5 atm of oxygen pressure. The results showed a linear increase of the Tafel slope with temperature in the low current density region, but the Tafel slope was found to be independent of temperature in the high current density region. The values of the activation energy for oxygen reduction at the platinum/Nafion interface are nearly the same as those obtained at the platinum/trifluoromethane sulfonic acid interface but less than values obtained at the Pt/H3PO4 and Pt/HClO4 interfaces. The diffusion coefficient of oxygen in Nafion increases with temperature while its solubility decreases with temperature. These temperatures also depend on the water content of the membrane.

  3. In situ electrochemical investigations of the kinetic and thermodynamic properties of nickel-metal hydride traction batteries

    NASA Astrophysics Data System (ADS)

    Yang, Xiao Guang; Liaw, Bor Yann

    Although large ampere hour nickel-metal hydride (Ni-MH) traction batteries are in the stage of being commercialized for electric and hybrid vehicle applications, little is known about their performance characteristics. By using a standard Hg/HgO reference electrode in a commercial Ni-MH battery, we were able to conduct in situ measurements to determine both kinetic and thermodynamic properties of the system, including the characteristics of individual electrodes. Using the galvanostatic intermittent titration technique (GITT), we simultaneously and effectively determined the open-circuit voltage of the battery, the equilibrium electrode potentials, and the diffusion coefficient of proton and hydrogen in the nickel and metal hydride electrode, respectively, as a function of the states of charge (SOC). Using the current-step excitation technique, we found that the internal resistance of the battery primarily comes from the metal hydride electrode, which is greater by one order of magnitude than that of the Ni electrode. The cyclic linear micro-polarization experiments, on the other hand, showed that the charge-transfer resistance of the electrochemical reaction at the metal hydride electrode is about twice larger than that of the Ni counterpart above 20% SOC. In comparison, the internal resistance is an order of magnitude smaller than those of the electrochemical charge-transfer reactions. The micro-polarization technique also allowed us to calculate the exchange current densities of the respective electrode electrochemical reactions and the associated specific exchange current densities. These in situ, simple but detailed, characterizations of the thermodynamic and kinetic properties of the Ni-MH system provided valuable information for better understanding of the battery performance.

  4. An investigation of the effect of surface impurities on the adsorption kinetics of hydrogen chemisorbed onto iron

    NASA Technical Reports Server (NTRS)

    Shanabarger, Mickey R.

    1991-01-01

    The goal was to develop an understanding of heterogeneous kinetic processes for those molecular species which produce gaseous hydrogen degradation of the mechanical properties of metallic structural materials. Although hydrogen degradation of metallic materials is believed to result from dissolved protonic hydrogen, the heterogeneous hydrogen interface transport processes often dominate the kinetics of the degradation process. The initial step in the interface transport process is the dissociative chemisorption of the molecular species at the metal surface followed by hydrogen absorption into and transport through the bulk. Modern advanced aerospace applications often require the use of structural materials in high pressure hydrogen environments at temperatures which range from low cryogenic temperatures to very high temperatures (1300 K and greater). Materials proposed for these applications, such as the titanium aluminides, beta-titanium alloys, nickel- and cobalt-based superalloys, molybdenum-rhenium alloys, beryllium, and various beryllides, need to possess a high degree of immunity from hydrogen induced degradation of mechanical properties. In the present program, the interaction of hydrogen with the surfaces of alpha-2 (Ti3Al) titanium aluminide, gamma (TiAl) titanium aluminide, and beryllium were studied. The interaction of low pressure hydrogen with gamma titanium aluminide and beryllium was found to be relatively weak, in the sense that adsorption leads to a low surface concentration of dissociated hydrogen, i.e., the chemisorption process is reversible at room temperature (300 K) for gamma titanium aluminide and the sticking coefficient for chemisorption is extremely small for beryllium. Hydrogen was found to interact readily with alpha-2 titanium aluminide to form a stable surface hydride at 300 K. These results correlate well with other recent studies which show that the mechanical properties for alpha-2 titanium aluminide are readily degraded in

  5. Experimental and Numerical Investigation of Guest Molecule Exchange Kinetics based on the 2012 Ignik Sikumi Gas Hydrate Field Trial

    NASA Astrophysics Data System (ADS)

    Ruprecht Yonkofski, C. M.; Horner, J.; White, M. D.

    2015-12-01

    In 2012 the U.S. DOE/NETL, ConocoPhillips Company, and Japan Oil, Gas and Metals National Corporation jointly sponsored the first field trial of injecting a mixture of N2-CO2 into a CH4-hydrate bearing formation beneath the permafrost on the Alaska North Slope. Known as the Ignik Sikumi #1 Gas Hydrate Field Trial, this experiment involved three stages: 1) the injection of a N2-CO2 mixture into a targeted hydrate-bearing layer, 2) a 4-day pressurized soaking period, and 3) a sustained depressurization and fluid production period. Data collected during the three stages of the field trial were made available after a thorough quality check. The Ignik Sikumi #1 data set is extensive, but contains no direct evidence of the guest-molecule exchange process. This study uses numerical simulation to provide an interpretation of the CH4/CO2/N2 guest molecule exchange process that occurred at Ignik Sikumi #1. Simulations were further informed by experimental observations. The goal of the scoping experiments was to understand kinetic exchange rates and develop parameters for use in Iġnik Sikumi history match simulations. The experimental procedure involves two main stages: 1) the formation of CH4 hydrate in a consolidated sand column at 750 psi and 2°C and 2) flow-through of a 77.5/22.5 N2/CO2 molar ratio gas mixture across the column. Experiments were run both above and below the hydrate stability zone in order to observe exchange behavior across varying conditions. The numerical simulator, STOMP-HYDT-KE, was then used to match experimental results, specifically fitting kinetic behavior. Once this behavior is understood, it can be applied to field scale models based on Ignik Sikumi #1.

  6. A Microstructural and Kinetic Investigation of the KCl-Induced Corrosion of an FeCrAl Alloy at 600 °C

    SciTech Connect

    Israelsson, Niklas; Unocic, Kinga A.; Hellström, K.; Jonsson, T.; Norell, M.; Svensson, J. -E.; Johansson, L. -G.

    2015-03-18

    In this paper, the corrosion behaviour of a FeCrAl alloy was investigated at 600 °C in O2 + H2O with solid KCl applied. A kinetics and microstructural investigation showed that KCl accelerates corrosion and that potassium chromate formation depletes the protective scale in Cr, thus triggering the formation of a fast-growing iron-rich scale. Iron oxide was found to grow both inward and outward, on either side of the initial oxide. A chromia layer is formed with time underneath the iron oxide. Finally, it was found that although the alloy does not form a continuous pure alumina scale at the investigated temperature, aluminium is, however, always enriched at the oxide/alloy interface.

  7. KINETIC AND STRUCTURAL INVESTIGATIONS INTO THE ALLOSTERIC AND PH EFFECT ON SUBSTRATE SPECIFICITY OF HUMAN EPITHELIAL 15-LIPOXYGENASE-2

    PubMed Central

    Joshi, Netra; Hoobler, Eric K.; Perry, Steven; Diaz, Giovanni; Fox, Brian; Holman, Theodore R.

    2013-01-01

    Lipoxygenases, important enzymes in inflammation, can regulate their substrate specificity by allosteric interactions with its own hydroperoxide products. In the current work, addition of both 13-(S) hydroxy-9Z,11E-octadecadienoic acid (13-(S)-HODE) and 13-(S)-hydroperoxy-6Z,9Z,11E-octadecatrienoic acid (13-(S)-HOTrE) to human epithelial 15-lipoxygenase-2 (15-LOX-2) increases the kcat/KM substrate specificity ratio of arachidonic acid (AA) and (γ)-linolenic acid (GLA) by 4-fold. 13-(S)-HODE achieves this change by activating kcat/KM AA but inhibiting kcat/KM GLA, which indicates that the allosteric structural changes at the active site discriminates between the length and unsaturation differences of AA and GLA to achieve opposite kinetics effects. The substrate specificity ratio is further increased, 11-fold total, by increasing pH, suggesting mechanistic differences between the pH and allosteric effects. Interestingly, the loss of the PLAT domain affects substrate specificity, but does not eliminate the allosteric properties of 15-LOX-2, indicating that the allosteric site is located in the catalytic domain. However, the removal of the PLAT domain does change the magnitude of the allosteric effect. These data suggest that the PLAT domain moderates the communication pathway between the allosteric and catalytic sites, thus affecting substrate specificity. These results are discussed in the context of protein dimerization and other structural changes. PMID:24171444

  8. Thermal stability and crystallization kinetics of Cu-Zr-Al-Ag BMGs investigated with isothermal electrical resistance measurement

    NASA Astrophysics Data System (ADS)

    Wang, Li-Fang; Cui, Xiao; Zhang, Qi-Dong; Zu, Fang-Qiu

    2014-07-01

    The thermal stability and crystallization kinetics of the Cu x Zr84- x Al8Ag8 ( x = 42, 40, 38, and 36) bulk metallic glasses (BMGs) were studied by measurement of isothermal electrical-resistance. As the composition becomes richer in Zr, the longer incubation time at the same relative annealing temperature, and the larger local activation energy needed to achieve the same crystallized volume-fraction, indicate improved thermal stability, which resists crystallization. The improved thermal stability is attributed to a denser atomic random-stacking structure and larger negative heat-of-mixing. During isothermal annealing processes, the four BMGs exhibited the same nucleation mechanism, which is a decreasing rate of nucleation over time. However, the crystal growth mechanisms of the four BMGs are different. The crystallization of the Cu36Zr48Al8Ag8 and Cu38Zr46Al8Ag8 BMGs is interface-controlled growth, contrasting with diffusion-controlled growth for the Cu40Zr44Al8Ag8 and Cu42Zr42Al8Ag8 alloys. The different growth modes may be caused by fluctuations in composition due to changes in the quantity and distribution of Cu-rich and Ag-rich regions.

  9. Kinetic Monte Carlo Investigation of the Effects of Vacancy Pairing on Oxygen Diffusivity in Yttria-Stabilized Zirconia

    NASA Technical Reports Server (NTRS)

    Good, Brian S.

    2011-01-01

    Yttria-stabilized zirconia s high oxygen diffusivity and corresponding high ionic conductivity, and its structural stability over a broad range of temperatures, have made the material of interest for use in a number of applications, for example, as solid electrolytes in fuel cells. At low concentrations, the stabilizing yttria also serves to increase the oxygen diffusivity through the presence of corresponding oxygen vacancies, needed to maintain charge neutrality. At higher yttria concentration, however, diffusivity is impeded by the larger number of relatively high energy migration barriers associated with yttrium cations. In addition, there is evidence that oxygen vacancies preferentially occupy nearest-neighbor sites around either dopant or Zr cations, further affecting vacancy diffusion. We present the results of ab initio calculations that indicate that it is energetically favorable for oxygen vacancies to occupy nearest-neighbor sites adjacent to Y ions, and that the presence of vacancies near either species of cation lowers the migration barriers. Kinetic Monte Carlo results from simulations incorporating this effect are presented and compared with results from simulations in which the effect is not present.

  10. Investigating the chemical and isotopic kinetics of aerobic methane oxidation in the Northern US Atlantic Margin, Hudson Canyon

    NASA Astrophysics Data System (ADS)

    Chan, E. W.; Kessler, J. D.; Shiller, A. M.; Redmond, M. C.; Arrington, E. C.; Valentine, D. L.

    2015-12-01

    Recent discoveries of methane seepage along the US Atlantic margin have led to speculation on the fate of the released methane. Here we examine the kinetics of aerobic methane oxidation to gain a fundamental understanding of this methane sink. In order to look at this process in its entirety, a unique mesocosm incubation system was developed with a Dissolved Gas Analyzer System (DGAS) to monitor in real time the chemical and isotopic changes involved with aerobic methane oxidation. This system measures changes in methane, carbon dioxide, and oxygen concentrations as well as the stable carbon isotopes of methane and carbon dioxide with time. In addition samples are strategically removed to characterize trace metals, nutrients, cell counts, and microbial community genetics. This presentation will detail the results obtained from samples collected inside the Hudson Canyon at the edge of the methane clathrate stability zone and outside the Hudson Canyon, not influenced by the methane seepage. These results show that in both environments along the Atlantic margin, methane was consumed aggressively but the timing of consumption varied based on location. In addition, these results are leading to insights into the chemical requirements needed for aerobic methane oxidation and the resulting isotopic fractionation.

  11. An Investigation Of Photodynamic Therapy In The Treatment Of Pancreatic Carcinoma: Dihematoporphyrin Ether Uptake And Photobleaching Kinetics

    NASA Astrophysics Data System (ADS)

    Mang, Thomas S.; Wieman, Thomas J.

    1988-02-01

    Results of dihematoporphyrin ether (DHE) uptake and fluorescence kinetics show that the concentration in the pancreas is on the order of 40-60 μg DHE/g of tissue at an injected dose of 40 mg/kg. Previously concentrations on this order have only been found in organs of the reticuloendothelial system. Two intrapancreatic carcinoma models, one of acinar origin (rat) and one of ductal orgin (hamster), were studied. Both showed equal or higher concentrations of DHE as compared to normal pancreas when fluorescence measurements and chemical extraction procedures were performed. Photodynamic therapy (PDT) treatment of the normal pancreas and pancreatic tumors yielded atypical results. When the normal pancreas with DHE present is exposed to 630 nm light from a dye laser (75 mW/cm2, 30 min), the normal photobleaching measurable by fluorescence decay does not occur. Yet, the pancreatic tumor responds with a relatively normal fluorescence decay pattern, with hemorrhaging and a resultant loss of measurable DHE concentration. These results represent the emergence of an entirely new modality, with substantial potential for the treatment of cancer of the pancreas.

  12. An investigation of the effect of surface impurities on the adsorption kinetics of hydrogen chemisorbed onto iron

    NASA Technical Reports Server (NTRS)

    Shanabarger, Mickey R.

    1994-01-01

    The goal of this program has been to develop an understanding of heterogeneous kinetic processes for those molecular species which produce gaseous hydrogen degradation of the mechanical properties of metallic structural materials. During the present program, the interaction of hydrogen with the surfaces of alpha-2 (Ti3Al) titanium aluminide, gamma (TiAl) titanium aluminide, and beryllium were studied. The interaction of low pressure hydrogen with gamma titanium aluminide and beryllium was found to be relatively weak. Weak in the sense that adsorption leads to a low surface concentration of dissociated hydrogen, i.e., the chemisorption process is reversible at room temperature (300 K) for gamma titanium aluminide and the sticking coefficient for chemisorption is extremely small for beryllium. Hydrogen was found to interact readily with alpha-2 titanium aluminide to form a stable surface hydride at 300 K. These results correlate well with other recent studies which show that the mechanical properties for alpha-2 titanium aluminide are readily degraded in hydrogen while gamma titanium aluminide exhibits less degradation and beryllium essentially no degradation. The interaction of oxygen with the surface of several of these materials was studied. More recently, preliminary hydrogen permeation studies were completed for three high temperature alloys, Incoloy 909, Mo-47.5Re (wt. %), and this past year, Haynes 188.

  13. An Investigation into the Kinetics and Mechanism of the Removal of Cyanobacteria by Extract of Ephedra equisetina Root

    PubMed Central

    Yan, Rong; Ji, Hongli; Wu, Yonghong; Kerr, Philip G.; Fang, Yanming; Yang, Linzhang

    2012-01-01

    An aqueous extract of Ephedra equisetina root was found to induce cyanobacterial cell death. The extract displayed no negative effects on the fish populations but instead, improved the habitat conditions for the growth of macrophytes, zooplankton and bacteria because the inhibiting effects of the extracts on cyanobacteria helped clear up the water column. The removal kinetics of cyanobacteria by E. equisetina extract appears to be a first order process with the rate constant being extract-dose-dependent. Compounds including the flavonoids found in E. equisetina root kill the cyanobacteria in vitro at a dose of 5.0 µg extract per 100 mL water or above. The extract constituents act to disrupt the thylakoid membrane, interrupt the electronic transport, decrease the effective quantum yield, and eventually lead to the failure of photosynthesis in Microcystis aeruginosa. This study presents an easily-deployed, natural and promising approach for controlling cyanobacterial blooms as an emergency measure, and also provides insight into the dynamics and mechanism of the extract consisting of multiple compounds synergistically removing algae. PMID:22870313

  14. Investigation of the Icosahedral Z-Phase in Aluminium Transition Metal Alloys and Rapidly Solidified Al-Alloys

    DTIC Science & Technology

    1986-09-01

    Rev. Lett., 53, 1951 (1984). - A Script& NETALLURGICA Vol. 20, pp. 745-750, 1986 Pergamon Press Ltd. Printed in the U.S.A. All rights reserved...single- and two-sided jet polishing were utilized. In addition, some of the flakes were argon-ion . - - thinned using standard procedures. Subsequently...Reeied 26 Fabruay 198, accepted 14 April 1986) Electrohydrodynamic (EHD) atomization has boen used to rapidly solidify micron and submicron size

  15. A Microstructural and Kinetic Investigation of the KCl-Induced Corrosion of an FeCrAl Alloy at 600 °C

    DOE PAGES

    Israelsson, Niklas; Unocic, Kinga A.; Hellström, K.; ...

    2015-03-18

    In this paper, the corrosion behaviour of a FeCrAl alloy was investigated at 600 °C in O2 + H2O with solid KCl applied. A kinetics and microstructural investigation showed that KCl accelerates corrosion and that potassium chromate formation depletes the protective scale in Cr, thus triggering the formation of a fast-growing iron-rich scale. Iron oxide was found to grow both inward and outward, on either side of the initial oxide. A chromia layer is formed with time underneath the iron oxide. Finally, it was found that although the alloy does not form a continuous pure alumina scale at the investigatedmore » temperature, aluminium is, however, always enriched at the oxide/alloy interface.« less

  16. Investigation of Kinetics of crystallization Processes of S15-Se85, S15-Se81-Cu4 Chalcogenide glasses

    NASA Astrophysics Data System (ADS)

    Samudrala, Kavitha; Babu Devarasetty, Suresh

    2016-09-01

    In the present work, S15-Se85, S15-Se81-Cu4 chalcogenide glasses are prepared by using conventional melt quenching technique. The as-prepared samples are studied by experimental techniques like X-ray Diffraction (XRD), Differential Scanning Calorimetry (DSC). XRD studies have confirmed that the as-prepared samples are amorphous in nature. It is clear from DSC studies that the as-prepared samples are glassy in nature. Kinetic analysis of the crystallization process of as-prepared glasses is carried using DSC curves. Activation energy for glass transition and Activation energy for crystallization are determined using Kissinger method. Activation energy for glass transition of S15-Se85 and S15-Se81-Cu4 glasses is found to be 84.5076 and 275.801 KJ/Mole respectively. Activation energy for crystallization of S15-Se85 glass is found to be 106.2622 KJ/Mole for 1st peak while Activation energy for crystallization of S15-Se81-Cu4 glasses is found to be 97.93 KJ/Mole for 1st peak and 84.20 KJ/Mole for 2nd peak. Kauzmann temperature (Tk) is determined from the heating rate dependent glass transition and crystallization temperatures. Tk value for S15-Se85 glass sample is 236.680K (1st peak) and for S15-Se81-Cu4 is 283.530K (1st peak) and 286.330K (2n peak). Avrami Index (n) is also determined for as-prepared glasses. Avrami Index (n) value for S15-Se85 glass sample is 1.8 (1st peak) and for S15-Se81-Cu4 is 2.9 (1st peak) and 1.4 (2nd peak). The crystalline phases by thermal treatment of as-prepared glasses are identified using XRD patterns.

  17. In situ transmission electron microscopy investigation of the interfacial reaction between Ni and Al during rapid heating in a nanocalorimeter

    SciTech Connect

    Grapes, Michael D. E-mail: david.lavan@nist.gov; LaGrange, Thomas; Reed, Bryan W.; Campbell, Geoffrey H.; Woll, Karsten; LaVan, David A. E-mail: david.lavan@nist.gov; Weihs, Timothy P. E-mail: david.lavan@nist.gov

    2014-11-01

    The Al/Ni formation reaction is highly exothermic and of both scientific and technological significance. In this report, we study the evolution of intermetallic phases in this reaction at a heating rate of 830 K/s. 100-nm-thick Al/Ni bilayers were deposited onto nanocalorimeter sensors that enable the measurement of temperature and heat flow during rapid heating. Time-resolved transmission electron diffraction patterns captured simultaneously with thermal measurements allow us to identify the intermetallic phases present and reconstruct the phase transformation sequence as a function of time and temperature. The results show a mostly unaltered phase transformation sequence compared to lower heating rates.

  18. Synthesis of ultrathin poly(methyl methacrylate) model coatings bound via organosilanes to zinc and investigation of their delamination kinetics.

    PubMed

    Iqbal, Danish; Rechmann, Julian; Sarfraz, Adnan; Altin, Abdulrahman; Genchev, Georgi; Erbe, Andreas

    2014-10-22

    Polymer coatings are widely used to protect metals from corrosion. Coating adhesion to the base material is critical for good protection, but coatings may fail because of cathodic delamination. Most of the experimental studies on cathodic delamination use polymers to study the corrosion behavior under conditions where the interfacial chemistry at the metal(oxide)/polymer interface is not well-defined. Here, ultrathin linear and cross-linked poly(methyl methacrylate) [PMMA] coatings that are covalently bound to oxide-covered zinc via a silane linker have been prepared. For preparation, zinc was functionalized with vinyltrimethoxysilane (VTS), yielding a vinyl monomer-covered surface. These samples were subjected to thermally initiated free radical polymerization in the presence of methyl methacrylate (MMA) to yield surface-bound ultrathin PMMA films of 10-20 nm thickness, bound to the surface via Zn-O-Si bonds. A similar preparation was also carried out in the presence of different amounts of the cross-linkers ethylene glycol diacrylate and hexanediol diacrylate. Functionalized and polymer-coated zinc samples were characterized by infrared (IR) spectroscopy, secondary ion mass spectrometry (SIMS), ellipsometry, and X-ray photoelectron spectroscopy (XPS). Coating stability toward cathodic delamination has been evaluated by scanning Kelvin probe (SKP) experiments. In all cases, the covalently linked coatings show lower delamination rates of 0.02-0.2 mm h(-1) than coatings attached to the surface without covalent bonds (rates ∼10 mm h(-1)). Samples with a higher fraction of cross-linker delaminate slower, with rates down to 0.03-0.04 mm h(-1), compared to ∼0.3 mm h(-1) without cross-linker. Samples with longer hydrophobic alkyl chains also delaminate slower, with the lowest observed delamination rate of 0.028 mm h(-1) using hexanediol diacrylate. For the coatings studied here, delamination kinetics is not diffusion limited, but the rate is controlled by a chemical

  19. Toward mechanistic understanding of nuclear reprocessing chemistries by quantifying lanthanide solvent extraction kinetics via microfluidics with constant interfacial area and rapid mixing.

    PubMed

    Nichols, Kevin P; Pompano, Rebecca R; Li, Liang; Gelis, Artem V; Ismagilov, Rustem F

    2011-10-05

    The closing of the nuclear fuel cycle is an unsolved problem of great importance. Separating radionuclides produced in a nuclear reactor is useful both for the storage of nuclear waste and for recycling of nuclear fuel. These separations can be performed by designing appropriate chelation chemistries and liquid-liquid extraction schemes, such as in the TALSPEAK process (Trivalent Actinide-Lanthanide Separation by Phosphorus reagent Extraction from Aqueous Komplexes). However, there are no approved methods for the industrial scale reprocessing of civilian nuclear fuel in the United States. One bottleneck in the design of next-generation solvent extraction-based nuclear fuel reprocessing schemes is a lack of interfacial mass transfer rate constants obtained under well-controlled conditions for lanthanide and actinide ligand complexes; such rate constants are a prerequisite for mechanistic understanding of the extraction chemistries involved and are of great assistance in the design of new chemistries. In addition, rate constants obtained under conditions of known interfacial area have immediate, practical utility in models required for the scaling-up of laboratory-scale demonstrations to industrial-scale solutions. Existing experimental techniques for determining these rate constants suffer from two key drawbacks: either slow mixing or unknown interfacial area. The volume of waste produced by traditional methods is an additional, practical concern in experiments involving radioactive elements, both from disposal cost and experimenter safety standpoints. In this paper, we test a plug-based microfluidic system that uses flowing plugs (droplets) in microfluidic channels to determine absolute interfacial mass transfer rate constants under conditions of both rapid mixing and controlled interfacial area. We utilize this system to determine, for the first time, the rate constants for interfacial transfer of all lanthanides, minus promethium, plus yttrium, under TALSPEAK

  20. Rapid Ti(III) reduction of perchlorate in the presence of beta-alanine: kinetics, pH effect, complex formation, and beta-alanine effect.

    PubMed

    Wang, Chao; Huang, Zhengdao; Lippincott, Lee; Meng, Xiaoguang

    2010-03-15

    Ti(III) reduction of perchlorate might be a useful method for the treatment of highly perchlorate-contaminated water. Though the reaction rate was usually low, we observed that beta-alanine (HOOCCH(2)CH(2)NH(2)) could significantly promote the reaction. A complete (>99.9%) perchlorate removal was obtained in a solution containing [ClO(4)(-)]=1.0mM, [Ti(III)]=40 mM, and [beta-alanine]=120 mM after 2.5h of reaction under 50 degrees C. The effects of both pH and complex formation on the reaction were then studied. The results showed that without beta-alanine the optimal pH was 2.3. When pH increased from 1.6 to 2.3, the reduction rate increased remarkably. In the pH range >2.3, however, the reduction was significantly inhibited, attributed to the formation of Ti(III) precipitate. The presence of beta-alanine at a molar ratio of [beta-alanine]:[Ti(III)]=3:1 significantly increased the reduction rate of perchlorate even at near neutral pH. This is because beta-alanine formed complexes with Ti(III), which greatly improved the total soluble [Ti(III)] in the pH range between 3.5 and 6. The findings may lead to the development of rapid treatment methods for intermittent and small stream of highly perchlorate-contaminated water, which are resulted from the manufacturing, storage, handling, use and/or disposal of large quantities of perchlorate salts.

  1. In Situ Localized Surface Plasmon Resonance (LSPR) Spectroscopy to Investigate Kinetics of Chemical Bath Deposition of CdS Thin Films

    DOE PAGES

    Kalyanaraman, Ramki; Taz, Humaira; Ruther, Rose E.; ...

    2015-02-11

    Techniques that can characterize the early stages of thin film deposition from liquid phase processes can aid greatly in our understanding of mechanistic aspects of chemical bath deposition (CBD). Here we have used localized surface plasmon resonance (LSPR) spectroscopy to monitor in-situ the kinetics of early-stage growth of cadmium sulfide (CdS) thin films on Ag nanoparticle on quartz substrates. Real-time shift during CdS deposition showed that the LSPR wavelength red shifted rapidly due to random deposition of CdS on the substrate, but saturated at longer times. LSPR modeling showed that these features could be interpreted as an initial deposition ofmore » CdS islands followed by preferential deposition onto itself. The CdS also showed significantly enhanced Raman signals up to 170 times due to surface enhanced raman scattering (SERS) from the CdS/Ag NP regions. The ex-situ SERS effect supported the LSPR shift suggesting that these techniques could be used to understand nucleation and growth phenomena from the liquid phase.« less

  2. In Situ Localized Surface Plasmon Resonance (LSPR) Spectroscopy to Investigate Kinetics of Chemical Bath Deposition of CdS Thin Films

    SciTech Connect

    Kalyanaraman, Ramki; Taz, Humaira; Ruther, Rose E.; Nanda, Jagjit

    2015-02-11

    Techniques that can characterize the early stages of thin film deposition from liquid phase processes can aid greatly in our understanding of mechanistic aspects of chemical bath deposition (CBD). Here we have used localized surface plasmon resonance (LSPR) spectroscopy to monitor in-situ the kinetics of early-stage growth of cadmium sulfide (CdS) thin films on Ag nanoparticle on quartz substrates. Real-time shift during CdS deposition showed that the LSPR wavelength red shifted rapidly due to random deposition of CdS on the substrate, but saturated at longer times. LSPR modeling showed that these features could be interpreted as an initial deposition of CdS islands followed by preferential deposition onto itself. The CdS also showed significantly enhanced Raman signals up to 170 times due to surface enhanced raman scattering (SERS) from the CdS/Ag NP regions. The ex-situ SERS effect supported the LSPR shift suggesting that these techniques could be used to understand nucleation and growth phenomena from the liquid phase.

  3. Kinetic Atom.

    ERIC Educational Resources Information Center

    Wilson, David B.

    1981-01-01

    Surveys the research of scientists like Joule, Kelvin, Maxwell, Clausius, and Boltzmann as it comments on the basic conceptual issues involved in the development of a more precise kinetic theory and the idea of a kinetic atom. (Author/SK)

  4. Steam explosion pretreatment of wheat straw to improve methane yields: investigation of the degradation kinetics of structural compounds during anaerobic digestion.

    PubMed

    Theuretzbacher, Franz; Lizasoain, Javier; Lefever, Christopher; Saylor, Molly K; Enguidanos, Ramon; Weran, Nikolaus; Gronauer, Andreas; Bauer, Alexander

    2015-03-01

    Wheat straw can serve as a low-cost substrate for energy production without competing with food or feed production. This study investigated the effect of steam explosion pretreatment on the biological methane potential and the degradation kinetics of wheat straw during anaerobic digestion. It was observed that the biological methane potential of the non steam exploded, ground wheat straw (276 l(N) kg VS(-1)) did not significantly differ from the best steam explosion treated sample (286 l(N) kg VS(-1)) which was achieved at a pretreatment temperature of 140°C and a retention time of 60 min. Nevertheless degradation speed was improved by the pretreatment. Furthermore it was observed that compounds resulting from chemical reactions during the pretreatment and classified as pseudo-lignin were also degraded during the anaerobic batch experiments. Based on the rumen simulation technique, a model was developed to characterise the degradation process.

  5. Spectroscopic investigation on kinetics, thermodynamics and mechanism for electron transfer reaction of iron(III) complex with sulphur centered radical in stimulated biological system.

    PubMed

    Deepalakshmi, S; Sivalingam, A; Kannadasan, T; Subramaniam, P; Sivakumar, P; Brahadeesh, S T

    2014-04-24

    Electron transfer reactions of biological organic sulphides with several metal ions to generate sulphide radical cations are a great concern in biochemical process. To understand the mechanism, a stimulated biological system having model compounds, iron(III)-bipyridyl complex with thio-diglycolic acid (TDGA) was investigated. Spectroscopic study reveals the kinetics and thermodynamics of the reaction in aqueous perchloric acid medium. The reaction follows first and fractional order of 0.412 with respect to [Fe(bpy)3](3+) and TDGA, respectively. The oxidation is insensitive to variation in [H(+)] but slightly decreases with increase in ionic strength ([I]). Addition of acrylamide, a radical scavenger has no effect on the rate of the reaction. The high negative value of ΔS(#) (-74.3±1.09 J K(-1) mol(-1)) indicates the complex formed has a definite orientation higher than the reactants. Based on the above results, a suitable reaction mechanism for this reaction is proposed.

  6. Kinetic and mechanistic investigation of the sequential hydrogenation of phenylacetylene catalyzed by OsHCl(CO)(PR sub 3 ) sub 2 (PR sub 3 = PMe-t-Bu sub 2 and P-i-Pr sub 3 )

    SciTech Connect

    Esteruelas, M.A.; Oro, L.A.; Sola, E.; Valero, C. ); Meyer, U.; Werner, H. ); Andriollo, A.; Sanchez-Delgado, R.A.

    1989-09-13

    The reactivities of the hydrido carbonyl complexes OsHCl(CO)(PR{sub 3}){sub 2} (PR{sub 3} = PMe-t-Bu{sub 2} (1), P-i-Pr{sub 3} (2)) toward hydrogen, alkynes, and oxygen have been studied. The solutions of 1 and 2 are rapidly decolorized upon contact with H{sub 2} under ambient conditions; the decolorized solution of 2 shows in benzene-d{sub 6} a {sup 1}H NMR spectrum that is consistent with the formation of the dihydrogen compound OsHCl({eta}{sup 2}-H{sub 2})(CO)(P-i-Pr{sub 3}){sub 2} (3). The reactivity of 1 and 2 toward alkynes depends on the type of alkyne used. The title complexes react with acetylene, propyne, and phenylacetylene by insertion to give the five-coordinate vinylosmium compounds Os(CH=CHR)Cl(CO)(Pr{sub 3}){sub 2} (7 and 8); the same starting materials in the presence of t-BuC{triple bond}CH and PhC{triple bond}CPh are completely inert. The kinetic investigation of this reaction provides evidence that indicates that the formation of styryl derivatives is the step that determines the selectivity for the hydrogenation to the alkene.

  7. Spectroscopic and kinetic investigation of the reactions of peroxyacetic acid with Burkholderia pseudomallei catalase-peroxidase, KatG.

    PubMed

    Ivancich, Anabella; Donald, Lynda J; Villanueva, Jacylyn; Wiseman, Ben; Fita, Ignacio; Loewen, Peter C

    2013-10-15

    Catalase-peroxidases or KatGs can utilize organic peroxyacids and peroxides instead of hydrogen peroxide to generate the high-valent ferryl-oxo intermediates involved in the catalase and peroxidase reactions. In the absence of peroxidatic one-electron donors, the ferryl intermediates generated with a low excess (10-fold) of peroxyacetic acid (PAA) slowly decay to the ferric resting state after several minutes, a reaction that is demonstrated in this work by both stopped-flow UV-vis absorption measurements and EPR spectroscopic characterization of Burkholderia pseudomallei KatG (BpKatG). EPR spectroscopy showed that the [Fe(IV)═O Trp330(•+)], [Fe(IV)═O Trp139(•)], and [Fe(IV)═O Trp153(•)] intermediates of the peroxidase-like cycle of BpKatG ( Colin, J. Wiseman, B. Switala, J. Loewen, P. C. Ivancich, A. ( 2009 ) J. Am. Chem. Soc. 131 , 8557 - 8563 ), formed with a low excess of PAA at low temperature, are also generated with a high excess (1000-fold) of PAA at room temperature. However, under high excess conditions, there is a rapid conversion to a persistent [Fe(IV)═O] intermediate. Analysis of tryptic peptides of BpKatG by mass spectrometry before and after treatment with PAA showed that specific tryptophan (including W330, W139, and W153), methionine (including Met264 of the M-Y-W adduct), and cysteine residues are either modified with one, two, or three oxygen atoms or could not be identified in the spectrum because of other undetermined modifications. It was concluded that these oxidized residues were the source of electrons used to reduce the excess of PAA to acetic acid and return the enzyme to the ferric state. Treatment of BpKatG with PAA also caused a loss of catalase activity towards certain substrates, consistent with oxidative disruption of the M-Y-W adduct, and a loss of peroxidase activity, consistent with accumulation of the [Fe(IV)═O] intermediate and the oxidative modification of the W330, W139, and W153. PAA, but not H2O2 or tert

  8. Enzyme Kinetics.

    ERIC Educational Resources Information Center

    Moe, Owen; Cornelius, Richard

    1988-01-01

    Conveys an appreciation of enzyme kinetic analysis by using a practical and intuitive approach. Discusses enzyme assays, kinetic models and rate laws, the kinetic constants (V, velocity, and Km, Michaels constant), evaluation of V and Km from experimental data, and enzyme inhibition. (CW)

  9. Quantitative kinetic investigation of triazole-gold(I) complex catalyzed [3,3]-rearrangement of propargyl ester.

    PubMed

    Xi, Yumeng; Wang, Qiaoyi; Su, Yijin; Li, Minyong; Shi, Xiaodong

    2014-02-28

    The triazole-gold(I) complex catalyzed [3,3]-rearrangement of propargyl ester has been quantitatively investigated through in situ IR. First order dependence of the initial rates on [Au] and [propargyl ester] suggested that the turnover-limiting step is the associative ligand substitution. The activation enthalpy was also determined to be 7.8 kcal mol(-1). TA-Au catalysts with different triazole derivatives were also tested, giving a linear free energy relationship with a ρ value of 0.74.

  10. Influence of C60 co-deposition on the growth kinetics of diindenoperylene-From rapid roughening to layer-by-layer growth in blended organic films

    NASA Astrophysics Data System (ADS)

    Lorch, C.; Novák, J.; Banerjee, R.; Weimer, S.; Dieterle, J.; Frank, C.; Hinderhofer, A.; Gerlach, A.; Carla, F.; Schreiber, F.

    2017-02-01

    We investigated the growth of the two phase-separating materials diindenoperylene (DIP) and buckminsterfullerene C60 with different mixing ratio in real-time and in situ by X-ray scattering experiments. We found that at room temperature, mixtures with an excess of DIP show a growth mode which is very close to the perfect layer-by-layer limit with DIP crystallites forming over the entire film thickness. An unexpected increase in the island size is observed for these mixtures as a function of film thickness. On the other hand, equimolar and C60 dominated mixtures grow with poor crystallinity but form very smooth films. Additionally, it is observed that higher substrate temperatures lead to an increase in the length scale of phase separation with film thickness.

  11. Kinetics and Thermodynamics of the Reaction between the (•)OH Radical and Adenine: A Theoretical Investigation.

    PubMed

    Milhøj, Birgitte O; Sauer, Stephan P A

    2015-06-18

    The accessibility of all possible reaction paths for the reaction between the nucleobase adenine and the (•)OH radical is investigated through quantum chemical calculations of barrier heights and rate constants at the ωB97X-D/6-311++G(2df,2pd) level with Eckart tunneling corrections. First the computational method is validated by considering the hydrogen abstraction from the heterocyclic N9 nitrogen in adenine as a test system. Geometries for all molecules in the reaction are optimized with four different DFT exchange-correlation functionals (B3LYP, BHandHLYP, M06-2X, and ωB97X-D), in combination with Pople and Dunning basis sets, all of which have been employed in similar investigations in the literature. Improved energies are obtained through single point calculations with CCSD(T) and the same basis sets, and reaction rate constants are calculated for all methods both without tunneling corrections and with the Wigner, Bell, and Eckart corrections. In comparison to CCSD(T)//BHandHLYP/aug-cc-pVTZ reference results, the ωB97X-D/6-311++G(2df,2pd) method combined with Eckart tunneling corrections provides a sensible compromise between accuracy and time. Using this method, all subreactions of the reaction between adenine and the (•)OH radical are investigated. The total rate constants for hydrogen abstraction and addition for adenine are predicted with this method to be 1.06 × 10(-12) and 1.10 × 10(-12) cm(3) molecules(-1) s(-1), respectively. Abstractions of H61 and H62 contribute the most, while only addition to the C8 carbon is found to be of any significance, in contrast to previous claims that addition is the dominant reaction pathway. The overall rate constant for the complete reaction is found to be 2.17 × 10(-12) cm(3) molecules(-1) s(-1), which agrees exceptionally well with experimental results.

  12. Pictures of a thousand words: Investigating the neural mechanisms of reading with extremely rapid event-related fMRI

    PubMed Central

    Yarkoni, Tal; Speer, Nicole K.; Balota, David A.; McAvoy, Mark P.; Zacks, Jeffrey M.

    2008-01-01

    Reading is one of the most important skills human beings can acquire, but has proven difficult to study naturalistically using functional magnetic resonance imaging (fMRI). We introduce a novel Event-Related Reading (ERR) fMRI approach that enables reliable estimation of the neural correlates of single-word processing during reading of rapidly presented narrative text (200–300 ms / word). Application to an fMRI experiment in which subjects read coherent narratives and made no overt responses revealed widespread effects of orthographic, phonological, contextual, and semantic variables on brain activation. Word-level variables predicted activity in classical language areas as well as the inferotemporal visual word form area, specifically supporting a role for the latter in mapping visual forms onto articulatory or acoustic representations. Additional analyses demonstrated that ERR results replicate across experiments and predict reading comprehension. The ERR approach represents a powerful and extremely flexible new approach for studying reading and language behavior with fMRI. PMID:18554928

  13. COMBINED THEORETICAL AND EXPERIMENTAL INVESTIGATION OF MECHANISMS AND KINETICS OF VAPOR-PHASE MERCURY UPTAKE BY CARBONACOUES SURFACES

    SciTech Connect

    Radisav D. Vidic

    2002-05-01

    The first part of this study evaluated the application of a versatile optical technique to study the adsorption and desorption of model adsorbates representative of volatile polar (acetone) and non-polar (propane) organic compounds on a model carbonaceous surface under ultra high vacuum (UHV) conditions. The results showed the strong correlation between optical differential reflectance (ODR) and adsorbate coverage determined by temperature programmed desorption (TPD). ODR technique was proved to be a powerful tool to investigate surface adsorption and desorption from UHV to high pressure conditions. The effects of chemical functionality and surface morphology on the adsorption/desorption behavior of acetone, propane and mercury were investigated for two model carbonaceous surfaces, namely air-cleaved highly oriented pyrolytic graphite (HOPG) and plasma-oxidized HOPG. They can be removed by thermal treatment (> 500 K). The presence of these groups almost completely suppresses propane adsorption at 90K and removal of these groups leads to dramatic increase in adsorption capacity. The amount of acetone adsorbed is independent of surface heat treatment and depends only on total exposure. The effects of morphological heterogeneity is evident for plasma-oxidized HOPG as this substrate provides greater surface area, as well as higher energy binding sites. Mercury adsorption at 100 K on HOPG surfaces with and without chemical functionalities and topological heterogeneity created by plasma oxidation occurs through physisorption. The removal of chemical functionalities from HOPG surface enhances mercury physisorption. Plasma oxidation of HOPG provides additional surface area for mercury adsorption. Mercury adsorption by activated carbon at atmospheric pressure occurs through two distinct mechanisms, physisorption below 348 K and chemisorption above 348 K. No significant impact of oxygen functionalities was observed in the chemisorption region. The key findings of this study

  14. Kinetics of actinide complexation reactions

    SciTech Connect

    Nash, K.L.; Sullivan, J.C.

    1997-09-01

    Though the literature records extensive compilations of the thermodynamics of actinide complexation reactions, the kinetics of complex formation and dissociation reactions of actinide ions in aqueous solutions have not been extensively investigated. In light of the central role played by such reactions in actinide process and environmental chemistry, this situation is somewhat surprising. The authors report herein a summary of what is known about actinide complexation kinetics. The systems include actinide ions in the four principal oxidation states (III, IV, V, and VI) and complex formation and dissociation rates with both simple and complex ligands. Most of the work reported was conducted in acidic media, but a few address reactions in neutral and alkaline solutions. Complex formation reactions tend in general to be rapid, accessible only to rapid-scan and equilibrium perturbation techniques. Complex dissociation reactions exhibit a wider range of rates and are generally more accessible using standard analytical methods. Literature results are described and correlated with the known properties of the individual ions.

  15. Quantum chemical investigation on the mechanism and kinetics of OH radical-initiated atmospheric oxidation of PCB-47.

    PubMed

    Sun, Yanhui; Zhang, Qingzhu; Wang, Hui; Wang, Wenxing

    2015-08-01

    The OH radical-initiated atmospheric oxidation degradation of 2,2',4,4'-tetrachlorobiphenyl (PCB-47) was investigated by using quantum chemical calculations. All possible pathways involved in the oxidation process were discussed. Potential barriers and reaction heats have been obtained to assess the energetically favorable reaction pathways and the relatively stable products. The study shows that the OH radicals are more likely to attack the C3 and C5 atom of the aromatic ring in the PCB-47 molecule to form PCB-OH adducts. Subsequent reactions are the addition of O2 or NO2 molecule to the PCB-OH adducts at the ortho position of the OH group. Water molecule plays an important role during the whole degradation process. The individual and overall rate constants were calculated by using the Rice-Ramsperger-Kassel-Marcus (RRKM) theory over the temperature range of 180-370K. At 298K, the atmospheric lifetime of PCB-47 determined by OH radicals is about 9.1d. The computational results are crucial to risk assessment and pollution prevention of PCBs.

  16. Experimental model for the investigation of kinetic and/or dynamic interactions between drugs and ethanol in humans.

    PubMed

    Hartmann, D; Flückiger, A; Ziegler, W H; Timm, U; Zell, M

    1988-04-01

    This study was performed to establish an experimental method for the investigation of interactions between ethanol and drugs under predictable and controlled conditions. The model was tested with flumazenil (Ro 15-1788), a short-acting benzodiazepine antagonist with an elimination half-life of 1 h. Six healthy volunteers (5 males, 1 female) were administered ethanol by intravenous infusion with stepwise changing rates. The infusion rates were adapted to each subject on the basis of individual disposition parameters of ethanol, which were derived from preceding short-term infusions of 120 min duration (1.0 mg/kg in males, 0.8 mg/kg in the female). This two-step procedure led to individual ethanol plasma levels between 1.47 +/- 0.04 and 1.71 +/- 0.03 g/L, which were reached after 2.5 h and thereafter maintained over another 6 h. Within the period of constant ethanol levels, single doses of flumazenil and placebo, respectively, were injected intravenously as a bolus (2 min) in a double-blind fashion according to a randomized two-way crossover design. Three subjects received a dose of 0.10 mg/kg of flumazenil, and the remaining three subjects received a dose of 0.20 mg/kg. Evaluation of the plasma concentration time curves of flumazenil did not reveal evidence of an effect of ethanol on the pharmacokinetics of this drug.

  17. Rapid Metagenomic Next-Generation Sequencing during an Investigation of Hospital-Acquired Human Parainfluenza Virus 3 Infections

    PubMed Central

    Zerr, Danielle M.; Qin, Xuan; Adler, Amanda L.; Sampoleo, Reigran; Kuypers, Jane M.; Englund, Janet A.; Jerome, Keith R.

    2016-01-01

    ABSTRACT Metagenomic next-generation sequencing (mNGS) is increasingly used for the unbiased detection of viruses, bacteria, fungi, and eukaryotic parasites in clinical samples. Whole-genome sequencing (WGS) of clinical bacterial isolates has been shown to inform hospital infection prevention practices, but this technology has not been utilized during potential respiratory virus outbreaks. Here, we report on the use of mNGS to inform the real-time infection prevention response to a cluster of hospital-acquired human parainfluenza 3 virus (HPIV3) infections at a children's hospital. Samples from 3 patients with hospital-acquired HPIV3 identified over a 12-day period on a general medical unit and 10 temporally associated samples from patients with community-acquired HPIV3 were analyzed. Our sample-to-sequencer time was <24 h, while our sample-to-answer turnaround time was <60 h with a hands-on time of approximately 6 h. Eight (2 cases and 6 controls) of 13 samples had sufficient sequencing coverage to yield the whole genome for HPIV3, while 10 (2 cases and 8 controls) of 13 samples gave partial genomes and all 13 samples had >1 read for HPIV3. Phylogenetic clustering revealed the presence of identical HPIV3 genomic sequence in the two of the cases with hospital-acquired infection, consistent with the concern for recent transmission within the medical unit. Adequate sequence coverage was not recovered for the third case. This work demonstrates the promise of mNGS for providing rapid information for infection prevention in addition to microbial detection. PMID:27795347

  18. Using 13C-labeled benzene and Raman gas spectroscopy to investigate respiration and biodegradation kinetics following soil contamination

    NASA Astrophysics Data System (ADS)

    Jochum, Tobias; Popp, Juergen; Frosch, Torsten

    2016-04-01

    Soil and groundwater contamination with benzene can cause serious environmental damages. However, many soil microorganisms are capable to adapt and known to strongly control the fate of organic contamination. Cavity enhanced Raman gas spectroscopy (CERS) was applied to investigate the short-term response of indigenous soil bacteria to a sudden surface contamination with benzene regarding the temporal variations of gas products and their exchange rates with the adjacent atmosphere. 13C-labeled benzene was spiked on a silty-loamy soil column (sampled from Hainich National Park, Germany) in order to track and separate the changes in heterotrophic soil respiration - involving 12CO2 and O2 - from the microbial process of benzene degradation, which ultimately forms 13CO2.1 The respiratory quotient (RQ) of 0.98 decreased significantly after the spiking and increased again within 33 hours to a value of 0.72. This coincided with maximum 13CO2 concentration rates (0.63 μ mol m-2 s-1), indicating highest benzene degradation at 33 hours after the spiking event. The diffusion of benzene in the headspace and the biodegradation into 13CO2 were simultaneously monitored and 12 days after the benzene spiking no measurable degradation was detected anymore.1 The RQ finally returned to a value of 0.96 demonstrating the reestablished aerobic respiration. In summary, this study shows the potential of combining Raman gas spectroscopy and stable isotopes to follow soil microbial biodegradation dynamics while simultaneously monitoring the underlying respiration behavior. Support by the Collaborative Research Center 1076 Aqua Diva is kindly acknowledged. We thank Beate Michalzik for soil analysis and discussion. 1. T. Jochum, B. Michalzik, A. Bachmann, J. Popp and T. Frosch, Analyst, 2015, 140, 3143-3149.

  19. A novel P700 redox kinetics probe for rapid, non-intrusive and whole-tissue determination of photosystem II functionality, and the stoichiometry of the two photosystems in vivo.

    PubMed

    Jia, Husen; Dwyer, Simon A; Fan, Da-Yong; Han, Yaqin; Badger, Murray R; von Caemmerer, Susanne; Chow, Wah Soon

    2014-11-01

    We sought a rapid, non-intrusive, whole-tissue measure of the functional photosystem II (PS II) content in leaves. Summation of electrons, delivered by a single-turnover flash to P700(+) (oxidized PS I primary donor) in continuous background far-red light, gave a parameter S in absorbance units after taking into account an experimentally determined basal electron flux that affects P700 redox kinetics. S was linearly correlated with the functional PS II content measured by the O(2) yield per single-turnover repetitive flash in Arabidopsis thaliana expressing an antisense construct to the PsbO (manganese-stabilizing protein in PS II) proteins of PS II (PsbO mutants). The ratio of S to z(max) (total PS I content in absorbance units) was comparable to the PS II/PS I reaction-center ratio in wild-type A. thaliana and in control Spinacea oleracea. Both S and S/z(max) decreased in photoinhibited spinach leaf discs. The whole-tissue functional PS II content and the PS II/photosystem I (PS I) ratio can be non-intrusively monitored by S and S/z(max), respectively, using a quick P700 absorbance protocol compatible with modern P700 instruments.

  20. Investigation of the photochemical reactivity of soot particles derived from biofuels toward NO2. A kinetic and product study.

    PubMed

    Romanías, Manolis N; Dagaut, Philippe; Bedjanian, Yuri; Andrade-Eiroa, Auréa; Shahla, Roya; Emmanouil, Karafas S; Papadimitriou, Vassileios C; Spyros, Apostolos

    2015-03-12

    In the current study, the heterogeneous reaction of NO2 with soot and biosoot surfaces was investigated in the dark and under illumination relevant to atmospheric conditions (J(NO2) = 0.012 s(-1)). A flat-flame burner was used for preparation and collection of soot samples from premixed flames of liquid fuels. The biofuels were prepared by mixing 20% v/v of (i) 1-butanol (CH3(CH2)3OH), (ii) methyl octanoate (CH3(CH2)6COOCH3), (iii) anhydrous diethyl carbonate (C2H5O)2CO and (iv) 2,5 dimethyl furan (CH3)2C4H2O additive compounds in conventional kerosene fuel (JetA-1). Experiments were performed at 293 K using a low-pressure flow tube reactor (P = 9 Torr) coupled to a quadrupole mass spectrometer. The initial and steady-state uptake coefficients, γ0 and γ(ss), respectively, as well as the surface coverage, N(s), were measured under dry and humid conditions. Furthermore, the branching ratios of the gas-phase products NO (∼80-100%) and HONO (<20%) were determined. Soot from JetA-1/2,5-dimethyl furan was the most reactive [γ0 = (29.1 ± 5.8) × 10(-6), γ(ss)(dry) = (9.09 ± 1.82) × 10(-7) and γ(ss)(5.5%RH) = (14.0 ± 2.8)(-7)] while soot from JetA-1/1-butanol [γ0 = (2.72 ± 0.544) × 10(-6), γ(ss)(dry) = (4.57 ± 0.914) × 10(-7), and γ(ss)(5.5%RH) = (3.64 ± 0.728) × 10(-7)] and JetA-1/diethyl carbonate [γ0 = (2.99 ± 0.598) × 10(-6), γ(ss)(dry) = (3.99 ± 0.798) × 10(-7), and γ(ss)(5.5%RH) = (4.80 ± 0.960) × 10(-7)] were less reactive. To correlate the chemical reactivity with the physicochemical properties of the soot samples, their chemical composition was analyzed employing Raman spectroscopy, NMR, and high-performance liquid chromatography. In addition, the Brunauer-Emmett-Teller adsorption isotherms and the particle size distributions were determined employing a Quantachrome Nova 2200e gas sorption analyzer. The analysis of the results showed that factors such as (i) soot mass collection rate, (ii) porosity of the particles formed, (iii

  1. [Investigations on the physiology of the glands of carnivorous plants : IV. The kinetics of chloride secretion by the gland tissue of Nepenthes].

    PubMed

    Lüttge, U

    1966-03-01

    The transport of chloride in isolated tissue from Nepenthes pitchers was investigated using (36)Cl(-), an Aminco-Cotlove chloride-titrator for the determinations of Cl(-) concentrations, and KCN and AsO 4 (-) -as metabolic inhibitors.The tissue was brought in contact with different experimental solutions (=medium). The surface corresponding to the outside of the pitchers was cut with a razor blade to remove the cutinized epidermal layer. At this surface the Cl(-) uptake from the medium is a metabolic process which depends on the Cl(-)-concentration of the medium in a manner that corresponds to the MICHAELIS-MENTEN kinetics. The Michaelis-constant of this transport step was 3×10(-2)M. The Cl(-)-efflux into the medium, however, is a passive process.The opposite surface of the tissue slices (corresponding to the inside of the pitchers) carries the glands. The chloride secretion taking place here is also dependent on metabolism. In vitro it occurs even when a high gradient of chloride concentration has been set up between the medium and the solution which is in contact with the glands. In vivo the Cl(-)-concentration of the pitcher fluid and the amount of Cl(-) per gram of tissue water are almost equal.The rôle of chloride in the physiology of Nepenthes is still under investigation, A correlation between the chloride content of the pitcher fluid and its enzymatic activity (Casein-test), however, could already be demonstrated.

  2. Investigating and managing the rapid emergence of white-nose syndrome, a novel, fatal, infectious disease of hibernating bats

    USGS Publications Warehouse

    Foley, Janet; Clifford, Deana; Castle, Kevin; Cryan, Paul M.; Ostfeld, Richard S.

    2011-01-01

    White-nose syndrome (WNS) is a fatal disease of bats that hibernate. The etiologic agent of WNS is the fungus Geomyces destructans, which infects the skin and wing membranes. Over 1 million bats in six species in eastern North America have died from WNS since 2006, and as a result several species of bats may become endangered or extinct. Information is lacking on the pathogenesis of G. destructans and WNS, WNS transmission and maintenance, individual and site factors that contribute to the probability of an outbreak of WNS, and spatial dynamics of WNS spread in North America. We considered how descriptive and analytical epidemiology could be used to fill these information gaps, including a four-step (modified) outbreak investigation, application of a set of criteria (Hill's) for assessing causation, compartment models of disease dynamics, and spatial modeling. We cataloged and critiqued adaptive-management options that have been either previously proposed for WNS or were helpful in addressing other emerging diseases of wild animals. These include an ongoing program of prospective surveillance of bats and hibernacula for WNS, treatment of individual bats, increasing population resistance to WNS (through vaccines, immunomodulators, or other methods), improving probability of survival from starvation and dehydration associated with WNS, modifying hibernacula environments to eliminate G. destructans, culling individuals or populations, controlling anthropogenic spread of WNS, conserving genetic diversity of bats, and educating the public about bats and bat conservation issues associated with WNS.

  3. Rapid Radiations and the Race to Redundancy: An Investigation of the Evolution of Australian Elapid Snake Venoms.

    PubMed

    Jackson, Timothy N W; Koludarov, Ivan; Ali, Syed A; Dobson, James; Zdenek, Christina N; Dashevsky, Daniel; Op den Brouw, Bianca; Masci, Paul P; Nouwens, Amanda; Josh, Peter; Goldenberg, Jonathan; Cipriani, Vittoria; Hay, Chris; Hendrikx, Iwan; Dunstan, Nathan; Allen, Luke; Fry, Bryan G

    2016-10-26

    Australia is the stronghold of the front-fanged venomous snake family Elapidae. The Australasian elapid snake radiation, which includes approximately 100 terrestrial species in Australia, as well as Melanesian species and all the world's sea snakes, is less than 12 million years old. The incredible phenotypic and ecological diversity of the clade is matched by considerable diversity in venom composition. The clade's evolutionary youth and dynamic evolution should make it of particular interest to toxinologists, however, the majority of species, which are small, typically inoffensive, and seldom encountered by non-herpetologists, have been almost completely neglected by researchers. The present study investigates the venom composition of 28 species proteomically, revealing several interesting trends in venom composition, and reports, for the first time in elapid snakes, the existence of an ontogenetic shift in the venom composition and activity of brown snakes (Pseudonaja sp.). Trends in venom composition are compared to the snakes' feeding ecology and the paper concludes with an extended discussion of the selection pressures shaping the evolution of snake venom.

  4. Rapid Radiations and the Race to Redundancy: An Investigation of the Evolution of Australian Elapid Snake Venoms

    PubMed Central

    Jackson, Timothy N. W.; Koludarov, Ivan; Ali, Syed A.; Dobson, James; Zdenek, Christina N.; Dashevsky, Daniel; op den Brouw, Bianca; Masci, Paul P.; Nouwens, Amanda; Josh, Peter; Goldenberg, Jonathan; Cipriani, Vittoria; Hay, Chris; Hendrikx, Iwan; Dunstan, Nathan; Allen, Luke; Fry, Bryan G.

    2016-01-01

    Australia is the stronghold of the front-fanged venomous snake family Elapidae. The Australasian elapid snake radiation, which includes approximately 100 terrestrial species in Australia, as well as Melanesian species and all the world’s true sea snakes, may be less than 12 million years old. The incredible phenotypic and ecological diversity of the clade is matched by considerable diversity in venom composition. The clade’s evolutionary youth and dynamic evolution should make it of particular interest to toxinologists, however, the majority of species, which are small, typically inoffensive, and seldom encountered by non-herpetologists, have been almost completely neglected by researchers. The present study investigates the venom composition of 28 species proteomically, revealing several interesting trends in venom composition, and reports, for the first time in elapid snakes, the existence of an ontogenetic shift in the venom composition and activity of brown snakes (Pseudonaja sp.). Trends in venom composition are compared to the snakes’ feeding ecology and the paper concludes with an extended discussion of the selection pressures shaping the evolution of snake venom. PMID:27792190

  5. Kinetic investigation of the oxidation of naval excess hazardous materials in supercritical water for the design of a transpiration-wall reactor

    SciTech Connect

    Rice, S.F.; Hanush, R.G.; Hunter, T.B.

    1997-01-01

    Experiments were conducted in Sandia`s supercritical fluids reactor (SFR) to generate data for the design of a transpiration-wall supercritical water oxidation (SCWO) reactor. The reactor is intended for the disposal of hazardous material generated on naval vessels. The design parameters for the system require an accurate knowledge of destruction efficiency vs. time and temperature. Three candidate materials were selected for testing. The experiments consisted of oxidizing these materials in the SFR at isothermal conditions over the temperature range of 400-550C at 24.1 MPa. A small extrapolation of the results shows that these materials can be adequately destroyed (to 99.9% destruction removal efficiency, DRE, based on total organic carbon (TOC) in the effluent) in approximately 5 seconds at 600C. The results vary smoothly and predictably with temperature such that extrapolation to higher temperatures beyond the experimental capabilities of the SFR can be made with reasonable confidence. The preliminary design of the transpiration-wall reactor has a rapid heat-up section within the reactor vessel that requires the addition of a fuel capable of quickly reacting with oxygen at temperatures below 500C. Candidate alcohols and JP-5 jet fuel were evaluated in this context. Oxidation rates for the alcohols were examined using in situ Raman spectroscopy. In addition, the potential utility of supplying the oxidizer line with hydrogen peroxide as an additive to enhance rapid initiation of the feed at unusually low temperatures was investigated. Experiments were conducted in the Supercritical Constant Volume Reactor (SCVR) using hydrogen peroxide as the initial oxidizing species. The results show that this concept as a method of enhancing low temperature reactivity appears to fail because thermal decomposition of the hydrogen peroxide is more rapid than the fuel oxidation rate at low temperatures. 8 refs., 16 figs., 5 tabs.

  6. Density functional theory investigation of competitive free-radical processes during the thermal cracking of methylated polyaromatics: estimation of kinetic parameters.

    PubMed

    Leininger, J-Philippe; Minot, Christian; Lorant, François; Behar, Françoise

    2007-04-26

    Density functional B3LYP and BH&HLYP calculations with the 6-31G** basis set have been performed to investigate elementary reactions playing an important role in the pyrolysis of 1-methylnaphthalene. The pathways describing the destiny of the main radicals, H, methyl, hydromethylnaphthyl and methylnaphthyl, have been studied. At low temperature, addition of H atoms on the aromatic ring is favored over hydrogen abstraction. Except at low temperature (below 400 K), the hydromethylnaphthyl radical undergoes preferentially a loss of hydrogen rather than a bimolecular hydrogen transfer with methylnaphthalene or addition reaction on methylnaphthalene forming a hydrogenated dimer. In the range 400-750 K, the formation of methane by hydrogen abstraction of methyl radical on methylnaphthalene is predominant compared to the formation of hydrodimethylnaphthalenes by addition reaction. Rate constants of reactions describing the formation of heavy products like methyldinaphthylmethanes or dimethylbinaphthalenes have been calculated and discussed. They are also compared to recombination reactions from the literature. Rate constants of these reactions have been computed using transition state theory and can be integrated in kinetic radical schemes of methylated polyaromatic compounds pyrolysis from geological to laboratory conditions.

  7. Non-isothermal crystallization kinetics and glass-forming ability of Ti41Zr25Be28Fe6 bulk metallic glass investigated by differential scanning calorimetry

    NASA Astrophysics Data System (ADS)

    Gong, Pan; Zhao, Shaofan; Wang, Xin; Yao, Kefu

    2015-07-01

    The non-isothermal crystallization kinetics and glass-forming ability of Ti41Zr25Be28Fe6 glassy alloy were investigated by differential scanning calorimetry. The activation energies corresponding to the characteristic temperatures have been calculated by Kissinger and Ozawa equations. Based on Kissinger-Akahira-Sunose and Ozawa-Flynn-Wall models, it has been found that the local activation energy is higher at the beginning of the crystallization process for the first exothermic peak. The local Avrami exponent indicates that the first-step crystallization is mainly a high-dimensional nucleation and growth with an increasing nucleation rate. According to the calculated fragility index, Ti41Zr25Be28Fe6 alloy can be classified as "strong glass former." The studied alloy also possesses a critical size up to centimeter order, and the high glass-forming ability is probably related to the relatively low Gibbs energy difference between the liquid and crystalline states. The critical cooling rate of Ti41Zr25Be28Fe6 glassy alloy has also been determined using Barandiaran-Colmenero's method.

  8. Theoretical investigation on the kinetics and mechanisms of hydroxyl radical-induced transformation of parabens and its consequences for toxicity: Influence of alkyl-chain length.

    PubMed

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

    2016-03-15

    As emerging organic contaminants (EOCs), the ubiquitous presence of preservative parabens in water causes a serious environmental concern. Hydroxyl radical ((•)OH) is a strong oxidant that can degrade EOCs through photochemistry in surface water environments as well as in advanced oxidation processes (AOPs). To better understand the degradation mechanisms, kinetics, and products toxicity of the preservative parabens in aquatic environments and AOPs, the (•)OH-initiated degradation reactions of the four parabens were investigated systematically using a computational approach. The four studied parabens with increase of alkyl-chain length were methylparaben (MPB), ethylparaben (EPB), propylparaben (PPB), and dibutylparaben (BPB). Results showed that the four parabens can be initially attacked by (•)OH through (•)OH-addition and H-abstraction routes. The (•)OH-addition route was more important for the degradation of shorter alkyl-chain parabens like MPB and EPB, while the H-abstraction route was predominant for the degradation of parabens with longer alkyl-chain for example PPB and BPB. In assessing the aquatic toxicity of parabens and their degradation products using the model calculations, the products of the (•)OH-addition route were found to be more toxic to green algae than original parabens. Although all degradation products were less toxic to daphnia and fish than corresponding parental parabens, they could be still harmful to these aquatic organisms. Furthermore, as alkyl-chain length increased, the ecotoxicity of parabens and their degradation products was found to be also increased.

  9. Parametric Investigation of the Kinetics of Growth of Carbon-Nanotube Arrays on Iron Nanoparticles in the Process of Chemical Vapor Deposition of Hydrocarbons

    NASA Astrophysics Data System (ADS)

    Futko, S. I.; Shulitski, B. G.; Labunov, V. A.; Ermolaevaa, E. M.

    2015-03-01

    On the basis of the kinetic model of synthesis of carbon nanotubes on iron nanoparticles in the process of chemical vapor deposition of hydrocarbons, the parametric dependences of characteristics of arrays of vertically oriented nanotubes on the temperature of their synthesis, the concentration of acetylene in a reactor, and the diameter of the catalyst nanoparticles were investigated. It is shown that the maximum on the temperature dependence of the rate of growth of carbon nanotubes, detected in experiments at a temperature of ~700oC is due to the competing processes of increasing the catalytic activity of iron nanoparticles and decreasing the acetylene concentration because of the signifi cant gas-phase decomposition of acetylene in the reactor before it enters the substrate with the catalyst. Our calculations have shown that the indicated maximum arises near the transition point separating the low-temperature region where multiwall nanotubes are predominantly synthesized from the higher-temperature region of generation of single-wall nanotubes in the process of chemical vapor deposition of hydrocarbons.

  10. A Heavy-Atom Isotope Effect and Kinetic Investigation of the Hydrolysis of Semicarbazide by Urease from Jack Bean (Canavalia ensiformis) †

    PubMed Central

    Marlier, John F.; Fogle, Emily J.; Cleland, W.W.

    2009-01-01

    A kinetic investigation of the hydrolysis of semicarbazide by urease gives a relatively flat log V/K vs. pH plot between pH 5 and 8. A log Vm vs. pH plot shows a shift of the optimum Vm toward lower pH when compared to urea. These results are explained in terms of the binding of the outer-N of the –NHNH2 group in semicarbazide to an active site residue with a relatively low pKa (∼6). Heavy-atom isotope effects for both leaving groups have been determined. For the –NHNH2 side 15kobs = 1.0045, whereas for the –NH2 side 15kobs = 1.0009. This is evidence that –NHNH2 leaves prior to –NH2. Using previous data from the urease-catalyzed hydrolysis of formamide, the commitment factors for semicarbazide and urea hydrolysis are estimated as 2.7 and 1.2, respectively. The carbonyl-C isotope effect is 13kobs = 1.0357 which is consistent with the transition state occurring either during formation or breakdown of the tetrahedral intermediate. PMID:18817416

  11. Experimental and numerical investigations of heat transport and crystallization kinetics in laser-induced modification of barium strontium titanate thin films

    NASA Astrophysics Data System (ADS)

    Baldus, O.; Waser, R.

    2005-04-01

    Barium strontium titanate (BST) has a large application potential in microelectronics due to its implementation as a high-permittivity dielectric in thin-film capacitors. Technologies are therefore being investigated for the deposition of the ceramics as thin films onto semiconductor components. A two-step process will be presented in this paper: first, the deposition of an amorphous ceramic thin film on a platinum-coated silicon wafer and, secondly, the laser sintering of this film. A laser process with pulsed UV light of 248-nm and 193-nm wavelength and approximately 20-ns pulse length allows us to reduce the thermal load on the substrate during the sintering process by minimizing the interaction time between the heating source and the ceramic layer. The goal of this work is to investigate fundamental aspects of the solid-state physics and process technology during the laser sintering of amorphous, electroceramic thin films. Adjusting the film thicknesses prevents damage to the ceramic thin films by the laser treatment. Planar test structures are manufactured and characterized structurally and electrically. Characterization of the BST films reveals clearly improved dielectric properties in comparison to the amorphous films. The real part of the dielectric constant can be raised three- to fivefold at 10 kHz, while the imaginary part decreases by nearly an order of magnitude. Chemical analysis does not indicate any significant changes in the stoichiometry of the thin films due to the laser process. The laser-induced changes proceed similarly to the crystallization of the amorphous films in the furnace. Parallel to the experimental work, a numerical simulation model is developed, which, on the basis of thermal conduction, the Johnson-Mehl-Avrami crystallization kinetics, and thermoelasticity, models the temperature, crystallization, and mechanical load of the thin films. The simulation calculations are correlated with the results of the analysis of the laser

  12. Unanimous Model for Describing the Fast Bioluminescence Kinetics of Ca(2+) -regulated Photoproteins of Different Organisms.

    PubMed

    Eremeeva, Elena V; Bartsev, Sergey I; van Berkel, Willem J H; Vysotski, Eugene S

    2017-03-01

    Upon binding their metal ion cofactors, Ca(2+) -regulated photoproteins display a rapid increase of light signal, which reaches its peak within milliseconds. In the present study, we investigate bioluminescence kinetics of the entire photoprotein family. All five recombinant hydromedusan Ca(2+) -regulated photoproteins-aequorin from Aequorea victoria, clytin from Clytia gregaria, mitrocomin from Mitrocoma cellularia and obelins from Obelia longissima and Obelia geniculata-demonstrate the same bioluminescent kinetics pattern. Based on these findings, for the first time we propose a unanimous kinetic model describing the bioluminescence mechanism of Ca(2+) -regulated photoproteins.

  13. Removal of organic matter from surface water during coagulation with sludge flotation and rapid filtration - a full-scale technological investigation.

    PubMed

    Pruss, Alina

    2015-01-01

    Coagulation with sludge flotation and rapid filtration was selected as a surface water treatment technology to be optimised with a full-scale investigation, which was carried out in Poland between August and October 2013. The river water treated was characterized by low alkalinity, high-temperature variability and a high organic matter content. In the course of technological studies, the processes of coagulation with sludge flotation and rapid filtration were analysed. The studies were performed in the most adverse conditions for the applied technology i.e. during the period of algal bloom and subsequent decomposition of dead plankton. Throughout the study, the river water contained mainly dissolved organic matter, with occasional increases in the concentration of the undissolved fraction during algal bloom. The undissolved total organic carbon (TOC) fraction was effectively removed through coagulation while small doses of ClO₂added prior to coagulation enhanced the process. The process of coagulation using high-coagulant doses at pH = 6.5 did not provide a reduction in the TOC value below the level of 4 mg C/L required for treated water. The effect was achieved by adding powdered activated carbon (PAC) before the filters. The coagulation products were characterised by low-hydraulic resistance which should be taken into account at the stage of water delivery to the filters, after flotation.

  14. A theoretical investigation on kinetics, mechanism, and thermochemistry of the gas-phase reactions of methyl fluoroacetate with OH radicals and fate of alkoxy radical.

    PubMed

    Mishra, Bhupesh Kumar; Deka, Ramesh Chandra

    2014-09-25

    We theoretically investigated OH-initiated hydrogen abstraction reactions of methyl fluoroacetate (MFA) CH2FC(O)OCH3 at the MPWB1K level of theory in conjunction with the 6-31+G(d,p) basis set. Thermodynamic and kinetic data are computed using the comparatively accurate G2(MP2) method. Two most stable conformers of MFA are identified, and the energy difference between them is found to be only 0.32 kcal mol(-1). Both of them are considered for rate coefficient calculations, and the contribution from each of the conformers is found to be quite significant. We propose an indirect mechanism due to validation of pre- and post-reactive complexes. The rate parameters are determined using canonical transition state theory and energetics at the G2(MP2) level. The temperature dependence of the rate constant can be described by the Arrhenius expressions: k = 8.79 × 10(-13) exp[(-377.27 ± 64)/T] cm(3) molecule(-1) s(-1) over a temperature range of 250-450 K. The ΔfH°298 for CH2FC(O)OCH3, CH2FC(O)OC(•)H2, and C(•)HFC(O)OCH3 are also computed using an isodesmic procedure. The OH-driven atmospheric lifetime of MFA was estimated to be 24 days. A mechanistic study to shed light on the atmospheric degradation and the sole fate for the consumption of CH2FC(O)OCH2O(•) radical has also been reported.

  15. Investigating the chemical mechanisms of the functionalization and fragmentation of hydrocarbons in the heterogeneous oxidation by OH using a stochastic kinetics model

    NASA Astrophysics Data System (ADS)

    Wiegel, A. A.; Wilson, K. R.; Hinsberg, B.; Houle, F. A.

    2014-12-01

    While the heterogeneous oxidation of atmospheric organic aerosols influences their effects on climate, air quality, and visibility, a more detailed understanding of the chemical mechanisms in heterogeneous oxidation is crucial for improving models of their chemical evolution in the atmosphere. Previous experimental work in our lab has shown two general reaction pathways for organic aerosol upon oxidation: functionalization, which adds additional oxygen functional groups to the carbon skeleton, and fragmentation, which leads to C-C bond scission and lower molecular weight oxidized products. Furthermore, these pathways were also found to be dependent on molecular structure, with more branched or oxidized hydrocarbons undergoing more fragmentation than less branched or oxidized hydrocarbons. However, while the mechanisms of hydrocarbon oxidation have been studied extensively in the gas phase, to what extent the gas phase mechanisms of hydrocarbon oxidation can be reliably applied to heterogeneous or bulk oxidation in aerosol remains unclear. To investigate the role of the condensed phase and molecular structure in the mechanism of heterogeneous organic aerosol oxidation, stochastic kinetics models are developed and compared to measurements of the products in the oxidation of hydrocarbons. Within the aerosol bulk, condensed phase rate coefficients and product branching ratios for peroxy reactions lead to different product distributions than those expected from gas phase peroxy reactions due to the presence of the liquid radical cage at the reaction site. As a result, tertiary alcohols and ketones were found to be the predominate products in the oxidation of squalane as observed in experiments. As the aerosol becomes further oxidized, β-scission of alkoxy radicals with neighboring functional groups is the primary fragmentation pathway leading to lower volatility products. In conjunction with this fragmentation mechanism, elimination of CO2 from acyloxy radicals was

  16. Kinetic and Modeling Investigation to Provide Design Guidelines for the NREL Dilute-Acid Process Aimed at Total Hydrolysis/Fractionation of Lignocellulosic Biomass: July 1998

    SciTech Connect

    Lee, Y. Y.; Iyer, P.; Xiang, Q.; Hayes, J.

    2004-08-01

    Following up on previous work, subcontractor investigated three aspects of using NREL ''pretreatment'' technology for total hydrolysis (cellulose as well as hemicellulose) of biomass. Whereas historic hydrolysis of biomass used either dilute acid or concentrated acid technology for hydrolysis of both hemicellulose and cellulose, NREL has been pursuing very dilute acid hydrolysis of hemicellulose followed by enzymatic hydrolysis of cellulose. NREL's countercurrent shrinking-bed reactor design for hemicellulose hydrolysis (pretreatment) has, however, shown promise for total hydrolysis. For the first task, subcontractor developed a mathematical model of the countercurrent shrinking bed reactor operation and, using yellow poplar sawdust as a feedstock, analyzed the effect of: initial solid feeding rate, temperature, acid concentration, acid flow rate, Peclet number (a measure of backmixing in liquid flow), and bed shrinking. For the second task, subcontractor used laboratory trials, with yellow poplar sawdust and 0.07 wt% sulfuric acid at various temperatures, to verify the hydrolysis of cellulose to glucose (desired) and decomposition of glucose (undesired) and determine appropriate parameters for use in kinetic models. Unlike cellulose and hemicellulose, lignins, the third major component of biomass, are not carbohydrates that can be broken down into component sugars. They are, however, aromatic complex amorphous phenolic polymers that can likely be converted into low-molecular weight compounds suitable for production of fuels and chemicals. Oxidative degradation is one pathway for such conversion and hydrogen peroxide would be an attractive reagent for this, as it would leave no residuals. For the third task, subcontractor reacted lignin with hydrogen peroxide under various conditions and analyzed the resulting product mix.

  17. Thermoluminescence and P700 redox kinetics as complementary tools to investigate the cyclic/chlororespiratory electron pathways in stress conditions in barley leaves.

    PubMed

    Peeva, Violeta N; Tóth, Szilvia Z; Cornic, Gabriel; Ducruet, Jean-Marc

    2012-01-01

    Cyclic electron flow around photosystem I drives additional proton pumping into the thylakoid lumen, which enhances the protective non-photochemical quenching and increases ATP synthesis. It involves several pathways activated independently. In whole barley leaves, P700 oxidation under far-red illumination and subsequent P700(+) dark reduction kinetics provide a major probe of the activation of cyclic pathways. Two 'intermediate' and 'slow' exponential reduction phases are always observed and they become faster after high light illumination, but dark inactivation of the Benson-Calvin cycle causes the emergence of both a transient in the P700 oxidation and a 'fast' phase in the P700(+) reduction. We investigate here the afterglow (AG) thermoluminescence emission as another tool to detect the activation of cyclic electron pathways from stroma reductants to the acceptor side of photosystem II. This transfer is activated by warming, yielding an AG band at about 45°C. However, treatments that accelerate the 'intermediate' and 'slow' P700(+) reduction phases (brief anoxia, hexose infiltration, fast dehydration of excised leaves) also produced a downshift of this AG band. This pathway ascribable to NADPH dehydrogenase (NDH) would be triggered by a deficit in ATP, while the 'fast' reduction phase corresponding to the ferredoxin plastoquinone reductase pathway is triggered by an overreduction of the photosystem I acceptor pool and is undetected in thermoluminescence. Contrastingly, slow dehydration of unwatered plants did not cause faster reduction of P700(+) nor temperature downshift of the AG band, that is no induction of the NDH pathway, whereas an increased intensity of the AG band indicated a strong NADPH + ATP assimilatory potential.

  18. Rapid Evaporation of microbubbles

    NASA Astrophysics Data System (ADS)

    Gautam, Jitendra; Esmaeeli, Asghar

    2008-11-01

    When a liquid is heated to a temperature far above its boiling point, it evaporates abruptly. Boiling of liquid at high temperatures can be explosive and destructive, and poses a potential hazard for a host of industrial processes. Explosive boiling may occur if a cold and volatile liquid is brought into contact with a hot and non-volatile liquid, or if a liquid is superheated or depressurized rapidly. Such possibilities are realized, for example, in the depressurization of low boiling point liquefied natural gas (LNG) in the pipelines or storage tanks as a result of a leak. While boiling of highly heated liquids can be destructive at macroscale, the (nearly) instantaneous pace of the process and the release of large amount of kinetic energy make the phenomena extremely attractive at microscale where it is possible to utilize the released energy to derive micromechanical systems. For instance, there is currently a growing interest in micro-explosion of liquid for generation of micro bubbles for actuation purposes. The aim of the current study is to gain a fundamental understanding of the subject using direct numerical simulations. In particular, we seek to investigate the boundary between stable and unstable nucleus growth in terms of the degree of liquid superheat and to compare the dynamics of unstable and stable growth.

  19. An investigation of the effect of surface impurities on the adsorption kinetics of hydrogen chemisorbed onto iron. Annual status report, 1 January-31 December 1993

    SciTech Connect

    Shanabarger, M.R.

    1993-01-01

    The goal of this program was to develop an understanding of heterogeneous kinetic processes for those molecular species which produce gaseous hydrogen degradation of the mechanical properties of metallic structural materials. Although hydrogen degradation of metallic materials is believed to result from dissolved protonic hydrogen, the heterogeneous hydrogen interface transport processes often dominate the kinetics of degradation. The initial step in the interface transport process is the dissociative chemisorption of the molecular species at the metal surface followed by hydrogen absorption into and transport through the bulk. The interaction of hydrogen with the surfaces of alpha-2(Ti3Al) titanium aluminide, gamma(TiAl) titanium aluminide, and beryllium were studied.

  20. Microwave gallium-68 radiochemistry for kinetically stable bis(thiosemicarbazone) complexes: structural investigations and cellular uptake under hypoxia† †Electronic supplementary information (ESI) available. CCDC 1001632–1001634. For ESI and crystallographic data in CIF or other electronic format see DOI: 10.1039/c5dt02537k Click here for additional data file. Click here for additional data file.

    PubMed Central

    Alam, Israt S.; Arrowsmith, Rory L.; Cortezon-Tamarit, Fernando; Twyman, Frazer; Kociok-Köhn, Gabriele; Botchway, Stanley W.; Dilworth, Jonathan R.

    2016-01-01

    We report the microwave synthesis of several bis(thiosemicarbazones) and the rapid gallium-68 incorporation to give the corresponding metal complexes. These proved kinetically stable under ‘cold’ and ‘hot’ biological assays and were investigated using laser scanning confocal microscopy, flow cytometry and radioactive cell retention studies under normoxia and hypoxia. 68Ga complex retention was found to be 34% higher in hypoxic cells than in normoxic cells over 30 min, further increasing to 53% at 120 min. Our data suggests that this class of gallium complexes show hypoxia selectivity suitable for imaging in living cells and in vivo tests by microPET in nude athymic mice showed that they are excreted within 1 h of their administration. PMID:26583314

  1. Comprehensive investigations of kinetics of alkaline hydrolysis of TNT (2,4,6-trinitrotoluene), DNT (2,4-dinitrotoluene), and DNAN (2,4-dinitroanisole).

    PubMed

    Sviatenko, Liudmyla; Kinney, Chad; Gorb, Leonid; Hill, Frances C; Bednar, Anthony J; Okovytyy, Sergiy; Leszczynski, Jerzy

    2014-09-02

    Combined experimental and computational techniques were used to analyze multistep chemical reactions in the alkaline hydrolysis of three nitroaromatic compounds: 2,4,6-trinitrotoluene (TNT), 2,4-dinitrotoluene (DNT), and 2,4-dinitroanisole (DNAN). The study reveals common features and differences in the kinetic behavior of these compounds. The analysis of the predicted pathways includes modeling of the reactions, along with simulation of UV-vis spectra, experimental monitoring of reactions using LC/MS techniques, development of the kinetic model by designing and solving the system of differential equations, and obtaining computationally predicted kinetics for decay and accumulation of reactants and products. Obtained results suggest that DNT and DNAN are more resistant to alkaline hydrolysis than TNT. The direct substitution of a nitro group by a hydroxide represents the most favorable pathway for all considered compounds. The formation of Meisenheimer complexes leads to the kinetic first-step intermediates in the hydrolysis of TNT. Janovsky complexes can also be formed during hydrolysis of TNT and DNT but in small quantities. Methyl group abstraction is one of the suggested pathways of DNAN transformation during alkaline hydrolysis.

  2. Ziegler-Natta and metallocene-catalyzed isotactic polypropylene: A comprehensive investigation and comparison using crystallization kinetics, fiber spinning and thermal spunbonding

    NASA Astrophysics Data System (ADS)

    Bond, Eric Bryan

    Isotactic polypropylene (iPP) can be synthesized using conventional heterogeneous Ziegler-Natta (zniPP) and homogenous metallocene catalysts (miPP). The purpose of this work was to investigate and compare and contrast miPP resins to zniPP resins. The resins in this study were thoroughly characterized by cNMR and solution fractionation to determine the number, type and distribution of defects. The resins were then studied under isothermal and nonisothermal quiescent crystallization conditions to determine the bulk and crystal growth kinetics, crystal structure, crystallinity and thermal properties. The cNMR and xylene fractionation studies indicated the miPP resins had substantially more total defects in the crystallizable material than either of the zniPP resins in this study. Combined results from DSC, SAXS and WAXD indicated the miPP and zniPP resins have similar alpha-monoclinic equilibrium melting temperatures (T m0), despite the differences in defect content, type and distribution. The presence of atactic material was found to lower the observed equilibrium melting temperature of a particular resin, whether miPP or zniPP. The isothermal crystallization studies showed the miPP resins readily produce the gamma-crystal structure. The zniPP resins also produced small amounts of the gamma-structure, at high crystallization temperatures. Defects were found to be excluded from the crystal under isothermal crystallization conditions. For crystallization under isothermal crystallization conditions, the observed linear growth rates were found to be dependent upon defect content. Under nonisothermal conditions, the growth rate was found to depend mostly on the molecular weight. Fiber spinning studies showed that the molecular weight and molecular weight distribution of an iPP resin is largely determined by the point of crystallization in the spinline, the crystallization temperature and as-spun filament properties. Increasing the molecular weight (also increasing the

  3. Rapid estimation of readily leachable triazine residues in soils using automatic kinetic bioaccessibility assays followed by on-line sorptive clean-up as a front-end to liquid chromatography.

    PubMed

    Vida, Ana C F; Cocovi-Solberg, David J; Zagatto, Elias A G; Miró, Manuel

    2016-08-15

    An automatic batchwise bioaccessibility test was proposed for on-line monitoring of readily mobile pools of ametryn and atrazine residues in agricultural soils with different physicochemical properties. A 0.01molL(-1) CaCl2 solution mimicking rainwater percolation through the soil profiles was used for the herbicide extractions. The extract aliquots were successively sampled at regular time intervals in order to investigate the extraction kinetics. For extract clean-up and retention of freely dissolved target species, 30mg of restricted-access like copolymer were used as in-line sorptive material followed by elution with methanol and on-line heart-cut injection towards a C18 silica reversed-phase monolithic column (100×4.6mm) in a liquid chromatographic system. A mathematical model emphasized that the readily available pools vs time can be in most instances described by a first-order exponential equation, thus an asymptotical value is approached. Consequently, the leaching assays can be performed without attaining chemical equilibrium. Enhancement factors and detection limits were 10.2 and 18.8, and 0.40 and 0.37mgkg(-1) for ametryn and atrazine, respectively. The automatic method features good repeatability for leaching tests (r.s.d.: 11.8-10.2% for sandy and 3.7-6.2% for clayey soil). Reliable data, demonstrated with relative recoveries in the soil leachates ranging from 86 to 104%, were achieved in less than 35min, thus avoiding the need for up to 24h as recommended by standard leaching methods.

  4. Reaction kinetics of hydrothermal carbonization of loblolly pine.

    PubMed

    Reza, M Toufiq; Yan, Wei; Uddin, M Helal; Lynam, Joan G; Hoekman, S Kent; Coronella, Charles J; Vásquez, Victor R

    2013-07-01

    Hydrothermal carbonization (HTC) is a pretreatment process to convert diverse feedstocks to homogeneous energy-dense solid fuels. Understanding of reaction kinetics is necessary for reactor design and optimization. In this study, the reaction kinetics and effects of particle size on HTC were investigated. Experiments were conducted in a novel two-chamber reactor maintaining isothermal conditions for 15s to 30 min reaction times. Loblolly pine was treated at 200, 230, and 260°C. During the first few minutes of reaction, the solid-product mass yield decreases rapidly while the calorific value increases rapidly. A simple reaction mechanism is proposed and validated, in which both hemicellulose and cellulose degrade in parallel first-order reactions. Activation energy of hemicellulose and cellulose degradation were determined to be 30 and 73 kJ/mol, respectively. For short HTC times, both reaction and diffusion effects were observed.

  5. Applications of kinetic theory

    SciTech Connect

    Gidaspow, D.

    1992-01-01

    The overall objective of this investigation is to develop experimentally verified models for circulating fluidized bed (CFB) combustors. This report presents the author's derivation of analytical solutions useful in understanding the operation of a CFB. The report is in a form of a chapter that reviews the kinetic theory applications.

  6. Effects of oral temazepam on slow waves during non-rapid eye movement sleep in healthy young adults: a high-density EEG investigation

    PubMed Central

    Plante, DT; Goldstein, MR; Cook, JD; Smith, R; Riedner, BA; Rumble, ME; Jelenchick, L; Roth, A; Tononi, G; Benca, RM; Peterson, MJ

    2016-01-01

    Slow waves are characteristic waveforms that occur during non-rapid eye movement (NREM) sleep that play an integral role in sleep quality and brain plasticity. Benzodiazepines are commonly used medications that alter slow waves, however, their effects may depend on the time of night and measure used to characterize slow waves. Prior investigations have utilized minimal scalp derivations to evaluate the effects of benzodiazepines on slow waves, and thus the topography of changes to slow waves induced by benzodiazepines has yet to be fully elucidated. This study used high-density electroencephalography (hdEEG) to evaluate the effects of oral temazepam on slow wave activity, incidence, and morphology during NREM sleep in 18 healthy adults relative to placebo. Temazepam was associated with significant decreases in slow wave activity and incidence, which were most prominent in the latter portions of the sleep period. However, temazepam was also associated with a decrease in the magnitude of high-amplitude slow waves and their slopes in the first NREM sleep episode, which was most prominent in frontal derivations. These findings suggest that benzodiazepines produce changes in slow waves throughout the night that vary depending on cortical topography and measures used to characterize slow waves. Further research that explores the relationships between benzodiazepine-induced changes to slow waves and the functional effects of these waveforms is indicated. PMID:26779596

  7. Effects of oral temazepam on slow waves during non-rapid eye movement sleep in healthy young adults: A high-density EEG investigation.

    PubMed

    Plante, D T; Goldstein, M R; Cook, J D; Smith, R; Riedner, B A; Rumble, M E; Jelenchick, L; Roth, A; Tononi, G; Benca, R M; Peterson, M J

    2016-03-01

    Slow waves are characteristic waveforms that occur during non-rapid eye movement (NREM) sleep that play an integral role in sleep quality and brain plasticity. Benzodiazepines are commonly used medications that alter slow waves, however, their effects may depend on the time of night and measure used to characterize slow waves. Prior investigations have utilized minimal scalp derivations to evaluate the effects of benzodiazepines on slow waves, and thus the topography of changes to slow waves induced by benzodiazepines has yet to be fully elucidated. This study used high-density electroencephalography (hdEEG) to evaluate the effects of oral temazepam on slow wave activity, incidence, and morphology during NREM sleep in 18 healthy adults relative to placebo. Temazepam was associated with significant decreases in slow wave activity and incidence, which were most prominent in the latter portions of the sleep period. However, temazepam was also associated with a decrease in the magnitude of high-amplitude slow waves and their slopes in the first NREM sleep episode, which was most prominent in frontal derivations. These findings suggest that benzodiazepines produce changes in slow waves throughout the night that vary depending on cortical topography and measures used to characterize slow waves. Further research that explores the relationships between benzodiazepine-induced changes to slow waves and the functional effects of these waveforms is indicated.

  8. Aggregation kinetics of single-walled carbon nanotubes investigated using mechanically wrapped multinuclear complexes: probing the tube-tube repulsive barrier.

    PubMed

    Ameen, Anjail A; Giordano, Andrea N; Alston, Jeffrey R; Forney, Michael W; Herring, Natalie P; Kobayashi, Shiho; Ridlen, Shawn G; Subaran, Sarah S; Younts, Thomas J; Poler, J C

    2014-03-28

    The rational design of supraparticle assemblies requires a detailed understanding of directed assembly processes. The stability of dispersions of nanoscale materials, like single-walled carbon nanotubes (SWCNTs), is still not fully understood, nor are the mechanisms of aggregation and assembly. A detailed balance of attractive van der Waals type interactions with various repulsive barrier mechanisms is needed to control the assembly of industrially viable and functional hybrid-nanoscale supraparticles. We report a detailed study of SWCNT dispersion stability and aggregation kinetics as a function of the nature of the coagulant used in various solvent systems. We explore three classes of coagulants that vary in charge, size, shape, solvation energy, and the ability to bind to the SWCNTs. We use these kinetic data to assess the tube-solvent-coagulant-tube interactions. We compare the relative contributions from two types of repulsive barriers. We find that tube-mediated structured solvent around the SWCNTs does not sufficiently describe our measured kinetic data. A DLVO type, electrical double layer repulsion is used to rationalize our observations. The data presented in this paper require a more detailed theoretical understanding of the physico-chemical environment near nanoparticle surfaces such as aggregating SWCNTs.

  9. Synthesis of Depo-Medrol-chitosan hydrogel as new drug slow-release appliance and investigation of release kinetics by high-performance liquid chromatography.

    PubMed

    Alizadeh, Reza; Jabbari, Sara Majd; Zarnani, Amir H; Barghi, Hamidreza

    2016-09-01

    The present study deals with preparation and optimization of a novel chitosan hydrogel-based matrix by suspension cross-linking method for controlled release of Depo-Medrol. The controlled release of Depo-Medrol for effective Rheumatoid arthritis disease has become an imperative field in the drug delivery system. In this context, it was intended to optimize loading circumstances by experimental design and also study the release kinetics of Depo-Medrol entrapped in the chitosan matrix in order to obtain maximal efficiency for drug loading. The optimum concentrations of chitosan (2.5 g), glutaraldehyde (3.05 μL) and Depo-Medrol (0.1 mg) were set up to achieve the highest value of drug loaded and the most sustained release from the chitosan matrix. In vitro monitoring of drug release kinetic using high-performance liquid chromatography showed that 73% of the Depo-Medrol was released within 120 min, whereas remained drug was released during the next 67 h. High correlation between first-order and Higuchi's kinetic models indicates a controlled diffusion of Depo-Medrol through the surrounding media. Moreover, recovery capacity >82% and entrapment efficiency of 58-88% were achieved under optimal conditions. Therefore, the new synthesized Depo Medrol-chitosan is an applicable appliance for arthritis therapy by slow release mechanism. Copyright © 2016 John Wiley & Sons, Ltd.

  10. Quantum chemical investigation on the mechanism and kinetics of PBDE photooxidation by ·OH: a case study for BDE-15.

    PubMed

    Zhou, Jing; Chen, Jingwen; Liang, Chi-Hsiu; Xie, Qing; Wang, Ya-Nan; Zhang, Siyu; Qiao, Xianliang; Li, Xuehua

    2011-06-01

    Computational approaches are crucial to risk assessment and pollution prevention of newly synthesized compounds prior to large-scale production and commercialization. Understanding the kinetics and mechanism of the tropospheric reaction of semivolatile organic compounds with ·OH is an indispensable component of risk assessment. In this study, we show that the density functional theory (DFT) can be successfully employed to probe the kinetics and mechanism of atmospheric photooxidation of polybrominated diphenyl ethers (PBDEs) by ·OH, taking 4,4'-dibromodiphenyl ether (BDE-15) as a case. The predicted products (HO-PBDEs, brominated phenols and Br(2)) and overall rate constant (k(OH)) at 298 K are consistent with the experimental results. Two pathways leading to formation of HO-PBDEs are identified: Br substitution by ·OH, and abstraction of H gem to ·OH in BDE-OH adducts by O(2). This study offers a cost-effective way for probing the atmospheric indirect photooxidation kinetics and mechanism of PBDEs.

  11. Investigations on the conditional kinetic and thermodynamic stability of aquatic humic substance-metal complexes by means of EDTA exchange, ultrafiltration and atomic spectrometry.

    PubMed

    Van den Bergh, J; Jakubowski, B; Burba, P

    2001-09-13

    The conditional metal availability and the kinetic stability of humic substance-metal species in humic-rich waters (e.g. bog water) was characterized by means of EDTA exchange. For this purpose a combined procedure consisting of time-controlled ligand exchange by EDTA, species differentiation by a fast single-stage tangential-flow ultrafiltration (TF-UF) technique (cut-off 1 kDa) and sensitive atomic spectrometry methods (e.g. AAS, ICP-OES, TXRF) was developed. The kinetics and the yield of the EDTA exchange served as operational parameters for assessing the kinetic stability and EDTA availability of HS-metal species, respectively. Considerable fractions of natural HS-metal species studied were shown to be EDTA-inert (e.g. 31% of the total Fe, 44% of the total Al) even after long reaction times (48 h), in contrast to artificial ones formed in solutions of isolated HS. Moreover, the conditional thermodynamic stability of HS-metal complexes formed by successive loading of an aquatic reference HS (HO14) with a number of heavy metal ions (e.g. Cr(III), Cu(II), Fe(III), Mn(II), Zn(II)) was also evaluated discriminating the free metal concentrations by means of TF-UF. In addition, from the loading isotherms obtained conditional complexation capacities could be derived for the studied HS exhibiting the order Fe(III)>Cu(II)>Cr(III)>Co(II)>Mn(II).

  12. Dilute-sulfuric acid pretreatment of corn stover in pilot-scale reactor: investigation of yields, kinetics, and enzymatic digestibilities of solids.

    PubMed

    Schell, Daniel J; Farmer, Jody; Newman, Millie; McMillan, James D

    2003-01-01

    Corn stover is a domestic feedstock that has potential to produce significant quantities of fuel ethanol and other bioenergy and biobased products. However, comprehensive yield and carbon mass balance information and validated kinetic models for dilute-sulfuric acid (H2SO4) pretreatment of corn stover have not been available. This has hindered the estimation of process economics and also limited the ability to perform technoeconomic modeling to guide research. To better characterize pretreatment and assess its kinetics, we pretreated corn stover in a continuous 1 t/d reactor. Corn stover was pretreated at 20% (w/w) solids concentration over a range of conditions encompassing residence times of 3-12 min, temperatures of 165- 195 degrees C, and H2SO4 concentrations of 0.5-1.4% (w/w). Xylan conversion yield and carbon mass balance data were collected at each run condition. Performance results were used to estimate kinetic model parameters assuming biphasic hemicellulose hydrolysis and a hydrolysis mechanism incorporating formation of intermediate xylo-oligomers. In addition, some of the pretreated solids were tested in a simultaneous saccharification and fermentation (SSF) process to measure the reactivity of their cellulose component to enzymatic digestion by cellulase enzymes. Monomeric xylose yields of 69-71% and total xylose yields (monomers and oligomers) of 70-77% were achieved with performance level depending on pretreatment severity. Cellulose conversion yields in SSF of 80-87% were obtained for some of the most digestible pretreated solids.

  13. Multiple-step kinetic mechanism of DNA-independent ATP binding and hydrolysis by Escherichia coli replicative helicase DnaB protein: quantitative analysis using the rapid quench-flow method.

    PubMed

    Rajendran, S; Jezewska, M J; Bujalowski, W

    2000-11-10

    The kinetic mechanism of DNA-independent binding and hydrolysis of ATP by the E. coli replicative helicase DnaB protein has been quantitatively examined using the rapid quench-flow technique. Single-turnover studies of ATP hydrolysis, in a non-interacting active site of the helicase, indicate that bimolecular association of ATP with the site is followed by the reversible hydrolysis of nucleotide triphosphate and subsequent conformational transition of the enzyme-product complex. The simplest mechanism, which describes the data, is a three-step sequential process defined by:¿eqalign¿¿¿rm Helicase+ATP¿&¿mathop¿¿rightleftharpoons¿ ¿k_1¿_¿k_¿-1¿¿¿¿rm (H-ATP)¿¿mathop¿¿rightleftharpoons¿ ¿k_2¿_¿k_¿-2¿¿¿¿rm (H-ADP¿cdot Pi)¿¿cr &¿mathop¿¿rightleftharpoons¿ ¿k_3¿_¿k_¿-3¿¿¿¿rm (H-ADP¿cdot Pi)¿ *¿The sequential character of the mechanism excludes conformational transitions of the DnaB helicase prior to ATP binding. Analysis of relaxation times and amplitudes of the reaction allowed us to estimate all rate and equilibrium constants of partial steps of the proposed mechanism. The intrinsic binding constant for the formation of the (H-ATP) complex is K(ATP)=(1.3+/-0.5)x10(5) M(-1). The analysis of the data indicates that a part of the ATP binding energy originates from induced structural changes of the DnaB protein-ATP complex prior to ATP hydrolysis. The equilibrium constant of the chemical interconversion is K(H)=k(2)/k(-2) approximately 2 while the subsequent conformational transition is characterized by K(3)=k(3)/k(-3) approximately 30. The low value of K(H) and the presence of the subsequent energetically favorable conformational step(s) strongly suggest that free energy is released from the enzyme-product complex in the conformational transitions following the chemical step and before the product release.The combined application of single and multiple-turnover approaches show that all six nucleotide-binding sites of the Dna

  14. Theoretical and Experimental Investigation of Thermodynamics and Kinetics of Thiol-Michael Addition Reactions: A Case Study of Reversible Fluorescent Probes for Glutathione Imaging in Single Cells.

    PubMed

    Chen, Jianwei; Jiang, Xiqian; Carroll, Shaina L; Huang, Jia; Wang, Jin

    2015-12-18

    Density functional theory (DFT) was applied to study the thermodynamics and kinetics of reversible thiol-Michael addition reactions. M06-2X/6-31G(d) with the SMD solvation model can reliably predict the Gibbs free energy changes (ΔG) of thiol-Michael addition reactions with an error of less than 1 kcal·mol(-1) compared with the experimental benchmarks. Taking advantage of this computational model, the first reversible reaction-based fluorescent probe was developed that can monitor the changes in glutathione levels in single living cells.

  15. Kinetic and X-ray crystallographic investigations of substituted 2-thio-6-oxo-1,6-dihydropyrimidine-benzenesulfonamides acting as carbonic anhydrase inhibitors.

    PubMed

    Vullo, Daniela; Supuran, Claudiu T; Scozzafava, Andrea; De Simone, Giuseppina; Monti, Simona Maria; Alterio, Vincenzo; Carta, Fabrizio

    2016-08-15

    Herein we report an in vitro kinetic evaluation against the most relevant human carbonic anhydrase (hCA, EC 4.2.1.1) isoforms (I, II, IX and XII) of a small series of lactate dehydrogenase (LDH, EC 1.1.1.27) inhibitors. All compounds contain a primary sulfonamide zinc-binding group (ZBG) substituted with the 2-thio-6-oxo-1,6-dihydropyrimidine scaffold. By means of X-ray crystallographic experiments we explored the ligand-enzyme binding modes, thus highlighting the contribution of the 2-thio-6-oxo-1,6-dihydropyrimidine moiety to the stabilization of the complex.

  16. Probing the electrostatics and pharmacological modulation of sequence-specific binding by the DNA-binding domain of the ETS family transcription factor PU.1: a binding affinity and kinetics investigation.

    PubMed

    Munde, Manoj; Poon, Gregory M K; Wilson, W David

    2013-05-27

    Members of the ETS family of transcription factors regulate a functionally diverse array of genes. All ETS proteins share a structurally conserved but sequence-divergent DNA-binding domain, known as the ETS domain. Although the structure and thermodynamics of the ETS-DNA complexes are well known, little is known about the kinetics of sequence recognition, a facet that offers potential insight into its molecular mechanism. We have characterized DNA binding by the ETS domain of PU.1 by biosensor-surface plasmon resonance (SPR). SPR analysis revealed a striking kinetic profile for DNA binding by the PU.1 ETS domain. At low salt concentrations, it binds high-affinity cognate DNA with a very slow association rate constant (≤10(5)M(-)(1)s(-)(1)), compensated by a correspondingly small dissociation rate constant. The kinetics are strongly salt dependent but mutually balance to produce a relatively weak dependence in the equilibrium constant. This profile contrasts sharply with reported data for other ETS domains (e.g., Ets-1, TEL) for which high-affinity binding is driven by rapid association (>10(7)M(-)(1)s(-)(1)). We interpret this difference in terms of the hydration properties of ETS-DNA binding and propose that at least two mechanisms of sequence recognition are employed by this family of DNA-binding domain. Additionally, we use SPR to demonstrate the potential for pharmacological inhibition of sequence-specific ETS-DNA binding, using the minor groove-binding distamycin as a model compound. Our work establishes SPR as a valuable technique for extending our understanding of the molecular mechanisms of ETS-DNA interactions as well as developing potential small-molecule agents for biotechnological and therapeutic purposes.

  17. Experimental Investigation of the Primary and Secondary Deuterium Kinetic Isotope Effects for Epoxidation of Alkenes and Ethylene with m-Chloroperoxybenzoic Acid.

    PubMed

    Koerner, Terry; Slebocka-Tilk, H.; Brown, R. S.

    1999-01-08

    The secondary deuterium kinetic isotope effect (DKIE) for the epoxidation of ethylene and d(4)-ethylene by m-chloroperoxybenzoic acid (MCPBA) is determined to be 0.83, or 0.95/alpha-H. The second-order rate constants for MCPBA and MCPBA-O-D epoxidation of a variety of alkenes that differ in the steric access to the double bond (anti-sesquinorbornene (2), tetramethylethylene (3), adamantylideneadamantane (4), 7-norbornylidene-7'-norbornane (5), bis(bicyclo[3.3.1.]non-9-ylidene) (6), bis(homoadamantane) (7), cyclohexene (8), 1-octene (9), trans-5-decene (10) and 2-methyl-1-pentene (11)) have been determined in dichloroethane at 25 degrees C using UV kinetics, and the primary DKIE, k(OH)/k(OD), is 1.05 +/- 0.05 in all cases. By comparison of the rates of epoxidation of sterically encumbered alkenes, it is suggested that the spiro epoxidation transition state is favored over a planar one. The products of the epoxidation of anti-sesquinorbornene are determined to be the epoxide and a cis-hydroxy ester, the latter most probably being formed by acid-catalyzed ring opening of the epoxide by in situ-produced m-chlorobenzoic acid produced in situ to form a beta-hydroxy carbocation and carboxylate ion pair that collapses to product.

  18. Prediction of kinematic and kinetic performance in a drop vertical jump with individual anthropometric factors in adolescent female athletes: implications for cadaveric investigations.

    PubMed

    Bates, Nathaniel A; Myer, Gregory D; Hewett, Timothy E

    2015-04-01

    Anterior cruciate ligament injuries are common, expensive to repair, and often debilitate athletic careers. Robotic manipulators have evaluated knee ligament biomechanics in cadaveric specimens, but face limitations such as accounting for variation in bony geometry between specimens that may influence dynamic motion pathways. This study examined individual anthropometric measures for significant linear relationships with in vivo kinematic and kinetic performance and determined their implications for robotic studies. Anthropometrics and 3D motion during a 31 cm drop vertical jump task were collected in high school female basketball players. Anthropometric measures demonstrated differential statistical significance in linear regression models relative to kinematic variables (p-range <0.01-0.95). However, none of the anthropometric relationships accounted for clinical variance or provided substantive univariate accuracy needed for clinical prediction algorithms (r(2) < 0.20). Mass and BMI demonstrated models that were significant (p < 0.05) and predictive (r(2) > 0.20) relative to peak flexion moment, peak adduction moment, flexion moment range, abduction moment range, and internal rotation moment range. The current findings indicate that anthropometric measures are less associated with kinematics than with kinetics. Relative to the robotic manipulation of cadaveric limbs, the results do not support the need to normalize kinematic rotations relative to specimen dimensions.

  19. A kinetic, mechanistic, and molecular mechanics investigation of olefin insertion into organoactinide-hydride bonds. Metal, olefin, ancillary ligand, and diastereoselection effects

    SciTech Connect

    Lin, Zerong; Marks, T.J. )

    1990-07-04

    This contribution reports a kinetic/mechanistic/stereochemical/molecular mechanics study of olefin insertion into the actinide-hydrogen bonds of Cp{prime}{sub 2}An(H)(OR) complexes (Cp{prime} = {eta}{sup 5}-(CH{sub 3}){sub 5}C{sub 5}; An = Th, U; R = achiral or chiral alkyl group). For the reaction Cp{prime}{sub 2}An(H)(O-t-Bu) + cyclohexene (An = Th), the rate law is first order in organoactinide and first order in olefin. For Cp{prime}{sub 2}Th(H)(OCH(t-Bu){sub 2}) + 1-hexene, k{sub Th{minus}H}/k{sub Th{minus}D} = 1.3 (2). A molecular mechanics/ molecular graphics analysis suggests that the sterically most favorable direction of olefin approach toward the actinide center is between the U-H and U-O bonds rather than from the side. These results provide additional insight into ancillary ligand effects on the kinetics of organo-f-element-catalyzed olefin hydrogenation.

  20. A novel population balance model to investigate the kinetics of in vitro cell proliferation: part II. Numerical solution, parameters' determination, and model outcomes.

    PubMed

    Fadda, Sarah; Cincotti, Alberto; Cao, Giacomo

    2012-03-01

    Based on the general theoretical model developed in Part I of this work, a series of numerical simulations related to the in vitro proliferation kinetics of adherent cells is here presented. First the complex task of assigning a specific value to all the parameters of the proposed population balance (PB) model is addressed, by also highlighting the difficulties arising when performing proper comparisons with experimental data. Then, a parametric sensitivity analysis is performed, thus identifying the more relevant parameters from a kinetics perspective. The proposed PB model can be adapted to describe cell growth under various conditions, by properly changing the value of the adjustable parameters. For this reason, model parameters able to mimic cell culture behavior under microgravity conditions are identified by means of a suitable parametric sensitivity analysis. Specifically, it is found that, as the volume growth parameter is reduced, proliferation slows down while cells arrest in G0/G1 or G2/M depending on the initial distribution of cell population. On the basis of this result, model capabilities have been tested by means of a proper comparison with literature experimental data related to the behavior of synchronized and not-synchronized cells under micro- and standard gravity levels.

  1. Efficiency enhancement of RELAP/PANBOX using adaptive spatial kinetics

    SciTech Connect

    Jackson, C.J.; Cacuci, D.G.; Finnemann, H.B.

    1996-12-31

    The coupled RELAP/PANBOX code system was developed to analyze more accurately those pressurized water reactor (PWR) plant transients in which the core neutron flux distribution changes significantly in time. Examples of such transients are those initiated by steam-line breaks and rapid boron dilution events. On the other hand, instances may occur during long thermal-hydraulic transients when the neutron flux shape varies slowly in time. During such slow transients, a one-dimensional (1-D) model in the axial direction or a point-kinetics model, rather than a three-dimensional (3-D) one, would suffice to calculate the power distribution. To switch between 3-D, 1-D, and/or point-kinetics models, it is very advantageous to generate the respective 1-D and/or point-kinetics parameters automatically and internally within the code. In this paper, the authors describe the features of an adaptive spatial kinetics algorithm that performs the switching process between 3-D and 1-D and/or point-kinetics models according to the physical phenomena underlying the specific plant transient under investigation. The adaptive algorithm has been implemented as a module of the core simulation package PANBOX and therefore does not disturb the subroutines that couple PANBOX to RELAP.

  2. Antigen-antibody selective recognition using LiTaO3 SH-SAW sensors: investigations on macromolecules effects on binding kinetic constants

    NASA Astrophysics Data System (ADS)

    Bergaoui, Y.; Zerrouki, C.; Fourati, N.; Fougnion, J. M.; Abdelghani, A.

    2011-10-01

    A gravimetric surface acoustic wave (SAW) biosensor, based on the biotin-streptavidin and antistreptavidin-streptavidin recognitions, has been carried out. A network analyser and a pulse excitation technique were used to monitor both amplitude and phase changes. The SAW biosensor presented a total selective recognition of streptavidin-antistreptavidin and HRPstreptavidin-antistreptavidin. The presence of HRP (Horseradish peroxidase) affects neither the selectivity nor the sensitivity (of order of 0.25°/nM) of the biosensor, nevertheless, it causes a reduction of binding kinetics by a factor ranging between 2 to 5, as well as a diminution of antistreptavidin saturation concentration (of 40%). Results showed that equilibrium constants can be different, depending on evaluation method (from saturation values or from linear part of the output signal variation according to solution concentration).

  3. Raman and NMR kinetics study of the formation of amidoamines containing N-hydroxyethyl groups and investigations on their Cu(II) complexes in water

    NASA Astrophysics Data System (ADS)

    Bergamonti, Laura; Graiff, Claudia; Tegoni, Matteo; Predieri, Giovanni; Bellot-Gurlet, Ludovic; Lottici, Pier Paolo

    2017-01-01

    Three amidoamines containing the N-hydroxyethyl group (HOEt), namely (HOEt)2N(CH2)2C(O)NH2 (1), [(HOEt)2N(CH2)2C(O)NH]2CH2 (2) and HOEtN[(CH2)2C(O)NH2]2 (3) have been synthesized by reacting diethanolamine HOEt2NH with acrylamide and N,N‧-methylenebisacrylamide (respectively 1 and 2) and ethanolamine HOEtNH2 with acrylamide (3). Four other compounds corresponding to 1 and 2, but derived from sec-amines Me2NH (4 and 5) and Et2NH (6 and 7) have been prepared for the sake of comparison of the spectroscopic features. All compounds have been obtained by the well-known aza-Michael addition between an N-nucleophile and an activated vinyl group. The reaction in water between diethanolamine and acrylamide leading to 1 has been monitored in situ by Raman and NMR spectroscopy, both techniques confirming second order kinetics and giving values for kinetic constants in excellent agreement. The coordination ability of 1 and 2 towards Cu2 + in water has been studied by the Job's plot method. Spectroscopic data indicate that ligand 1 prevalently forms a 4:1 Ligand/Metal complex with a (N,O3) coordination set on the equatorial plane of Cu2 +, whereas ligand 2, containing two amide functionalities bridged by a methylene group, appears able to form a 1:1 Ligand/Metal chelate species, again with a (N,O3) donor set around copper.

  4. Effect of Clay Nanoparticle Transport, Desorption Kinetics and Redox Equilibrium on Radionuclide Mobility in Fractured Rock investigated at the Grimsel Test Site (Switzerland)

    NASA Astrophysics Data System (ADS)

    Schaefer, T.; Huber, F. M.; Lagos, M.; Quinto, F.; Heck, S.; Martin, A. J.; Blechschmidt, I.; Lanyon, G. W.; Reiche, T.; Noseck, U.

    2015-12-01

    Transport of contaminants in crystalline environments might occur through dissolved species or attached to colloidal or nanoparticulate phases being mobile in water conducting features of the host rock. In this presentation we will discuss the mobility of clay nanoparticles as detected by laser-induced breakdown detection (LIBD) as a function of fracture surface roughness and groundwater chemistry. The on site observed Tc-99, U-233, Np-237, Pu-242 and Am-243 sorption/desorption kinetics with and without natural or synthetic clay minerals (smectites) are compared to laboratory studies under similar groundwater conditions. The desorption or redox kinetics were monitored over a duration of up to 426 days using natural fracture filling material as a concurrence ligand and monitoring the colloid attachment via detection of Al, Si, Ni and Zn as smectite structural elements. For trivalent actinides smectite desorption rates in the range of 1.2-3.7E-3 per hour could be determined and significantly lower desorption rates for tetravalent actinides were found. This results will be compared with field data of migration experiments performed at the Grimsel Test Site (GTS, Switzerland) using the same radionuclides and clay colloidal phases varying the fracture residence time by flow rate adjustment. Furthermore, the long-term actinide mobility will be addressed by presenting AMS/RIMS measurements of (a) samples collected several months into the tailing of the breakthrough curves not any longer detectable by HR-ICP-MS and (b) background samples of different GTS ground waters showing fallout U-236, whereas fallout Pu could not be detected indicating a much lower mobility under the given conditions.

  5. Theoretical investigations into the nucleation of silica growth in basic solution part II--derivation and benchmarking of a first principles kinetic model of solution chemistry.

    PubMed

    McIntosh, Grant J

    2013-10-28

    A kinetic model of silicate oligomerization in water, up to and including tetramer formation, has been compiled exclusively from rate constants derived from transition state theory based on either quantum chemical data (derived under a hybrid solvation framework) for all bond breaking-forming reactions, or using empirically-based approximated pKa's and diffusion coefficients for rate constants of pH-based and bimolecular steps. The rate constants, based on an exhaustive search of all relevant elementary steps, form the basis of our kinetic model; numerical solution of the resulting rate equations allows the simulation of the reaction system, given a set of initial conditions and with almost no restriction on concentrations, pH, or reaction time, in a matter of only minutes. The model, which we believe contains all possible isomers of both neutral and singly anionic clusters, has been extensively benchmarked and reproduces a number of important experimental observations in the range pH ≈ 4-10. In particular, it provides a good description of the dominant products; product yields and reaction times (also as a function of pH) are in agreement with experiment; the linear relationship between the log of the rate of silica dissolution and pH is well reproduced; the origin of silica scaling naturally arises; and we can also simulate the observed fourth order dependence of the rate of monomer consumption on H4SiO4 concentration. This should be a general approach to exploring solution phase chemistry, and could be a useful complement to more conventional molecular dynamics and Monte Carlo modelling approaches in understanding complex reaction networks in solution.

  6. Rapid Formation of Molecular Bromine from Deliquesced NaBr Aerosol in the Presence of Ozone and UV Light

    EPA Science Inventory

    The formation of gas-phase bromine from aqueous sodium bromide aerosols is investigated through a combination of chamber experiments and chemical kinetics modeling. Experiments show that Br2(g) is produced rapidly from deliquesced NaBr aerosols in the presence of OH radicals prod...

  7. Subsite structure of the endo-type chitin deacetylase from a deuteromycete, Colletotrichum lindemuthianum: an investigation using steady-state kinetic analysis and MS.

    PubMed

    Hekmat, Omid; Tokuyasu, Ken; Withers, Stephen G

    2003-09-01

    The endo-type chitin deacetylase (EC 3.5.1.41) from a deuteromycete, Colletotrichum lindemuthianum (ATCC 56676), catalyses the hydrolysis of the acetamido group of GlcNAc (2-acetamido-2-deoxy-D-glucose) residues in chitin or chito-oligosaccharides with a degree of polymerization (n) equal to or greater than 2. The steady-state kinetic parameters for the initial deacetylation reactions of (GlcNAc)(2-6) were determined using a direct, continuous spectrophotometric assay in combination with ESI-MS (electrospray ionization MS) analysis of the products. The dependence of the observed K(m) and k(cat)/K(m) on n suggests the presence of four enzyme subsites (-2, -1, 0 and +1) that interact with GlcNAc residues from the non-reducing end to the reducing end of the substrate. The turnover number (k (cat), 7 s(-1)) is independent of n and represents the intrinsic rate constant (k(int)) for the hydrolysis of the acetamido group in subsite 0. The subsite affinities for the GlcNAc residues were calculated from the observed k(cat)/K(m) values (A (-2), -11.0; A (-1), -1.5; A (0), -7.7; A (+1), -12.5 kJ x mol(-1)). The increments in the subsite affinities due to the recognition of the acetamido groups were calculated [DeltaDelta G ((N-acetyl))=3.3, 0, 4.0 and 0 kJ x mol(-1) for subsites -2, -1, 0 and +1 respectively]. The steady-state kinetic parameters for the second deacetylation reaction of (GlcNAc)(4) were also determined using (GlcNAcGlcNAcGlcNGlcNAc) as the substrate. The comparison of the experimental and theoretical values (calculated using the subsite affinities) suggests that the mono-deacetylated substrate binds strongly in a non-productive mode occupying all four subsites, thereby inhibiting the second deacetylation reaction.

  8. Kinetic buffers.

    PubMed

    Alibrandi, Giuseppe; Fabbrizzi, Luigi; Licchelli, Maurizio; Puglisi, Antonio

    2015-01-12

    This paper proposes a new type of molecular device that is able to act as an inverse proton sponge to slowly decrease the pH inside a reaction vessel. This makes the automatic monitoring of the concentration of pH-sensitive systems possible. The device is a composite formed of an alkyl chloride, which kinetically produces acidity, and a buffer that thermodynamically modulates the variation in pH value. Profiles of pH versus time (pH-t plots) have been generated under various experimental conditions by computer simulation, and the device has been tested by carrying out automatic spectrophotometric titrations, without using an autoburette. To underline the wide variety of possible applications, this new system has been used to realize and monitor HCl uptake by a di-copper(II) bistren complex in a single run, in a completely automatic experiment.

  9. Crystallization kinetic of Sb-V2O5-TeO2 glasses investigated by DSC and their elastic moduli and Poisson's ratio

    NASA Astrophysics Data System (ADS)

    Souri, Dariush

    2015-01-01

    Ternary tellurate glasses of the form xSb-(60-x)V2O5-40TeO2 (0≤x≤15 in mol%) were prepared by using the usual melt quenching method. Differential scanning calorimetry (DSC) at different heating rates (φ) was used to thermal analyze and to gain more insight in to the thermal stability, glass forming tendency and so calorimetric behavior of the present glasses. The glass transition temperature (Tg), the temperature corresponding to the onset of crystallization (Tx) and also the crystallization temperature (TCr) were obtained at different heating rates, to estimate the key kinetic parameter of activation energy of crystallization (ΔE) by using different empirical formulas. Also some other thermal parameters such as thermal stability and glass forming tendency were determined. It was found that Tg, Tx and TCr increase with increase in Sb content and also with increase in heating rate. Moreover, Makishima-Makenzie's theory was employed to evaluate the Poisson's ratio and elastic moduli, indicating a strong relation between elastic properties and the structure of glass. From the mechanical and thermal data and also the values of oxygen molar volume ( V O *), it was founded that the glass systems can be divided in to "two compositional regions"; so, results indicate that glasses with 10≤x≤15 (especially for x=12) are more thermal stable and strong glasses, which make them as more useful and promising materials in technological advantages and device manufacturing.

  10. Investigations of a compartmental model for leucine kinetics using non-linear mixed effects models with ordinary and stochastic differential equations.

    PubMed

    Berglund, Martin; Sunnåker, Mikael; Adiels, Martin; Jirstrand, Mats; Wennberg, Bernt

    2012-12-01

    Non-linear mixed effects (NLME) models represent a powerful tool to simultaneously analyse data from several individuals. In this study, a compartmental model of leucine kinetics is examined and extended with a stochastic differential equation to model non-steady-state concentrations of free leucine in the plasma. Data obtained from tracer/tracee experiments for a group of healthy control individuals and a group of individuals suffering from diabetes mellitus type 2 are analysed. We find that the interindividual variation of the model parameters is much smaller for the NLME models, compared to traditional estimates obtained from each individual separately. Using the mixed effects approach, the population parameters are estimated well also when only half of the data are used for each individual. For a typical individual, the amount of free leucine is predicted to vary with a standard deviation of 8.9% around a mean value during the experiment. Moreover, leucine degradation and protein uptake of leucine is smaller, proteolysis larger and the amount of free leucine in the body is much larger for the diabetic individuals than the control individuals. In conclusion, NLME models offers improved estimates for model parameters in complex models based on tracer/tracee data and may be a suitable tool to reduce data sampling in clinical studies.

  11. An investigation of the effect of surface impurities on the adsorption kinetics of hydrogen chemisorbed onto iron. Annual status report, 1 January-31 December 1994

    SciTech Connect

    Shanabarger, M.R.

    1994-12-01

    The goal of this program has been to develop an understanding of heterogeneous kinetic processes for those molecular species which produce gaseous hydrogen degradation of the mechanical properties of metallic structural materials. During the present program, the interaction of hydrogen with the surfaces of alpha-2 (Ti3Al) titanium aluminide, gamma (TiAl) titanium aluminide, and beryllium were studied. The interaction of low pressure hydrogen with gamma titanium aluminide and beryllium was found to be relatively weak. Weak in the sense that adsorption leads to a low surface concentration of dissociated hydrogen, i.e., the chemisorption process is reversible at room temperature (300 K) for gamma titanium aluminide and the sticking coefficient for chemisorption is extremely small for beryllium. Hydrogen was found to interact readily with alpha-2 titanium aluminide to form a stable surface hydride at 300 K. These results correlate well with other recent studies which show that the mechanical properties for alpha-2 titanium aluminide are readily degraded in hydrogen while gamma titanium aluminide exhibits less degradation and beryllium essentially no degradation. The interaction of oxygen with the surface of several of these materials was studied. More recently, preliminary hydrogen permeation studies were completed for three high temperature alloys, Incoloy 909, Mo-47.5Re (wt. %), and this past year, Haynes 188.

  12. In situ investigation of complex BaSO4 fiber generation in the presence of sodium polyacrylate. 1. Kinetics and solution analysis.

    PubMed

    Wang, Tongxin; Cölfen, Helmut

    2006-10-10

    Simple solution analysis of the formation mechanism of complex BaSO(4) fiber bundles in the presence of polyacrylate sodium salt, via a bioinspired approach, is reported. Titration of the polyacrylate solution with Ba(2+) revealed complex formation and the optimum ratio of Ba(2+) to polyacrylate for a slow polymer-controlled mineralization process. This is a much simpler and faster method to determine the appropriate additive/mineral concentration pairs as opposed to more common crystallization experiments in which the additive/mineral concentration is varied. Time-dependent pH measurements were carried out to determine the concentration of solution species from which BaSO(4) supersaturation throughout the fiber formation process can be calculated and the second-order kinetics of the Ba(2+) concentration in solution can be identified. Conductivity measurements, pH measurements, and analytical ultracentrifugation revealed the first formed species to be Ba-polyacrylate complexes. A combination of the solution analysis results and optical microscopic images allows a detailed picture of the complex precipitation and self-organization process, a particle-mediated process involving mesoscopic transformations, to be revealed.

  13. Synthesis of no carrier added F-18 16-fluorohexadecanoic acid (FHDA) and investigation of its labeled metabolites and its kinetics in the heart

    SciTech Connect

    DeGrado, T.R.; Bernstein, D.R.; Gatley, S.J.; Ng, C.K.; Holden, J.E.

    1984-01-01

    No carrier added FHDA was prepared via saponification of the product of silver oxide assisted reaction of near-anhydrous tetraethylammonium fluoride with methyl 16-iodohexadecanoate. The labeled fatty acid was injected into isolated perfused rat hearts. Coronary perfusate was collected for 4-9 minutes, when hearts were chilled and homogenized. F-18 in perfusate was analysed by HPLC (NH column; 50mM amm. acetate in 50% acetonitrile). Material with the same retention time as F-18 fluoroacetate (prepared by F-for-I exchange with ethyl iodoacetate) was found. Some F-18 stuck permanently to the column and was assigned as fluoride since the same fraction of label in perfusate was retained on alumina columns eluted with water. Anion exchange HPLC (SAX column; 20mM pot. phosphate, pH 7) of homogenates gave peaks corresponding to fluoroacetate plus fluoride and minor peaks which could be fluoroacetylCoA and fluorocitrate. The authors interpret their data as follows. Beta-oxidation of FHDA results in fluoroacetylCoA which either undergoes ''lethal synthesis'' to fluorocitrate or is hydrolysed to fluoroacetate which diffuses out of the heart. The source of the fluoride is not yet clear, but could complicate interpretation of FHDA kinetics measured in vivo with positron tomography. Clearance of label from FHDA in isolated perfused hearts was faster than for labeled 16-iodohexadecanoic acid, indicating that the F-18 tracer may be a more sensitive probe of myocardial fatty acid metabolism.

  14. Synthesis and kinetics investigation of meso-microporous Cu-SAPO-34 catalysts for the selective catalytic reduction of NO with ammonia.

    PubMed

    Liu, Jixing; Yu, Fuhong; Liu, Jian; Cui, Lifeng; Zhao, Zhen; Wei, Yuechang; Sun, Qianyao

    2016-10-01

    A series of meso-microporous Cu-SAPO-34 catalysts were successfully synthesized by a one-pot hydrothermal crystallization method, and these catalysts exhibited excellent NH3-SCR performance at low temperature. Their structure and physic chemical properties were characterized by means of X-ray diffraction patterns (XRD), Scanning electron microscopy (SEM), Transmission electron microscopy (TEM), N2 sorption-desorption, nuclear magnetic resonance (NMR), Inductively Coupled Plasma-Atomic Emission spectrometer (ICP-AES), X-ray absorption spectroscopy (XPS), Temperature-programmed desorption of ammonia (NH3-TPD), Ultraviolet visible diffuse reflectance spectroscopy (UV-Vis DRS) and Temperature programmed reduction (TPR). The analysis results indicate that the high activities of Cu-SAPO-34 catalysts could be attributed to the enhancement of redox property, the formation of mesopores and the more acid sites. Furthermore, the kinetic results verify that the formation of mesopores remarkably reduces diffusion resistance and then improves the accessibility of reactants to catalytically active sites. The 1.0-Cu-SAPO-34 catalyst exhibited the high NO conversion (>90%) among the wide activity temperature window in the range of 150-425°C.

  15. Enantiomeric separation of volatile organics by gas chromatography for the in situ analysis of extraterrestrial materials: kinetics and thermodynamics investigation of various chiral stationary phases.

    PubMed

    Freissinet, C; Buch, A; Szopa, C; Sternberg, R

    2013-09-06

    The performances of several commercial chiral capillary columns have been evaluated with the aim of determining the one most suitable for enantiomeric separation in a gas chromatograph onboard a space probe. We compared the GC-MS response of three capillary columns coated with different chiral stationary phases (CSP) using volatile chiral organic molecules which are potential markers of a prebiotic organic chemistry. The three different chiral capillary columns are Chirasil-Val, with an amino acid derivative CSP, ChiralDex-β-PM, with a CSP composed of dissolved permethylated β-cyclodextrins in polysiloxane, and Chirasil-Dex, with a CSP made of modified cyclodextrins chemically bonded to the polysiloxane backbone. Both kinetics and thermodynamics studies have been carried out to evaluate the chiral recognition potential in these different types of columns. The thermodynamic parameters also allow a better understanding of the driving forces affecting the retention and separation of the enantiomers. The Chirasil-Dex-CSP displays the best characteristics for an optimal resolution of the chiral compounds, without preliminary derivatization. This CSP had been chosen to be the only chiral column in the Sample Analysis at Mars (SAM) experiment onboard the current Mars Science Laboratory (MSL) mission, and is also part of the Mars Organic Molecules Analyzer (MOMA) gas chromatograph onboard the next Martian mission ExoMars. The use of this column could also be extended to all space missions aimed at studying chirality in space.

  16. Investigation of the Kinetics of the Ferrite/Austenite Phase Transformation in the HAZ of a 2205 Duplex Stainless Steel Weldment

    SciTech Connect

    Palmer, T A; Elmer, J W; Wong, J; Babu, S S; Vitek, J M

    2002-03-14

    A semi-quantitative map based on a series of spatially resolved X-ray diffraction (SRXRD) scans shows the progression of the ferrite ({delta})/austenite ({gamma}) phase balance throughout the HAZ during GTA welding of a 2205 duplex stainless steel (DSS). This map shows an unexpected decrease in the ferrite fraction on heating, followed by a recovery to the original ferrite fraction on cooling at locations within the HAZ. Even though such behavior is supported by thermodynamic calculations, it has not been confirmed by either experimental methods or have the kinetics been evaluated. Both Gleeble thermal simulations and time resolved x-ray diffraction measurements on spot welds in the 2205 DSS provide further evidence for this rather low-temperature transformation. On the other hand, calculations of the diffusion of alloying elements across the 6/y interface under a variety of conditions shed no further light on the driving force for this transformation. Further work on the mechanisms and driving forces for this transformation is on-going.

  17. Real-time investigation of human topoisomerase I reaction kinetics using an optical sensor: a fast method for drug screening and determination of active enzyme concentrations

    NASA Astrophysics Data System (ADS)

    Kristoffersen, Emil L.; Jørgensen, Line A.; Franch, Oskar; Etzerodt, Michael; Frøhlich, Rikke; Bjergbæk, Lotte; Stougaard, Magnus; Ho, Yi-Ping; Knudsen, Birgitta R.

    2015-05-01

    Human DNA topoisomerase I (hTopI) is a nuclear enzyme that catalyzes relaxation of super helical tension that arises in the genome during essential DNA metabolic processes. This is accomplished through a common reaction mechanism shared among the type IB topoisomerase enzymes, including eukaryotic and poxvirus topoisomerase I. The mechanism of hTopI is specifically targeted in cancer treatment using camptothecin derivatives. These drugs convert the hTopI activity into a cellular poison, and hence the cytotoxic effects of camptothecin derivatives correlate with the hTopI activity. Therefore, fast and reliable techniques for high throughput measurements of hTopI activity are of high clinical interest. Here we demonstrate potential applications of a fluorophore-quencher based DNA sensor designed for measurement of hTopI cleavage-ligation activities, which are the catalytic steps affected by camptothecin. The kinetic analysis of the hTopI reaction with the DNA sensor exhibits a characteristic burst profile. This is the result of a two-step ping-pong reaction mechanism, where a fast first reaction, the one creating the signal, is followed by a slower second reaction necessary for completion of the catalytic cycle. Hence, the burst profile holds information about two reactions in the enzymatic mechanism. Moreover, it allows the amount of active enzyme in the reaction to be determined. The presented results pave the way for future high throughput drug screening and the potential of measuring active hTopI concentrations in clinical samples for individualized treatment.Human DNA topoisomerase I (hTopI) is a nuclear enzyme that catalyzes relaxation of super helical tension that arises in the genome during essential DNA metabolic processes. This is accomplished through a common reaction mechanism shared among the type IB topoisomerase enzymes, including eukaryotic and poxvirus topoisomerase I. The mechanism of hTopI is specifically targeted in cancer treatment using

  18. Fourier transform infra-red (FTIR) spectroscopy investigation, dose effect, kinetics and adsorption capacity of phosphate from aqueous solution onto laterite and sandstone.

    PubMed

    Coulibaly, Lassina Sandotin; Akpo, Sylvain Kouakou; Yvon, Jacques; Coulibaly, Lacina

    2016-12-01

    Environmental pollution by phosphate in developing countries is growing with extensive and diffuse pollution. Solving these problem with intensive technologies is very expensive. Using natural sorbent such as laterite and sandstone could be a solution. The main objective of the study is to evaluate the P-removal efficiency of these materials under various solution properties. Laterite and sandstone used mainly contain very high levels of finely grained iron and aluminum oxy-hydroxides and diverse dioctahedral clays. Phosphate adsorption tests were carried out using crushed laterite and sandstone. Optimal doses and pH effects on phosphate adsorption were studied with a potassium hydrogeno-phosphate solution of 5 mg/L at 30 °C. The main results were that the optimal dosage is 15 and 20 mg/L respectively for laterite and sandstone. The phosphate adsorptions efficiency of laterite and sandstone are pH-dependent, they increase when the pH grows up to the Point of Zero Charge (PZC) and slowly decrease beyond. The adsorption capacities of the materials also increase proportionally with the initial phosphate concentration. The pseudo-second-order successfully described the kinetics of the phosphate adsorption on the two adsorbents. With this model, the adsorption capacity values are obtained, which give an idea of the maximum phosphate uptake that the laterite and sandstone could achieve. The changes on the FTIR spectra of raw materials and phosphate adsorbed material confirm the mechanism of chemisorptions. Considering the above, laterite and sandstone could be used as efficient and cheap adsorbent for the removal of phosphate in aqueous solution.

  19. Investigation of structure and composition control over active dissolution of Fe-Tc binary metallic waste forms by off-lattice kinetic Monte Carlo simulation

    NASA Astrophysics Data System (ADS)

    Taylor, Christopher D.; Liu, Xiang-Yang

    2013-03-01

    In this paper we develop and apply an atomistic framework for predicting the corrosion tendencies of metallic waste forms that are based on the iron-technetium (Fe-Tc) binary system. These elements were selected due to their importance for the development of metal alloy waste forms for fission product disposition. A kinetic Monte Carlo model based on an off-lattice, modified embedded atom method (MEAM) representation of the Fe-Tc binary system was applied to understand and predict the corrosion behavior of Fe-Tc alloys, as a function of structure (phase and surface-orientation) and composition. During active dissolution, metal atoms are in the free-corrosion state, in which there is a bare metal surface exposed to the environment. The Brønsted-Evans-Polanyi relationship was applied to link atomic cohesive energies, as evaluated using the parameterized MEAM potential, to activation barriers for dissolution. The active dissolution scenario may occur in situations where the passive film has either not formed, is electrochemically unstable, or has been damaged due to the application of stress or pitting attack. Our simulations of the active dissolution process suggest that the corrosion of candidate alloy waste forms will be highly sensitive to Tc loading, as well as phase selection. Hexagonally close-packed alloys are predicted to have lower corrosion rates compared to body-centered cubic. Similarly, ordered structures appear to have a stronger corrosion resistance than randomly dispersed alloys. Finally, our results indicate an optimal loading of Tc in the alloy, which is consistent with electrochemical corrosion experiments.

  20. Kinetics of stress fibers

    NASA Astrophysics Data System (ADS)

    Stachowiak, Matthew R.; O'Shaughnessy, Ben

    2008-02-01

    Stress fibers are contractile cytoskeletal structures, tensile actomyosin bundles which allow sensing and production of force, provide cells with adjustable rigidity and participate in various processes such as wound healing. The stress fiber is possibly the best characterized and most accessible multiprotein cellular contractile machine. Here we develop a quantitative model of the structure and relaxation kinetics of stress fibers. The principal experimentally known features are incorporated. The fiber has a periodic sarcomeric structure similar to muscle fibers with myosin motor proteins exerting contractile force by pulling on actin filaments. In addition the fiber contains the giant spring-like protein titin. Actin is continuously renewed by exchange with the cytosol leading to a turnover time of several minutes. In order that steady state be possible, turnover must be regulated. Our model invokes simple turnover and regulation mechanisms: actin association and dissociation occur at filament ends, while actin filament overlap above a certain threshold in the myosin-containing regions augments depolymerization rates. We use the model to study stress fiber relaxation kinetics after stimulation, as observed in a recent experimental study where some fiber regions were contractile and others expansive. We find that two distinct episodes ensue after stimulation: the turnover-overlap system relaxes rapidly in seconds, followed by the slow relaxation of sarcomere lengths in minutes. For parameter values as they have been characterized experimentally, we find the long time relaxation of sarcomere length is set by the rate at which actin filaments can grow or shrink in response to the forces exerted by the elastic and contractile elements. Consequently, the stress fiber relaxation time scales inversely with both titin spring constant and the intrinsic actin turnover rate. The model's predicted sarcomere velocities and contraction-expansion kinetics are in good

  1. Adsorption and desorption kinetics of carbofuran in acid soils.

    PubMed

    Bermúdez-Couso, Alipio; Fernández-Calviño, David; Pateiro-Moure, Miriam; Nóvoa-Muñoz, Juan Carlos; Simal-Gándara, Jesús; Arias-Estévez, Manuel

    2011-06-15

    Carbofuran adsorption and desorption were investigated in batch and stirred flow chamber (SFC) tests. The carbofuran adsorption capacity of the soils was found to be low and strongly dependent on their clay and organic carbon contents. Carbofuran sorption was due mainly (>80%) to fast adsorption processes governed by intraparticle diffusion. The adsorption kinetic constant for the pesticide ranged from 0.047 to 0.195 min(-1) and was highly correlated with constant n in the Freundlich equation (r=0.965, P<0.05). Batch tests showed carbofuran desorption to be highly variable and negatively correlated with eCEC and the clay content. The SFC tests showed that soil organic carbon (C) plays a key role in the irreversibility of carbofuran adsorption. Carbofuran desorption increased rapidly at C contents below 4%. The desorption kinetic constant for the compound (0.086-0.195 min(-1)) was generally higher than its adsorption kinetic constant; therefore, carbofuran is more rapidly desorbed than it is adsorbed in soil.

  2. Investigation of Lower Hybrid Drift Instability turbulence in the terrestrial magnetotail with fully kinetic, realistic mass ratio Multi-Level Multi-Domain simulations and comparison with observations

    NASA Astrophysics Data System (ADS)

    Innocenti, M. E.; Jiang, W.; Newman, D. L.; Goldman, M. V.; Markidis, S.; Lapenta, G.; Norgren, C.

    2015-12-01

    The kinetic, semi-implicit, adaptive Multi-Level Multi-Domain (MLMD) method is used to simulate, at realistic mass ratio, the development of turbulence generated by the Lower Hybrid Drift Instability (LHDI) in the terrestrial magnetotail over a large range of wavenumbers. The MLMD method reduces the cost of Particle in Cell (PIC) simulations by using higher temporal and spatial resolution only in a small part of the entire domain [Innocenti13, Beck14, Innocenti15]. This reduction in computational cost allows to increase the range of wavenumber simulated with respect to "traditional" PIC simulations and makes the MLMD method a useful approach to explore the multi scale nature of turbulent processes. The power spectra of the fluctuations of the perpendicular electric field and of the magnetic field are studied at wavenumbers and times that allow to appreciate the onset of the electrostatic and electromagnetic LHDI branches and of the ion-ion kink instability. The coupling between electric and magnetic field fluctuations observed in Norgren [2012] for high wavenumber LHDI waves in the terrestrial magnetotail is verified. A break in the magnetic field fluctuation spectra at kdi ˜ 30, with di the ion skin depth and k the perpendicular wavenumber, is observed at early simulated times, Ωcit < 6, with Ωci the ion cyclotron frequency. It is explained with the initial decoupling of electric and magnetic field fluctuations at intermediate and low wavenumbers prior to the development of the electromagnetic LHDI branch. It is observed that the coupling is mediated by the electron current in the electrostatic and electromagnetic LHDI wavenumber range and by the ion current in the kink instability wavenumber range. M. Innocenti, G. Lapenta, S. Markidis, A. Beck, and A. Vapirev, JCP 238, 115 - 140 (2013). A. Beck, M. Innocenti, G. Lapenta, and S. Markidis, JCP 271, 430 - 443 (2014). M. Innocenti, A. Beck, T. Ponweiser, S. Markidis, and G. Lapenta, CPC 189, 47 - 59 (2015

  3. Investigation of novel rapidly synergistic cloud point extraction pattern for bismuth in water and geological samples coupling with flame atomic absorption spectrometry determination.

    PubMed

    Wen, Xiaodong; Zhao, Yu; Deng, Qingwen; Ji, Shoulian; Zhao, Xia; Guo, Jie

    2012-04-01

    Rapidly synergistic cloud point extraction (RS-CPE) greatly simplified and accelerated the procedure of traditional cloud point extraction (CPE). In order to expand the application of RS-CPE, this work was carried out after the establishment of the improved extraction technique. The new established extraction method was firstly applied for bismuth extraction and determination coupled with flame atomic absorption spectrometry (FAAS) in this work. The improved RS-CPE was accomplished in the room temperature in 1 min. Non-ionic surfactant Triton X-100 (TX-100) was used as extractant. Octanol worked as cloud point revulsant and synergic reagent. TX-100 has a relatively high cloud point temperature (CPT), which limited its application in CPE. In this work, TX-100 accomplished the RS-CPE procedure in room temperature successfully. The factors influencing RS-CPE, such as concentrations of reagents, pH, conditions of phase separation, effect of environmental temperatures, salt effect and instrumental conditions, were studied systematically. Under the optimal conditions, the limit of detection (LOD) for bismuth was 4.0 μg L(-1), with sensitivity enhancement factor (EF) of 43. The proposed method greatly improved the sensitivity of FAAS for the determination of bismuth and was applied to the determination of trace bismuth in real and certified samples with satisfactory analytical results. The proposed method was rapid, simple, and sensitive.

  4. Investigation of magnetic nanoparticles for the rapid extraction and assay of alpha-emitting radionuclides from urine: Demonstration of a novel radiobioassay method

    SciTech Connect

    O'Hara, Matthew J.; Carter, Jennifer C.; Maclellan, Jay A.; Warner, Cynthia L.; Warner, Marvin G.; Addleman, Raymond S.

    2011-08-01

    In the event of an accidental or intentional release of radionuclides into a populated area, three things must occur in a timely manner: food and drinking water supplies must be determined to be safe to eat / drink, civilians and/or military personnel must be surveyed to ensure that they do not have external contamination, and they must be screened to ensure that significant ingestion or inhalation of radionuclides has not occurred (this paper is concerned with the latter). In the event of such a disaster, the volume of radiobioassays to be performed would be tremendous. If the event released significant levels of β- or α-emitting radionuclides, in vivo assays would be ineffective. Therefore, highly efficient and rapid analytical methods for radionuclide detection from submitted spot urine samples (≤ 50 mL) would be required. At present, the quantitative determination of α-emitting radionuclides from urine samples is highly labor intensive, and requires significant sample preparation and analysis time. Sorbent materials that provide effective collection and enable rapid assay could significantly streamline the radioanalytical process. We have demonstrated the use of paramagnetic nanoparticles as a novel class of extracting media for four α-emitting radionuclides of concern (Po, Ra, Am, and U) from chemically unmodified and pH 2 human urine. Herein the initial experimental sorption results are presented along with a novel method that utilizes paramagnetic nanoparticles for the extraction of radionuclides from unmodified human urine followed by the magnetic field-induced collection of the particles for subsequent α-counting-source preparation. Additionally, we construct a versatile human dose model that determines the detector count times required to estimate internal human dose at specific protective action thresholds. The model provides a means to assess a method’s detection capabilities and use fundamental health physics parameters and actual experimental

  5. Basic residue at position 14 is not required for fast assembly and disassembly kinetics in neural cadherin.

    PubMed

    Vunnam, Nagamani; Hammer, Nathan I; Pedigo, Susan

    2015-01-27

    In spite of their structural similarities, epithelial (E-) and neural (N-) cadherin are expressed at different types of synapses and differ significantly in their dimerization kinetics. Recent studies proposed a transient intermediate in E-cadherin as the key requirement for rapid disassembly kinetics of the adhesive dimer. This E-cadherin intermediate comprises four intermolecular ionic and H-bonding interactions between adhesive partners. These interactions are not preserved in N-cadherin except for a basic residue at the 14th position, which could stabilize the intermediate through either H-bonding or ionic interactions with the partner protomer. To investigate the origin of the rapid dimerization kinetics of N-cadherin in the presence of calcium, studies reported here systematically test the role of ionic and H-bonding interactions in dimerization kinetics using R14S, R14A, and R14E mutants of N-cadherin. Analytical size-exclusion chromatographic and bead aggregation studies showed two primary results. First, N-cadherin/R14S and N-cadherin/R14A mutants showed fast assembly and disassembly kinetics in the calcium-saturated state similar to that of wild-type N-cadherin. These results indicate that the fast disassembly of the calcium-saturated dimer of N-cadherin does not require a basic residue at the 14th position. Second, the dimerization kinetics of N-cadherin/R14E were slow in the calcium-saturated state, indicating that negative charge destabilizes the intermediate state. Taken together, these results indicate that the basic residue at the 14th position does not promote rapid dimerization kinetics but that an acidic amino acid in that position significantly impairs dimerization kinetics.

  6. Rapid analysis of bile acids in different biological matrices using LC-ESI-MS/MS for the investigation of bile acid transformation by mammalian gut bacteria.

    PubMed

    Wegner, Katrin; Just, Sarah; Gau, Laura; Mueller, Henrike; Gérard, Philippe; Lepage, Patricia; Clavel, Thomas; Rohn, Sascha

    2017-02-01

    Bile acids are important signaling molecules that regulate cholesterol, glucose, and energy homoeostasis and have thus been implicated in the development of metabolic disorders. Their bioavailability is strongly modulated by the gut microbiota, which contributes to generation of complex individual-specific bile acid profiles. Hence, it is important to have accurate methods at hand for precise measurement of these important metabolites. Here, a rapid and sensitive liquid chromatography-tandem mass spectrometry (LC-MS/MS) method for simultaneous identification and quantitation of primary and secondary bile acids as well as their taurine and glycine conjugates was developed and validated. Applicability of the method was demonstrated for mammalian tissues, biofluids, and cell culture media. The analytical approach mainly consists of a simple and rapid liquid-liquid extraction procedure in presence of deuterium-labeled internal standards. Baseline separation of all isobaric bile acid species was achieved and a linear correlation over a broad concentration range was observed. The method showed acceptable accuracy and precision on intra-day (1.42-11.07 %) and inter-day (2.11-12.71 %) analyses and achieved good recovery rates for representative analytes (83.7-107.1 %). As a proof of concept, the analytical method was applied to mouse tissues and biofluids, but especially to samples from in vitro fermentations with gut bacteria of the family Coriobacteriaceae. The developed method revealed that the species Eggerthella lenta and Collinsella aerofaciens possess bile salt hydrolase activity, and for the first time that the species Enterorhabdus mucosicola is able to deconjugate and dehydrogenate primary bile acids in vitro.

  7. A dietary intervention to elicit rapid and complex dietary changes for studies investigating the effects of diet on tissues collected during invasive surgical procedures.

    PubMed

    Schenk, Jeannette M; Neuhouser, Marian L; Lin, Daniel W; Kristal, Alan R

    2009-03-01

    Nutrition intervention trials in patients undergoing surgical treatment for cancer offer a unique opportunity to study the mechanisms and pathways that underlie diet and cancer associations in target tissues. However, due to the short time period between diagnosis and treatment, traditional dietary intervention methods are not feasible. This report describes a novel dietary intervention program designed to elicit rapid and complex dietary change during a condensed study period. The intervention, based on Consumer Information Processing, used standardized menus and exchange lists to guide food choices, and was delivered using a single, in-person session followed by telephone-based counseling. This intervention program was used in a small pilot study evaluating the short-term effects of dietary change in men with newly diagnosed prostate cancer. Eight men were randomly assigned to either a low-fat/low-glycemic load or standard American diet during the 4 weeks preceding prostate surgery. Participants completed 24-hour dietary recalls each week, and were weighed at baseline and at surgery. Compared to men in the standard American arm (n=4), men in the low-fat/low-glycemic arm (n=4) reported consuming less total fat (51.0+/-36.0 vs 93.5+/-8.4 g/day, P=0.06), and had a lower glycemic load (134.8+/-6.0 vs 266.3+/-36.8 units/day, P<0.001). Men in the low-fat/low-glycemic arm lost a mean of 5.3+/-1.7 kg and men in the standard American arm gained 0.8+/-4.5 kg (P=0.04). Results of this small pilot study suggest that a relatively simple and minimally burdensome dietary intervention can elicit rapid and complex dietary changes that are maintained over a 4-week study period. Further studies in larger and more diverse populations are needed to fully understand the potential of this novel intervention approach.

  8. Strengthening Student Interest and Learning of Watershed Science using a Case-History Investigation of a Rapidly Changing Semi-Arid Watershed

    NASA Astrophysics Data System (ADS)

    Huth, A. K.; Hall, M. K.

    2007-12-01

    In a changing climate, watershed disturbances such as drought, large-scale wildfires, and extreme rainfall patterns are on the rise, particularly in the southwestern U.S. Yet, at high-school grade levels, hydrology and watershed science get minimal coverage in classrooms. To address this situation, we developed a set of GIS- based student investigations on the affect of natural and human-induced disturbances on watershed hydrology. The case history focuses on the 2003 Aspen Fire in southern Arizona, but also incorporates investigations of undisturbed watersheds. We structured these investigations around recent hydrologic, geologic, and fire data collected by USGS, USFS, and University of Arizona scientists. The investigations encourage students to use Google Earth and MyWorld GIS to learn about the watersheds of the Santa Catalina Mountains in southern Arizona. Students use precipitation and streamflow data to discover the "normal" response of a semi-arid watershed to rainfall. Through spatial visualization and analysis of the data, they learn how and why a semi-arid watershed may become vulnerable to change due to "unusual" conditions. The large-scale Aspen wildfire and subsequent massive debris flows caused watershed instability and were used as teaching tools in these investigations. Field testing has focused on increasing usability and pedagogical effectiveness, whereas external peer reviews have addressed scientific accuracy. We found the overall response to these investigations by both students and teachers to be positive. The benefits of using real, scientific data in combination with spatial visualization tools to teach about a watershed's response to fire were measured using a survey assessment of student learning during field testing.

  9. The Heliopause Electrostatic Rapid Transit System (HERTS) Design, Trades, and Analyses Performed in the First Year of a Two Year Investigation

    NASA Technical Reports Server (NTRS)

    Wiegmann, Bruce M.

    2016-01-01

    The Heliopause Electrostatic Rapid Transit System (HERTS)1 was one of the seven total Phase II NASA Innovative Advanced Concepts (NIAC) that was down-selected in 2015 for continued funding and research. In Phase I we learned that a spacecraft propelled by an Electric Sail (E-Sail) can travel great astronomical distances, such as to the Heliopause region of the solar system (approx.100 to 120 AU) in approximately one quarter of the time (10 years) versus the time it took the Voyager spacecraft launched in 1977 (36 years). The current work within the Phase II NIAC effort builds upon the work that was done in the Phase I NIAC and is focused on: 1) Testing of plasma interaction with a charged wire in a unique MSFC test chamber, 2) Development of a Particle-in-Cell (PIC) models that are validated in the plasma testing and used to extrapolate to the E-Sail propulsion system design. 3) Further down select of a wire deployment and control approach from those narrowed down in the Phase I effort. This paper will document the findings to date (June, 2016) of the above focused areas.

  10. Rapid Prototyping

    NASA Technical Reports Server (NTRS)

    1999-01-01

    Javelin, a Lone Peak Engineering Inc. Company has introduced the SteamRoller(TM) System as a commercial product. The system was designed by Javelin during a Phase II NASA funded small commercial product. The purpose of the invention was to allow automated-feed of flexible ceramic tapes to the Laminated Object Manufacturing rapid prototyping equipment. The ceramic material that Javelin was working with during the Phase II project is silicon nitride. This engineered ceramic material is of interest for space-based component.

  11. Kinetics of moisture-induced hydrolysis in powder blends stored at and below the deliquescence relative humidity: investigation of sucrose-citric acid mixtures.

    PubMed

    Kwok, Kaho; Mauer, Lisa J; Taylor, Lynne S

    2010-11-24

    Previous studies have shown that deliquescent organic compounds frequently exhibit chemical instability when stored in environmental conditions above their deliquescence relative humidity (RH). The goal of the current study was to investigate the effect of atmospheric moisture on the long-term chemical stability of crystalline sucrose-citric acid mixtures following storage at RHs at and below the mutual deliquescence relative humidity (MDRH). Interestingly, it was found that sucrose hydrolysis can occur below the MDRH of 64% and was observed for samples stored at 54% RH. However, hydrolysis was not seen for samples stored at 33 or 43% RH. The rate of sucrose hydrolysis could be modeled by taking into account the rate and extent of moisture uptake, which in turn was dependent on the composition of the powder and the storage RH. A reaction mechanism initiated by capillary condensation and involving additional deliquescence lowering by the degradation products formed as a result of sucrose hydrolysis (glucose and fructose) was proposed.

  12. Kinetic controls on early karst aquifer porosity development

    SciTech Connect

    Groves, C.G. ); Howard, A.D. . Dept. of Environmental Sciences)

    1992-01-01

    A series of simulations using the newly developed model KARST has been performed to investigate limiting kinetic controls on limestone dissolution during the earliest stages of karst aquifer porosity development. This FORTRAN model couples fluid flow within and dissolution of circular cross section conduits, and considers surface reaction rates (both far from and close to thermodynamic equilibrium), mass transfer rates of reaction products to the bulk fluid, and rates of homogeneous reactions associated with dissolution of CO[sub 2] gas in water. Mass transfer theory for both laminar and turbulent flow cases is included. Runs were made with a wide variety of initial conditions of passage geometry, head gradient, and initial PCO[sub 2]. Results show a consistent pattern of kinetic control that varies as functions of time as well as position along the conduit. Slow, higher order surface reaction rates (close to equilibrium), diffusion rates, and rapid, lower order reaction rates (far from equilibrium) are found to be limiting steps at various times and location. Under no conditions in the simulations did the rate of CO[sub 2] hydration limit dissolution. Thresholds between the various kinetic regimes were found to be associated with a critical distance from equilibrium, as well as the transition from laminar to turbulent flow. As a result of interactions between flow and chemical conditions, passage growth (measure by fluid discharge rates) can be divided into an initial, slow period initiation and a more rapid one (enlargement). The onset of the enlargement phase was not found to coincide with any single kinetic event.

  13. Investigation of thermal decomposition as the kinetic process that causes the loss of crystalline structure in sucrose using a chemical analysis approach (part II).

    PubMed

    Lee, Joo Won; Thomas, Leonard C; Jerrell, John; Feng, Hao; Cadwallader, Keith R; Schmidt, Shelly J

    2011-01-26

    High performance liquid chromatography (HPLC) on a calcium form cation exchange column with refractive index and photodiode array detection was used to investigate thermal decomposition as the cause of the loss of crystalline structure in sucrose. Crystalline sucrose structure was removed using a standard differential scanning calorimetry (SDSC) method (fast heating method) and a quasi-isothermal modulated differential scanning calorimetry (MDSC) method (slow heating method). In the fast heating method, initial decomposition components, glucose (0.365%) and 5-HMF (0.003%), were found in the sucrose sample coincident with the onset temperature of the first endothermic peak. In the slow heating method, glucose (0.411%) and 5-HMF (0.003%) were found in the sucrose sample coincident with the holding time (50 min) at which the reversing heat capacity began to increase. In both methods, even before the crystalline structure in sucrose was completely removed, unidentified thermal decomposition components were formed. These results prove not only that the loss of crystalline structure in sucrose is caused by thermal decomposition, but also that it is achieved via a time-temperature combination process. This knowledge is important for quality assurance purposes and for developing new sugar based food and pharmaceutical products. In addition, this research provides new insights into the caramelization process, showing that caramelization can occur under low temperature (significantly below the literature reported melting temperature), albeit longer time, conditions.

  14. Kinetics of coal pyrolysis

    SciTech Connect

    Seery, D.J.; Freihaut, J.D.; Proscia, W.M. ); Howard, J.B.; Peters, W.; Hsu, J.; Hajaligol, M.; Sarofim, A. ); Jenkins, R.; Mallin, J.; Espindola-Merin, B. ); Essenhigh, R.; Misra, M.K. )

    1989-07-01

    This report contains results of a coordinated, multi-laboratory investigation of coal devolatilization. Data is reported pertaining to the devolatilization for bituminous coals over three orders of magnitude in apparent heating rate (100 to 100,000 + {degree}C/sec), over two orders of magnitude in particle size (20 to 700 microns), final particle temperatures from 400 to 1600{degree}C, heat transfer modes ranging from convection to radiative, ambient pressure ranging from near vacuum to one atmosphere pressure. The heat transfer characteristics of the reactors are reported in detail. It is assumed the experimental results are to form the basis of a devolatilization data base. Empirical rate expressions are developed for each phase of devolatilization which, when coupled to an awareness of the heat transfer rate potential of a particular devolatilization reactor, indicate the kinetics emphasized by a particular system reactor plus coal sample. The analysis indicates the particular phase of devolatilization that will be emphasized by a particular reactor type and, thereby, the kinetic expressions appropriate to that devolatilization system. Engineering rate expressions are developed from the empirical rate expressions in the context of a fundamental understanding of coal devolatilization developed in the course of the investigation. 164 refs., 223 figs., 44 tabs.

  15. Synthesis of an imprinted hybrid organic-inorganic polymeric sol-gel matrix toward the specific binding and isotherm kinetics investigation of creatinine.

    PubMed

    Chang, Yong-Sheun; Ko, Ting-Hsien; Hsu, Ting-Jung; Syu, Mei-Jywan

    2009-03-15

    Hybrid organic-inorganic polymeric sol-gel materials imprinted with creatinine template molecules were synthesized for the specific binding of creatinine. Creatinine is a metabolite from creatine and is the final product from kidney metabolism. Therefore, creatinine can be an important index to estimate the function of the kidney. It was then chosen as the target molecule in this work. To achieve the specific binding toward creatinine, molecular imprinting was used to create a polymeric matrix for the regarding purpose. Sol-gel was further added to create a rigid network structure for the absorption of creatinine. An inorganic precursor, tetraethoxysilane (TEOS), was mixed with an organic functional monomer, 2-acrylamido-2-methylpropane-sulfonic acid (AMPS), and the creatinine template to form a hybrid organic-inorganic imprinted polymer. The chemical functionality was achieved as well as a confined matrix via the polymerization and the hydrolysis-condensation of the sol-gel. The imprinting effect from the hybrid materials against the corresponding nonimprinted was investigated. BET (Brunauer-Emmett-Teller) analysis was carried out for the imprinted and the nonimprinted materials. The specificity of the hybrid materials was further examined by capping the surface silanol groups with chloro-trimethylsilane (CTMS) and 1,1,1,3,3,3-hexamethyldisilazane (HMDS), respectively. The capping effect was compared and discussed from the binding results. Selectivity of the materials toward creatinine was obtained using mixture solutions in the presence of creatinine and its analogues. Reutilization and storage stability of the hybrid organic-inorganic imprinted material were also studied. Additionally, the affinity distribution of the hybrid imprinted materials derived from the allosteric model was also analyzed from the adsorption isotherm data.

  16. Spectral method for a kinetic swarming model

    DOE PAGES

    Gamba, Irene M.; Haack, Jeffrey R.; Motsch, Sebastien

    2015-04-28

    Here we present the first numerical method for a kinetic description of the Vicsek swarming model. The kinetic model poses a unique challenge, as there is a distribution dependent collision invariant to satisfy when computing the interaction term. We use a spectral representation linked with a discrete constrained optimization to compute these interactions. To test the numerical scheme we investigate the kinetic model at different scales and compare the solution with the microscopic and macroscopic descriptions of the Vicsek model. Lastly, we observe that the kinetic model captures key features such as vortex formation and traveling waves.

  17. Chemical and Biological Kinetics

    NASA Astrophysics Data System (ADS)

    Emanuel', N. M.

    1981-10-01

    Examples of the application of the methods and ideas of chemical kinetics in various branches of chemistry and biology are considered and the results of studies on the kinetics and mechanisms of autoxidation and inhibited and catalysed oxidation of organic substances in the liquid phase are surveyed. Problems of the kinetics of the ageing of polymers and the principles of their stabilisation are discussed and certain trends in biological kinetics (kinetics of tumour growth, kinetic criteria of the effectiveness of chemotherapy, problems of gerontology, etc.) are considered. The bibliography includes 281 references.

  18. Diffusion Influenced Adsorption Kinetics.

    PubMed

    Miura, Toshiaki; Seki, Kazuhiko

    2015-08-27

    When the kinetics of adsorption is influenced by the diffusive flow of solutes, the solute concentration at the surface is influenced by the surface coverage of solutes, which is given by the Langmuir-Hinshelwood adsorption equation. The diffusion equation with the boundary condition given by the Langmuir-Hinshelwood adsorption equation leads to the nonlinear integro-differential equation for the surface coverage. In this paper, we solved the nonlinear integro-differential equation using the Grünwald-Letnikov formula developed to solve fractional kinetics. Guided by the numerical results, analytical expressions for the upper and lower bounds of the exact numerical results were obtained. The upper and lower bounds were close to the exact numerical results in the diffusion- and reaction-controlled limits, respectively. We examined the validity of the two simple analytical expressions obtained in the diffusion-controlled limit. The results were generalized to include the effect of dispersive diffusion. We also investigated the effect of molecular rearrangement of anisotropic molecules on surface coverage.

  19. Kinetics of fiber solidification

    PubMed Central

    Mercader, C.; Lucas, A.; Derré, A.; Zakri, C.; Moisan, S.; Maugey, M.; Poulin, P.

    2010-01-01

    Many synthetic or natural fibers are produced via the transformation of a liquid solution into a solid filament, which allows the wet processing of high molecular weight polymers, proteins, or inorganic particles. Synthetic wet-spun fibers are used in our everyday life from clothing to composite reinforcement applications. Spun fibers are also common in nature. Silk solidification results from the coagulation of protein solutions. The chemical phenomena involved in the formation of all these classes of fibers can be quite different but they all share the same fundamental transformation from a liquid to a solid state. The solidification process is critical because it governs the production rate and the strength that fibers can sustain to be drawn and wound. An approach is proposed in this work to investigate the kinetics of fiber solidification. This approach consists in circulating solidifying fibers in the extensional flow of a surrounding liquid. Such as polymers in extensional flows, the fibers break if resultant drag forces exceed the fiber tensile strength. The solidification kinetics of nanotube composite fibers serves as a validation example of this approach. The method could be extended to other systems and advance thereby the science and technology of fiber and textile materials. It is also a way to directly visualize the scission of chain-like systems in extensional flows. PMID:20937910

  20. Practical steady-state enzyme kinetics.

    PubMed

    Lorsch, Jon R

    2014-01-01

    Enzymes are key components of most biological processes. Characterization of enzymes is therefore frequently required during the study of biological systems. Steady-state kinetics provides a simple and rapid means of assessing the substrate specificity of an enzyme. When combined with site-directed mutagenesis (see Site-Directed Mutagenesis), it can be used to probe the roles of particular amino acids in the enzyme in substrate recognition and catalysis. Effects of interaction partners and posttranslational modifications can also be assessed using steady-state kinetics. This overview explains the general principles of steady-state enzyme kinetics experiments in a practical, rather than theoretical, way. Any biochemistry textbook will have a section on the theory of Michaelis-Menten kinetics, including derivations of the relevant equations. No specific enzymatic assay is described here, although a method for monitoring product formation or substrate consumption over time (an assay) is required to perform the experiments described.

  1. Modeling organic micro pollutant degradation kinetics during sewage sludge composting.

    PubMed

    Sadef, Yumna; Poulsen, Tjalfe Gorm; Bester, Kai

    2014-11-01

    Degradation of 13 different organic micro-pollutants in sewage sludge during aerobic composting at 5 different temperatures over a 52 day period was investigated. Adequacy of two kinetic models: a single first order, and a dual first order expression (using an early (first 7 days) and a late-time (last 45 days) degradation coefficient), for describing micro-pollutant degradation, and kinetic constant dependency on composting temperature were evaluated. The results showed that both models provide relatively good descriptions of the degradation process, with the dual first order model being most accurate. The single first order degradation coefficient was 0.025 d(-1) on average across all compounds and temperatures. At early times, degradation was about three times faster than at later times. Average values of the early and late time degradation coefficients for the dual first order model were 0.066 d(-1) and 0.022 d(-1), respectively. On average 30% of the initial micro-pollutant mass present in the compost was degraded rapidly during the early stages of the composting process. Single first order and late time dual first order kinetic constants were strongly dependent on composting temperature with maximum values at temperatures of 35-65°C. In contrast the early time degradation coefficients were relatively independent of composting temperature.

  2. Investigation of Health Risks and Their Prevention in the Rapid Climate Changes and the Rise of Pollution of the Atmosphere in the Mountain Region of the North Caucasus

    NASA Astrophysics Data System (ADS)

    Babyakin, Alexander; Polozkov, Igor; Golitsyn, Georgy; Efimenko, Natalia; Zherlitsina, Liubov; Povolotskaya, Nina; Senik, Irina; Chalaya, Elena; Artamonova, Maria; Pogarski, Fedor

    2010-05-01

    monitoring of blood pressure and ECG. For children with respiratory diseases PSRIC developed a number of effective methods to increase organism resistance to the effects of environmental factors through the use of artificial microclimate chambers and methods of climatic treatment. Thus, a comprehensive study has expanded our understanding of the impact of the environment on human health, to refine the criteria of selected biotropic situations related to the influence of atmospheric pollution, to improve the efficiency of the MWF system in mountain resorts of the North Caucasus, to develop ways to prevent meteopathies of patients with cardio-vascular and respiratory systems. The investigation was fulfilled in the frames of Program of Presidium of the Russian Academy of Sciences "Basic Sciences - for Medicine" and RFBR grant No. 07-05-12069-ofi_a.

  3. Interactions of fluoroquinolone antibacterial agents with aqueous chlorine: reaction kinetics, mechanisms, and transformation pathways.

    PubMed

    Dodd, Michael C; Shah, Amisha D; von Gunten, Urs; Huang, Ching-Hua

    2005-09-15

    Kinetics, products, and mechanistic aspects of reactions between free available chlorine (HOCl/OCl-), ciprofloxacin (CF), and enrofloxacin (EF) were extensively investigated to elucidate the behavior of fluoroquinolone antibacterial agents during water chlorination processes. Although the molecular structures of these two substrates differ only with respect to degree of N(4) amine alkylation, CF and EF exhibit markedly different HOCl reaction kinetics and transformation pathways. HOCI reacts very rapidly at CF's secondary N(4) amine, forming a chloramine intermediate that spontaneously decays in aqueous solution by concerted piperazine fragmentation. In contrast, HOCl reacts relatively slowly at EF's tertiary N(4) amine, apparently forming a highly reactive chlorammonium intermediate (R3N-(4)Cl+) that can catalytically halogenate EF or other substrates present in solution. Flumequine, a fluoroquinolone that lacks the characteristic piperazine ring, exhibits no apparent reactivity toward HOCI but appears to undergo facile halodecarboxylation in the presence of R3N(4)-Cl+ species derived from EF. Measured reaction kinetics were validated in real water matrixes by modeling CF and EF losses in the presence of free chlorine residuals. Combined chlorine (CC) kinetics were determined under selected conditions to evaluate the potential significance of reactions with chloramines. CF's rapid kinetics in direct reactions with HOCl, and relatively high reactivity toward CC, indicate that secondary amine-containing fluoroquinolones should be readily transformed during chlorination of real waters, whether applied chlorine doses are present as free or combined residuals. However, EF's slower HOCl reaction kinetics, recalcitrance toward CC, and participation in the catalytic halogenation cycle described herein suggest that tertiary amine-containing fluoroquinolones will be comparatively stable during most full-scale water chlorination processes.

  4. Label-Free Kinetics: Exploiting Functional Hemi-Equilibrium to Derive Rate Constants for Muscarinic Receptor Antagonists.

    PubMed

    Riddy, Darren M; Valant, Celine; Rueda, Patricia; Charman, William N; Sexton, Patrick M; Summers, Roger J; Christopoulos, Arthur; Langmead, Christopher J

    2015-10-01

    Drug receptor kinetics is as a key component in drug discovery, development, and efficacy; however, determining kinetic parameters has historically required direct radiolabeling or competition with a labeled tracer. Here we present a simple approach to determining the kinetics of competitive antagonists of G protein-coupled receptors by exploiting the phenomenon of hemi-equilibrium, the state of partial re-equilibration of agonist, antagonist, and receptor in some functional assays. Using functional [Ca(2+)]i-flux and extracellular kinases 1 and 2 phosphorylation assays that have short incubation times and therefore are prone to hemi-equilibrium "behaviors," we investigated a wide range of structurally and physicochemically distinct muscarinic acetylcholine receptor antagonists. Using a combined operational and hemi-equilibrium model of antagonism to both simulate and analyze data, we derived estimates of association and dissociation rates for the test set of antagonists, identifying both rapidly dissociating (4-DAMP, himbacine) and slowly dissociating (tiotropium, glycopyrrolate) ligands. The results demonstrate the importance of assay incubation time and the degree of receptor reserve in applying the analytical model. There was an excellent correlation between estimates of antagonist pK(B), k(on), and k(off) from functional assays and those determined by competition kinetics using whole-cell [(3)H]N-methylscopolamine binding, validating this approach as a rapid and simple method to functionally profile receptor kinetics of competitive antagonists in the absence of a labeled tracer.

  5. Rapid climate change

    SciTech Connect

    Morantine, M.C.

    1995-12-31

    Interactions between insolation changes due to orbital parameter variations, carbon dioxide concentration variations, the rate of deep water formation in the North Atlantic and the evolution of the northern hemisphere ice sheets during the most recent glacial cycle will be investigated. In order to investigate this period, a climate model is being developed to evaluate the physical mechanisms thought to be most significant during this period. The description of the model sub-components will be presented. The more one knows about the interactions between the sub-components of the climate system during periods of documented rapid climate change, the better equipped one will be to make rational decisions on issues related to impacts on the environment. This will be an effort to gauge the feedback processes thought to be instrumental in rapid climate shifts documented in the past, and their potential to influence the current climate. 53 refs.

  6. Effects of apolipoproteins on the kinetics of cholesterol exchange

    SciTech Connect

    Letizia, J.Y.; Phillips, M.C. )

    1991-01-22

    The effects of apolipoproteins on the kinetics of cholesterol exchange have been investigated by monitoring the transfer of ({sup 14}C)cholesterol from donor phospholipid/cholesterol complexes containing human apolipoproteins A, B, or C. Negatively charged discoidal and vesicular particles containing purified apolipoproteins complexed with lipid and a trace of ({sup 14}C)cholesterol were incubated with a 10-fold excess of neutral, acceptor, small unilamellar vesicles. The donor and acceptor particles were separated by chromatogrphy of DEAE-Sepharose, and the rate of movement of labeled cholesterol was analyzed as a first-order exchange process. The kinetics of exchange of cholesterol from both vesicular and discoidal complexes that contain apoproteins are consistent with an aqueous diffusion mechanism, as has been established previously for PC/cholesterol SUV. Apolipoproteins A-I, A-II, reduced and carboxymethylated A-11, and B-100 present in SUV at the same lipid/protein (w/w) ratio all enhance the rate of cholesterol exchange to about the same degree. Cholesterol molecules exchange more rapidly from discoidal complexes. Generally, as the diameter of apoprotein/phospholipid/cholesterol discs decreases, t{sub 1/2} for cholesterol exchange decreases. Since small bilayer discs have a relatively high ratio of boundary to face surface area, cholesterol molecules desorb more rapidly than from larger discs. The modulation of lipid packing by the apoprotein molecules present at the surface of lipoprotein particles affects the rate of cholesterol exchange from such particles.

  7. Equilibrium, kinetic and thermodynamic study of cesium adsorption onto nanocrystalline mordenite from high-salt solution.

    PubMed

    Lee, Keun-Young; Park, Minsung; Kim, Jimin; Oh, Maengkyo; Lee, Eil-Hee; Kim, Kwang-Wook; Chung, Dong-Yong; Moon, Jei-Kwon

    2016-05-01

    In this study, the equilibrium, kinetics and thermodynamics of cesium adsorption by nanocrystalline mordenite were investigated under cesium contamination with high-salt solution, simulating the case of an operation and decommissioning of nuclear facilities or an accident during the processes. The adsorption rate constants were determined using a pseudo second-order kinetic model. The kinetic results strongly demonstrated that the cesium adsorption rate of nano mordenite is extremely fast, even in a high-salt solution, and much faster than that of micro mordenite. In the equilibrium study, the Langmuir isotherm model fit the cesium adsorption data of nano mordenite better than the Freundlich model, which suggests that cesium adsorption onto nano mordenite is a monolayer homogeneous adsorption process. The obtained thermodynamic parameters indicated that the adsorption involved a very stable chemical reaction. In particular, the combination of rapid particle dispersion and rapid cesium adsorption of the nano mordenite in the solution resulted in a rapid and effective process for cesium removal without stirring, which may offer great advantages for low energy consumption and simple operation.

  8. Surface Area, and Oxidation Effects on Nitridation Kinetics of Silicon Powder Compacts

    NASA Technical Reports Server (NTRS)

    Bhatt, R. T.; Palczer, A. R.

    1998-01-01

    Commercially available silicon powders were wet-attrition-milled from 2 to 48 hr to achieve surface areas (SA's) ranging from 1.3 to 70 sq m/g. The surface area effects on the nitridation kinetics of silicon powder compacts were determined at 1250 or 1350 C for 4 hr. In addition, the influence of nitridation environment, and preoxidation on nitridation kinetics of a silicon powder of high surface area (approximately equals 63 sq m/g) was investigated. As the surface area increased, so did the percentage nitridation after 4 hr in N2 at 1250 or 1350 C. Silicon powders of high surface area (greater than 40 sq m/g) can be nitrided to greater than 70% at 1250 C in 4 hr. The nitridation kinetics of the high-surface-area powder compacts were significantly delayed by preoxidation treatment. Conversely, the nitridation environment had no significant influence on the nitridation kinetics of the same powder. Impurities present in the starting powder, and those accumulated during attrition milling, appeared to react with the silica layer on the surface of silicon particles to form a molten silicate layer, which provided a path for rapid diffusion of nitrogen and enhanced the nitridation kinetics of high surface area silicon powder.

  9. Effect of kinetic energy on the doping efficiency of cesium cations into superfluid helium droplets

    SciTech Connect

    Chen, Lei; Zhang, Jie; Freund, William M.; Kong, Wei

    2015-07-28

    We present an experimental investigation of the effect of kinetic energy on the ion doping efficiency of superfluid helium droplets using cesium cations from a thermionic emission source. The kinetic energy of Cs{sup +} is controlled by the bias voltage of a collection grid collinearly arranged with the droplet beam. Efficient doping from ions with kinetic energies from 20 eV up to 480 V has been observed in different sized helium droplets. The relative ion doping efficiency is determined by both the kinetic energy of the ions and the average size of the droplet beam. At a fixed source temperature, the number of doped droplets increases with increasing grid voltage, while the relative ion doping efficiency decreases. This result implies that not all ions are captured upon encountering with a sufficiently large droplet, a deviation from the near unity doping efficiency for closed shell neutral molecules. We propose that this drop in ion doping efficiency with kinetic energy is related to the limited deceleration rate inside a helium droplet. When the source temperature changes from 14 K to 17 K, the relative ion doping efficiency decreases rapidly, perhaps due to the lack of viable sized droplets. The size distribution of the Cs{sup +}-doped droplet beam can be measured by deflection and by energy filtering. The observed doped droplet size is about 5 × 10{sup 6} helium atoms when the source temperature is between 14 K and 17 K.

  10. Effect of kinetic energy on the doping efficiency of cesium cations into superfluid helium droplets.

    PubMed

    Chen, Lei; Zhang, Jie; Freund, William M; Kong, Wei

    2015-07-28

    We present an experimental investigation of the effect of kinetic energy on the ion doping efficiency of superfluid helium droplets using cesium cations from a thermionic emission source. The kinetic energy of Cs(+) is controlled by the bias voltage of a collection grid collinearly arranged with the droplet beam. Efficient doping from ions with kinetic energies from 20 eV up to 480 V has been observed in different sized helium droplets. The relative ion doping efficiency is determined by both the kinetic energy of the ions and the average size of the droplet beam. At a fixed source temperature, the number of doped droplets increases with increasing grid voltage, while the relative ion doping efficiency decreases. This result implies that not all ions are captured upon encountering with a sufficiently large droplet, a deviation from the near unity doping efficiency for closed shell neutral molecules. We propose that this drop in ion doping efficiency with kinetic energy is related to the limited deceleration rate inside a helium droplet. When the source temperature changes from 14 K to 17 K, the relative ion doping efficiency decreases rapidly, perhaps due to the lack of viable sized droplets. The size distribution of the Cs(+)-doped droplet beam can be measured by deflection and by energy filtering. The observed doped droplet size is about 5 × 10(6) helium atoms when the source temperature is between 14 K and 17 K.

  11. C3I Rapid Prototype Investigation.

    DTIC Science & Technology

    1986-01-01

    It was , against this set of functions and their organization that we began our .’- 52 eva *. lu ons -. lf People 7ZV. Kernl Imedde Funtion System...generator available to any system with a FORTRAN compiler. It has a descriptive language in which to describe a grammar . Then the grammar description...is translated into Fortran source for compilation and use. In addition it provides an interactive environment for developing a grammar . Data Base

  12. A Sensitive and Robust Enzyme Kinetic Experiment Using Microplates and Fluorogenic Ester Substrates

    ERIC Educational Resources Information Center

    Johnson, R. Jeremy; Hoops, Geoffrey C.; Savas, Christopher J.; Kartje, Zachary; Lavis, Luke D.

    2015-01-01

    Enzyme kinetics measurements are a standard component of undergraduate biochemistry laboratories. The combination of serine hydrolases and fluorogenic enzyme substrates provides a rapid, sensitive, and general method for measuring enzyme kinetics in an undergraduate biochemistry laboratory. In this method, the kinetic activity of multiple protein…

  13. Force Responses and Sarcomere Dynamics of Cardiac Myofibrils Induced by Rapid Changes in [Pi].

    PubMed

    Stehle, Robert

    2017-01-24

    The second phase of the biphasic force decay upon release of phosphate from caged phosphate was previously interpreted as a signature of kinetics of the force-generating step in the cross-bridge cycle. To test this hypothesis without using caged compounds, force responses and individual sarcomere dynamics upon rapid increases or decreases in concentration of inorganic phosphate [Pi] were investigated in calcium-activated cardiac myofibrils. Rapid increases in [Pi] induced a biphasic force decay with an initial slow decline (phase 1) and a subsequent 3-5-fold faster major decay (phase 2). Phase 2 started with the distinct elongation of a single sarcomere, the so-called sarcomere "give". "Give" then propagated from sarcomere to sarcomere along the myofibril. Propagation speed and rate constant of phase 2 (k+Pi(2)) had a similar [Pi]-dependence, indicating that the kinetics of the major force decay (phase 2) upon rapid increase in [Pi] is determined by sarcomere dynamics. In contrast, no "give" was observed during phase 1 after rapid [Pi]-increase (rate constant k+Pi(1)) and during the single-exponential force rise (rate constant k-Pi) after rapid [Pi]-decrease. The values of k+Pi(1) and k-Pi were similar to the rate constant of mechanically induced force redevelopment (kTR) and Ca(2+)-induced force development (kACT) measured at same [Pi]. These results indicate that the major phase 2 of force decay upon a Pi-jump does not reflect kinetics of the force-generating step but results from sarcomere "give". The other phases of Pi-induced force kinetics that occur in the absence of "give" yield the same information as mechanically and Ca(2+)-induced force kinetics (k+Pi(1) ∼ k-Pi ∼ kTR ∼ kACT). Model simulations indicate that Pi-induced force kinetics neither enable the separation of Pi-release from the rate-limiting transition f into force states nor differentiate whether the "force-generating step" occurs before, along, or after the Pi-release.

  14. Phenanthrene biodegradation kinetics in unsaturated soils

    SciTech Connect

    Johnson, C.R.; Scow, K.M.

    1995-12-31

    Organic compounds when sorbed to soil solids are thought to be unavailable to soil microorganisms. The biodegradation kinetics of sorbed chemicals should thus be influenced by sorption/desorption processes as well as by the metabolic capacities of soil microbes. In the research, phenanthrene, a hydrophobic polyaromatic hydrocarbon, was used as a model compound to investigate the biodegradation kinetics of strongly sorbing organic compounds in soil. Biodegradation kinetics for phenanthrene in seven soils with moisture contents near field capacity were measured during a six and one half month experiment. Phenanthrene biodegradation rates initially increased in all soils and then declined. The declining portion of the biodegradation rate versus time plots exhibited either first order or biphasic kinetics. Both first order and biphasic kinetics are consistent with models which link microbial degradation to substrate sorption/desorption from equilibrium and kinetically controlled sorption sites. No single rate constant or analytical expression adequately captured the complexity of the observed biodegradation rates. This result is again consonant with a process derived from coupled biological and physical systems. Biodegradation kinetics were quantified using a combination of fitted and descriptive parameters. Significant correlations exist between several of the descriptive parameters. The correlations observed between descriptive biodegradation parameters mirror correlations expected from the hypothesized underlying biological process and help evince the influence this underlying process exerts on observed biodegradation kinetics.

  15. Kinetic studies of ICF implosions

    DOE PAGES

    Kagan, Grigory; Herrmann, H. W.; Kim, Y. -H.; ...

    2016-05-26

    Here, kinetic effects on inertial confinement fusion have been investigated. In particular, inter-ion-species diffusion and suprathermal ion distribution have been analyzed. The former drives separation of the fuel constituents in the hot reacting core and governs mix at the shell/fuel interface. The latter underlie measurements obtained with nuclear diagnostics, including the fusion yield and inferred ion burn temperatures. Basic mechanisms behind and practical consequences from these effects are discussed.

  16. Liquefaction chemistry and kinetics: Hydrogen utilization studies

    SciTech Connect

    Rothenberger, K.S.; Warzinski, R.P.; Cugini, A.V.

    1995-12-31

    The objectives of this project are to investigate the chemistry and kinetics that occur in the initial stages of coal liquefaction and to determine the effects of hydrogen pressure, catalyst activity, and solvent type on the quantity and quality of the products produced. The project comprises three tasks: (1) preconversion chemistry and kinetics, (2) hydrogen utilization studies, and (3) assessment of kinetic models for liquefaction. The hydrogen utilization studies work will be the main topic of this report. However, the other tasks are briefly described.

  17. Kinetic ways of tailoring phases in high entropy alloys.

    PubMed

    He, Feng; Wang, Zhijun; Li, Yiyan; Wu, Qingfeng; Li, Junjie; Wang, Jincheng; Liu, C T

    2016-09-30

    The comprehensive performance of high entropy alloys (HEAs) depends on the phase selection significantly. However, up to now, investigations of the phase selection in HEAs mainly focused on the thermodynamic equilibrium phase, while kinetic ways of tailoring the phases in HEAs are seldom considered. In HEAs, the kinetics of sluggish diffusion and the numerous possible phases make the kinetics of phase transformation more complex and intriguing. Here, the kinetic effect in CoCrFeNiTi0.4 HEAs was investigated to reveal the possibility of controlling phase selection via kinetic ways for HEAs. The σ, γ' and R phases in the CoCrFeNiTi0.4 HEA can be controlled under different cooling rate both in solidification and solid transformation. The theoretical analyses revealed the kinetic effect on phase selection. The method proposed here, tailoring the phases with different kinetic ways, could be used to prepare promising HEAs with very rich composition design.

  18. Kinetic ways of tailoring phases in high entropy alloys

    NASA Astrophysics Data System (ADS)

    He, Feng; Wang, Zhijun; Li, Yiyan; Wu, Qingfeng; Li, Junjie; Wang, Jincheng; Liu, C. T.

    2016-09-01

    The comprehensive performance of high entropy alloys (HEAs) depends on the phase selection significantly. However, up to now, investigations of the phase selection in HEAs mainly focused on the thermodynamic equilibrium phase, while kinetic ways of tailoring the phases in HEAs are seldom considered. In HEAs, the kinetics of sluggish diffusion and the numerous possible phases make the kinetics of phase transformation more complex and intriguing. Here, the kinetic effect in CoCrFeNiTi0.4 HEAs was investigated to reveal the possibility of controlling phase selection via kinetic ways for HEAs. The σ, γ‧ and R phases in the CoCrFeNiTi0.4 HEA can be controlled under different cooling rate both in solidification and solid transformation. The theoretical analyses revealed the kinetic effect on phase selection. The method proposed here, tailoring the phases with different kinetic ways, could be used to prepare promising HEAs with very rich composition design.

  19. Rapid flow cytometry analysis of antimicrobial properties of nettle powder and cranberry powder

    NASA Astrophysics Data System (ADS)

    Hattuniemi, Maarit; Korhonen, Johanna; Jaakkola, Mari; Räty, Jarkko; Virtanen, Vesa

    2010-11-01

    Both nettle (Urtica dioica) and cranberry (Vaccinium oxycoccus) are widely known to have good influence on health. The aim of this study was to investigate antimicrobial properties of nettle powder and cranberry powder against Escherichia coli (E. coli) and monitor the growth of the bacteria by a rapid flow cytometry (FCM) method. For FCM measurements samples were stained with fluorescent dyes. The inhibitory effects of plant material on growth of E. coli were estimated by comparing the results of control sample (E. coli) to E. coli samples with plant material. FCM offers both a brilliant tool to investigate the kinetics of the growth of bacterium, since subsamples can be taken from the same liquid medium during the growing period and with fluorescent dyes a rapid method to investigate viability of the bacterium.

  20. Nanoscale microstructure effects on hydrogen behavior in rapidly solidified aluminum alloys

    SciTech Connect

    Tashlykova-Bushkevich, Iya I.

    2015-12-31

    The present work summarizes recent progress in the investigation of nanoscale microstructure effects on hydrogen behavior in rapidly solidified aluminum alloys foils produced at exceptionally high cooling rates. We focus here on the potential of modification of hydrogen desorption kinetics in respect to weak and strong trapping sites that could serve as hydrogen sinks in Al materials. It is shown that it is important to elucidate the surface microstructure of the Al alloy foils at the submicrometer scale because rapidly solidified microstructural features affect hydrogen trapping at nanostructured defects. We discuss the profound influence of solute atoms on hydrogen−lattice defect interactions in the alloys. with emphasis on role of vacancies in hydrogen evolution; both rapidly solidified pure Al and conventionally processed aluminum samples are considered.

  1. Rapid wall relaxation in elongating tissues. [Glycine max (L. ); Pisum sativum L

    SciTech Connect

    Matyssek, R.; Maruyama, S.; Boyer, J.S. )

    1988-01-01

    Reported differences in the relaxation of cell walls in enlarging stem tissues of soybean (Glycine max (L.) Merr.) and pea (Pisum sativum L.) cause measurements of the yield threshold turgor, an important growth parameter, to be in doubt. Using the pressure probe and guillotine psychrometer, the authors investigated wall relaxation in these species by excising the elongating tissue in air to remove the water supply. The authors found that the rapid kinetics usually exhibited by soybean could be delayed and made similar to the slow kinetics previously reported for pea if slowly growing or mature tissue was left attached to the rapidly growing tissue when relaxation was initiated. The greater the amount of attached tissue, the slower the relaxation, suggesting that slowly growing tissue acted as a water source. Consistent with this concept was a lower water potential in the rapidly elongating tissue than in the slowly growing tissue. If this tissue was removed from pea, relaxation became as rapid as usually exhibited by soybean. It is concluded that the true relaxation of cell walls to the yield threshold requires only a few minutes and that the yield threshold in the intact plant before excision. Under these conditions, the yield threshold was close to the turgor in the intact plant regardless of the species.

  2. Rapid shallow breathing

    MedlinePlus

    Tachypnea; Breathing - rapid and shallow; Fast shallow breathing; Respiratory rate - rapid and shallow ... Shallow, rapid breathing has many possible medical causes, including: Asthma Blood clot in an artery in the lung Choking Chronic obstructive ...

  3. Comparison of repassivation kinetics of stainless steels in chloride solution

    NASA Astrophysics Data System (ADS)

    Park, Chan-Jin; Kwon, Hyuk-Sang

    2005-08-01

    Using a rapid scratching electrode technique, the repassivation kinetics of type 304, 316, 444, and 2205 stainless steels (SS) were investigated in a chloride solution. The value of cBV in a log i(t) versus 1/q(t) plot as an effective measure of the repassivation rate was used to compare the reapssivation behaviors among the alloys. During repassivation, lower values of cBV for SS corresponded with faster repassivation rates with the formation of a more protective passive film. In a comparison of repassivation rates based on the alloy's cBV values, the best repassivation behavior was shown by 2205 SS, followed by 444 SS and 316 SS. However, 304 SS exhibited an inflection point in the log i(t) versus 1/q(t) curve, suggesting that dissolution by localized corrosion rather than SCC may occur in the alloy under given conditions.

  4. Kinetic modeling of the adsorption of basic dyes by kudzu.

    PubMed

    Allen, Stephen J; Gan, Quan; Matthews, Ronan; Johnson, Pauline A

    2005-06-01

    The use of kudzu, a rapidly growing, high-climbing perennial leguminous vine, for the adsorption of basic dyes from aqueous solution has been investigated at various initial dye concentrations, masses of kudzu, and agitation rates. The extent and rate of adsorption of the three basic dyes (Basic Red 22, Basic Yellow 21, and Basic Blue 3) were analyzed using a pseudo-first-order and a pseudo-second-order kinetic model. While both rate mechanisms provided an acceptable degree of correlation with the experimental sorption rate data, the pseudo-second-order model gave a much higher degree of correlation, suggesting that this model could be used in design and simulation applications.

  5. Kinetics of Aerobic Cometabolism of Chlorinated Solvents

    DTIC Science & Technology

    1998-07-01

    used to describe the cometabolic degradation of 4-chlorophenol in the presence of phenol by Pseudomonas put ida PpG4, an aromatic degrading... Pseudomonas cepacia G4, has shown the most rapid degradation kinetics, with a k1 for TCE that is comparable to that of M trichosporium OB3b. All mixed...competitive inhibition and cometabolism in the biodegradation of benzene, toluene, and p-xylene by two Pseudomonas isolates, Biotech. Bioeng. 41 : 1 057- 1

  6. Kinetics of the Reaction of O((sup 3)P) with CF3NO

    NASA Technical Reports Server (NTRS)

    Thorn, R. P.; Nicovich, J. M.; Cronkhite, J. M.; Wine, P. H.

    1997-01-01

    A laser flash photolysis-resonance fluorescence technique has been employed to study the kinetics of the reaction of O((sup 3)P) with CF3NO (k(2)) as a function of temperature. Our results are described by the Arrhenius expression k(2)(T) = (4.54 +/- 0.70) x 10(exp -l2)exp[(-560 +/- 46)/T] cu cm/molecule.s (243 K is less than or equal to T is less than or equal to 424 K); errors are 2 sigma and represent precision only. The O((sup 3)P) + CF3NO reaction is sufficiently rapid that CF3NO cannot be employed as a selective quencher for O2(alpha(1) Delta-g) in laboratory systems where O((sup 3)P) and O2(alpha 1 Delta g) coexist, and where O((sup 3)P) kinetics are being investigated.

  7. Transient state kinetics tutorial using the kinetics simulation program, KINSIM.

    PubMed Central

    Wachsstock, D H; Pollard, T D

    1994-01-01

    This article provides an introduction to a computer tutorial on transient state kinetics. The tutorial uses our Macintosh version of the computer program, KINSIM, that calculates the time course of reactions. KINSIM is also available for other popular computers. This program allows even those investigators not mathematically inclined to evaluate the rate constants for the transitions between the intermediates in any reaction mechanism. These rate constants are one of the insights that are essential for understanding how biochemical processes work at the molecular level. The approach is applicable not only to enzyme reactions but also to any other type of process of interest to biophysicists, cell biologists, and molecular biologists in which concentrations change with time. In principle, the same methods could be used to characterize time-dependent, large-scale processes in ecology and evolution. Completion of the tutorial takes students 6-10 h. This investment is rewarded by a deep understanding of the principles of chemical kinetics and familiarity with the tools of kinetics simulation as an approach to solve everyday problems in the laboratory. PMID:7811941

  8. Kinetically guided colloidal structure formation

    PubMed Central

    Hecht, Fabian M.; Bausch, Andreas R.

    2016-01-01

    The self-organization of colloidal particles is a promising approach to create novel structures and materials, with applications spanning from smart materials to optoelectronics to quantum computation. However, designing and producing mesoscale-sized structures remains a major challenge because at length scales of 10–100 μm equilibration times already become prohibitively long. Here, we extend the principle of rapid diffusion-limited cluster aggregation (DLCA) to a multicomponent system of spherical colloidal particles to enable the rational design and production of finite-sized anisotropic structures on the mesoscale. In stark contrast to equilibrium self-assembly techniques, kinetic traps are not avoided but exploited to control and guide mesoscopic structure formation. To this end the affinities, size, and stoichiometry of up to five different types of DNA-coated microspheres are adjusted to kinetically control a higher-order hierarchical aggregation process in time. We show that the aggregation process can be fully rationalized by considering an extended analytical DLCA model, allowing us to produce mesoscopic structures of up to 26 µm in diameter. This scale-free approach can easily be extended to any multicomponent system that allows for multiple orthogonal interactions, thus yielding a high potential of facilitating novel materials with tailored plasmonic excitation bands, scattering, biochemical, or mechanical behavior. PMID:27444018

  9. Large kinetic power in FRII radio jets

    NASA Astrophysics Data System (ADS)

    Ito, Hirotaka; Kino, Motoki; Kawakatu, Nozomu; Isobe, Naoki; Yamada, Shoichi

    2007-10-01

    We investigate the total kinetic powers ( L j) and ages ( t age) of powerful jets of four FR II radio sources (Cygnus A, 3C 223, 3C 284, and 3C 219) by the detail comparison of the dynamical model of expanding cocoons with observed ones. It is found that these sources have quite large kinetic powers with the ratio of L j to the Eddington luminosity ( L Edd) resides in 0.02< L j/ L Edd<10. Reflecting the large kinetic powers, we also find that the total energy stored in the cocoon ( E c) exceed the energy derived from the minimum energy condition ( E min ): 2< E c/ E min <160. This implies that a large amount of kinetic power is carried by invisible components such as thermal leptons (electron and positron) and/or protons.

  10. Diffusion influence on Michaelis-Menten kinetics

    NASA Astrophysics Data System (ADS)

    Kim, Hyojoon; Yang, Mino; Choi, Myung-Un; Shin, Kook Joe

    2001-07-01

    Influence of diffusion on the Michaelis-Menten kinetics is investigated with the renormalized kinetic theory recently proposed by Yang et al. [J. Chem. Phys. 108, 117; 108, 8557; 108, 9069 (1998)]. The nonlinearity predicted previously by Zhou [J. Phys. Chem. 101, 6642 (1997)] in the Lineweaver-Burk plot for the high concentration of substrate with his empirical expression and simulation is correctly obtained by the kinetic theory. We discuss possible errors in the estimation of reaction parameters caused by ignoring this nonlinearity in an experimental analysis (performed at even lower concentrations of the substrate). The time evolution of the production rate shows a peak before it reaches the steady-state value. The long time asymptotic relaxation of the deviation of the enzyme concentration from the steady-state value shows t-1/2 power-law behavior instead of the exponential decay predicted by the classical kinetics.

  11. Kinetic inhibition of natural gas hydrates in offshore drilling, production, and processing operations. Annual report, January 1--December 31, 1992

    SciTech Connect

    1992-12-31

    Natural gas hydrates are solid crystalline compounds which form when molecules smaller than n-butane contact molecules of water at elevated pressures and reduced temperatures, both above and below the ice point. Because these crystalline compounds plug flow channels, they are undesirable. In this project the authors proposed an alternate approach of controlling hydrate formation by preventing hydrate growth into a sizeable mass which could block a flow channel. The authors call this new technique kinetic inhibition, because while it allows the system to exist in the hydrate domain, it prevents the kinetic agglomeration of small hydrate crystals to the point of pluggage of a flow channel. In order to investigate the kinetic means of inhibiting hydrate formation, they held two consortium meetings, on June 1, 1990 and on August 31, 1990. At subsequent meetings, the authors determined the following four stages of the project, necessary to reach the goal of determining a new hydrate field inhibitor: (1) a rapid screening method was to be determined for testing the hydrate kinetic formation period of many surfactants and polymer candidates (both individually and combined), the present report presents the success of two screening apparatuses: a multi-reactor apparatus which is capable of rapid, high volume screening, and the backup screening method--a viscometer for testing with gas at high pressure; (2) the construction of two high, constant pressure cells were to experimentally confirm the success of the chemicals in the rapid screening apparatus; (3) in the third phase of the work, Exxon volunteered to evaluate the performance of the best chemicals from the previous two stages in their 4 inch I.D. Multiphase flow loop in Houston; (4) in the final phase of the work, the intention was to take the successful kinetic inhibition chemicals from the previous three stages and then test them in the field in gathering lines and wells from member companies.

  12. Chemical Kinetics Database

    National Institute of Standards and Technology Data Gateway

    SRD 17 NIST Chemical Kinetics Database (Web, free access)   The NIST Chemical Kinetics Database includes essentially all reported kinetics results for thermal gas-phase chemical reactions. The database is designed to be searched for kinetics data based on the specific reactants involved, for reactions resulting in specified products, for all the reactions of a particular species, or for various combinations of these. In addition, the bibliography can be searched by author name or combination of names. The database contains in excess of 38,000 separate reaction records for over 11,700 distinct reactant pairs. These data have been abstracted from over 12,000 papers with literature coverage through early 2000.

  13. A "Stationery" Kinetics Experiment.

    ERIC Educational Resources Information Center

    Hall, L.; Goberdhansingh, A.

    1988-01-01

    Describes a simple redox reaction that occurs between potassium permanganate and oxalic acid that can be used to prepare an interesting disappearing ink for demonstrating kinetics for introductory chemistry. Discusses laboratory procedures and factors that influence disappearance times. (CW)

  14. Thermal kinetic inductance detector

    DOEpatents

    Cecil, Thomas; Gades, Lisa; Miceli, Antonio; Quaranta, Orlando

    2016-12-20

    A microcalorimeter for radiation detection that uses superconducting kinetic inductance resonators as the thermometers. The detector is frequency-multiplexed which enables detector systems with a large number of pixels.

  15. Fundamentals of enzyme kinetics.

    PubMed

    Seibert, Eleanore; Tracy, Timothy S

    2014-01-01

    This chapter provides a general introduction to the kinetics of enzyme-catalyzed reactions, with a focus on drug-metabolizing enzymes. A prerequisite to understanding enzyme kinetics is having a clear grasp of the meanings of "enzyme" and "catalysis." Catalysts are reagents that can increase the rate of a chemical reaction without being consumed in the reaction. Enzymes are proteins that form a subset of catalysts. These concepts are further explored below.

  16. Quantitative Connection between Ensemble Thermodynamics and Single-Molecule Kinetics: A Case Study Using Cryogenic Electron Microscopy and Single-Molecule Fluorescence Resonance Energy Transfer Investigations of the Ribosome.

    PubMed

    Kinz-Thompson, Colin D; Sharma, Ajeet K; Frank, Joachim; Gonzalez, Ruben L; Chowdhury, Debashish

    2015-08-27

    At equilibrium, thermodynamic and kinetic information can be extracted from biomolecular energy landscapes by many techniques. However, while static, ensemble techniques yield thermodynamic data, often only dynamic, single-molecule techniques can yield the kinetic data that describe transition-state energy barriers. Here we present a generalized framework based upon dwell-time distributions that can be used to connect such static, ensemble techniques with dynamic, single-molecule techniques, and thus characterize energy landscapes to greater resolutions. We demonstrate the utility of this framework by applying it to cryogenic electron microscopy (cryo-EM) and single-molecule fluorescence resonance energy transfer (smFRET) studies of the bacterial ribosomal pre-translocation complex. Among other benefits, application of this framework to these data explains why two transient, intermediate conformations of the pre-translocation complex, which are observed in a cryo-EM study, may not be observed in several smFRET studies.

  17. Theoretical investigation of the origin of the multipeak structure of kinetic-energy-release spectra from charge-resonance-enhanced ionization of H{sub 2}{sup +} in intense laser fields

    SciTech Connect

    He Haixiang; Guo Yahui; Lu Ruifeng; Zhang Peiyu; Han Keli; He Guozhong

    2011-09-15

    The dynamics of hydrogen molecular ions in intense laser pulses (100 fs, I = 0.77 x 10{sup 14} W/cm{sup 2} to 2.5 x 10{sup 14} W/cm{sup 2}) has been studied, and the kinetic-energy-release spectra of Coulomb explosion channel have been calculated by numerically solving the time-dependent Schroedinger equation. In a recent experiment, a multipeak structure from charge-resonance-enhanced ionization is interpreted by a vibrational 'comb' at a critical nuclear distance. We found that the peaks could not be attributed to a single vibrational level but a collective contribution of some typical vibrational states in our calculated Coulomb explosion spectra, and the main peak shifts toward the low-energy region with increasing vibrational level, which is also different from the explanation in that experiment. We have also discussed the proton's kinetic-energy-release spectra for different durations with the same laser intensity.

  18. Kinetic Description of the Impedance Probe

    NASA Astrophysics Data System (ADS)

    Oberrath, Jens; Lapke, Martin; Mussenbrock, Thomas; Brinkmann, Ralf

    2011-10-01

    Active plasma resonance spectroscopy is a well known diagnostic method. Many concepts of this method are theoretically investigated and realized as a diagnostic tool, one of which is the impedance probe (IP). The application of such a probe in plasmas with pressures of a few Pa raises the question whether kinetic effects have to be taken into account or not. To address this question a kinetic model is necessary. A general kinetic model for an electrostatic concept of active plasma spectroscopy was presented by R.P. Brinkmann and can be used to describe the multipole resonance probe (MRP). In principle the IP is interpretable as a special case of the MRP in lower order. Thus, we are able to describe the IP by the kinetic model of the MRP. Based on this model we derive a solution to investigate the influence of kinetic effects to the resonance behavior of the IP. Active plasma resonance spectroscopy is a well known diagnostic method. Many concepts of this method are theoretically investigated and realized as a diagnostic tool, one of which is the impedance probe (IP). The application of such a probe in plasmas with pressures of a few Pa raises the question whether kinetic effects have to be taken into account or not. To address this question a kinetic model is necessary. A general kinetic model for an electrostatic concept of active plasma spectroscopy was presented by R.P. Brinkmann and can be used to describe the multipole resonance probe (MRP). In principle the IP is interpretable as a special case of the MRP in lower order. Thus, we are able to describe the IP by the kinetic model of the MRP. Based on this model we derive a solution to investigate the influence of kinetic effects to the resonance behavior of the IP. The authors acknowledge the support by the Deutsche Forschungsgemeinschaft (DFG) via the Ruhr University Research School and the Federal Ministry of Education and Research in frame of the PluTO project.

  19. Reaction kinetics of cellulose hydrolysis in subcritical and supercritical water

    NASA Astrophysics Data System (ADS)

    Olanrewaju, Kazeem Bode

    The uncertainties in the continuous supply of fossil fuels from the crisis-ridden oil-rich region of the world is fast shifting focus on the need to utilize cellulosic biomass and develop more efficient technologies for its conversion to fuels and chemicals. One such technology is the rapid degradation of cellulose in supercritical water without the need for an enzyme or inorganic catalyst such as acid. This project focused on the study of reaction kinetics of cellulose hydrolysis in subcritical and supercritical water. Cellulose reactions at hydrothermal conditions can proceed via the homogeneous route involving dissolution and hydrolysis or the heterogeneous path of surface hydrolysis. The work is divided into three main parts. First, the detailed kinetic analysis of cellulose reactions in micro- and tubular reactors was conducted. Reaction kinetics models were applied, and kinetics parameters at both subcritical and supercritical conditions were evaluated. The second major task was the evaluation of yields of water soluble hydrolysates obtained from the hydrolysis of cellulose and starch in hydrothermal reactors. Lastly, changes in molecular weight distribution due to hydrothermolytic degradation of cellulose were investigated. These changes were also simulated based on different modes of scission, and the pattern generated from simulation was compared with the distribution pattern from experiments. For a better understanding of the reaction kinetics of cellulose in subcritical and supercritical water, a series of reactions was conducted in the microreactor. Hydrolysis of cellulose was performed at subcritical temperatures ranging from 270 to 340 °C (tau = 0.40--0.88 s). For the dissolution of cellulose, the reaction was conducted at supercritical temperatures ranging from 375 to 395 °C (tau = 0.27--0.44 s). The operating pressure for the reactions at both subcritical and supercritical conditions was 5000 psig. The results show that the rate-limiting step in

  20. Quantifying kinetics from time series of single-molecule Förster resonance energy transfer efficiency histograms.

    PubMed

    Benke, Stephan; Nettels, Daniel; Hofmann, Hagen; Schuler, Benjamin

    2017-03-17

    Single-molecule fluorescence spectroscopy is a powerful approach for probing biomolecular structure and dynamics, including protein folding. For the investigation of nonequilibrium kinetics, Förster resonance energy transfer combined with confocal multiparameter detection has proven particularly versatile, owing to the large number of observables and the broad range of accessible timescales, especially in combination with rapid microfluidic mixing. However, a comprehensive kinetic analysis of the resulting time series of transfer efficiency histograms and complementary observables can be challenging owing to the complexity of the data. Here we present and compare three different methods for the analysis of such kinetic data: singular value decomposition, multivariate curve resolution with alternating least square fitting, and model-based peak fitting, where an explicit model of both the transfer efficiency histogram of each species and the kinetic mechanism of the process is employed. While each of these methods has its merits for specific applications, we conclude that model-based peak fitting is most suitable for a quantitative analysis and comparison of kinetic mechanisms.

  1. Quantifying kinetics from time series of single-molecule Förster resonance energy transfer efficiency histograms

    NASA Astrophysics Data System (ADS)

    Benke, Stephan; Nettels, Daniel; Hofmann, Hagen; Schuler, Benjamin

    2017-03-01

    Single-molecule fluorescence spectroscopy is a powerful approach for probing biomolecular structure and dynamics, including protein folding. For the investigation of nonequilibrium kinetics, Förster resonance energy transfer combined with confocal multiparameter detection has proven particularly versatile, owing to the large number of observables and the broad range of accessible timescales, especially in combination with rapid microfluidic mixing. However, a comprehensive kinetic analysis of the resulting time series of transfer efficiency histograms and complementary observables can be challenging owing to the complexity of the data. Here we present and compare three different methods for the analysis of such kinetic data: singular value decomposition, multivariate curve resolution with alternating least square fitting, and model-based peak fitting, where an explicit model of both the transfer efficiency histogram of each species and the kinetic mechanism of the process is employed. While each of these methods has its merits for specific applications, we conclude that model-based peak fitting is most suitable for a quantitative analysis and comparison of kinetic mechanisms.

  2. Thermodynamic, Kinetic, and Equilibrium Parameters for the Removal of Lead and Cadmium from Aqueous Solutions with Calcium Alginate Beads

    PubMed Central

    Alfaro-Cuevas-Villanueva, Ruth; Hidalgo-Vázquez, Aura Roxana; Cortés Penagos, Consuelo de Jesús; Cortés-Martínez, Raúl

    2014-01-01

    The sorption of cadmium (Cd) and lead (Pb) by calcium alginate beads (CAB) from aqueous solutions in batch systems was investigated. The kinetic and thermodynamic parameters, as well as the sorption capacities of CAB in each system at different temperatures, were evaluated. The rate of sorption for both metals was rapid in the first 10 minutes and reached a maximum in 50 minutes. Sorption kinetic data were fitted to Lagergren, pseudo-second-order and Elovich models and it was found that the second-order kinetic model describes these data for the two metals; comparing kinetic parameters for Cd and Pb sorption a higher kinetic rate (K2) for Pb was observed, indicating that the interaction between lead cations and alginate beads was faster than for cadmium. Similarly, isotherm data were fitted to different models reported in literature and it was found that the Langmuir-Freundlich (L-F) and Dubinin-Radushkevich (D-R) models describe the isotherms in all cases. CAB sorption capacity for cadmium was 27.4 mg/g and 150.4 mg/g for lead, at 25°C. Sorption capacities of Cd and Pb increase as temperature rises. According to the thermodynamic parameters, the cadmium and lead adsorption process was spontaneous and endothermic. It was also found that pH has an important effect on the adsorption of these metals by CAB, as more were removed at pH values between 6 and 7. PMID:24587740

  3. Kinetics and reversibility of micropollutant sorption in sludge.

    PubMed

    Barret, Maialen; Carrère, Hélène; Patau, Mathieu; Patureau, Dominique

    2011-10-01

    The fate of micropollutants throughout wastewater treatment systems is highly dependent on their sorption interactions with sludge matter. In this study, both the sorption and desorption kinetics of polycyclic aromatic hydrocarbons (PAHs) in activated sludge were shown to be very rapid in comparison to biodegradation kinetics. It was concluded that PAH transfer does not limit their biodegradation and that their fate is governed by the sorption/desorption equilibrium state. The effect of contact time between sludge and PAHs was also investigated. It was shown that aging did not influence the sorption/desorption equilibrium although PAH losses during aging suggest that sequestration phenomena had occurred. This implies that for PAH sorption assessment within treatment processes there is no need to include a contact time dimension. As a consequence, thanks to an innovative approach taking into account sorption equilibria and sequestration, this work has demonstrated that studies in the literature which, in main, deal with micropollutant sorption in sewage sludge with only a short contact time can be extrapolated to real systems in which sorption, desorption and aging occur.

  4. Alterations in glucose kinetics induced by pentobarbital anesthesia

    SciTech Connect

    Lang, C.H.; Bagby, G.J.; Hargrove, D.M.; Hyde, P.M.; Spitzer, J.J. )

    1987-12-01

    Because pentobarbital is often used in investigations related to carbohydrate metabolism, the in vivo effect of this drug on glucose homeostasis was studied. Glucose kinetics assessed by the constant intravenous infusion of (6-{sup 3}H)- and (U-{sup 14}C)glucose, were determined in three groups of catheterized fasted rats: conscious, anesthetized and body temperature maintained, and anesthetized but body temperature not maintained. After induction of anesthesia, marked hypothermia developed in rats not provided with external heat. Anesthetized rats that developed hypothermia showed a decrease in mean arterial blood pressure (25%) and heart rate (40%). Likewise, the plasma lactate concentration and the rates of glucose appearance, recycling, and metabolic clearance were reduced by 30-50% in the hypothermic anesthetized rats. Changes in whole-body carbohydrate metabolism were prevented when body temperature was maintained. Because plasma pentobarbital levels were similar between the euthermic and hypothermic rats during the first 2 h of the experiment, the rapid reduction in glucose metabolism in this latter group appears related to the decrease in body temperature. The continuous infusion of epinephrine produced alterations in glucose kinetics that were not different between conscious animals and anesthetized rats with body temperature maintained. Thus pentobarbital-anesthetized rats became hypothermic when kept at room temperature and exhibited marked decreases in glucose metabolism. Such changes were absent when body temperature was maintained during anesthesia.

  5. Kinetics of Uranium Extraction from Uranium Tailings by Oxidative Leaching

    NASA Astrophysics Data System (ADS)

    Zhang, Biao; Li, Mi; Zhang, Xiaowen; Huang, Jing

    2016-07-01

    Extraction of uranium from uranium tailings by oxidative leaching with hydrogen peroxide (H2O2) was studied. The effects of various extraction factors were investigated to optimize the dissolution conditions, as well as to determine the leaching kinetic parameters. The behavior of H2O2 in the leaching process was determined through scanning electron microscopy-energy dispersive x-ray spectroscopy (SEM-EDX) and x-ray diffraction analysis of leaching residues. Results suggest that H2O2 can significantly improve uranium extraction by decomposing the complex gangue structures in uranium tailings and by enhancing the reaction rate between uranium phases and the leaching agent. The extraction kinetics expression was changed from 1 - 3(1 - α)2/3 + 2(1 - α) = K 0(H2SO4)-0.14903(S/L)-1.80435( R o)0.20023 e -1670.93/T t ( t ≥ 5) to 1 - 3(1 - α)2/3 + 2(1 - α) = K 0(H2SO4)0.01382(S/L)-1.83275( R o)0.25763 e -1654.59/T t ( t ≥ 5) by the addition of H2O2 in the leaching process. The use of H2O2 in uranium leaching may help in extracting uranium more efficiently and rapidly from low-uranium-containing ores or tailings.

  6. Rapid Decisions From Experience

    PubMed Central

    Zeigenfuse, Matthew D.; Pleskac, Timothy J.; Liu, Taosheng

    2014-01-01

    In many everyday decisions, people quickly integrate noisy samples of information to form a preference among alternatives that offer uncertain rewards. Here, we investigated this decision process using the Flash Gambling Task (FGT), in which participants made a series of choices between a certain payoff and an uncertain alternative that produced a normal distribution of payoffs. For each choice, participants experienced the distribution of payoffs via rapid samples updated every 50 ms. We show that people can make these rapid decisions from experience and that the decision process is consistent with a sequential sampling process. Results also reveal a dissociation between these preferential decisions and equivalent perceptual decisions where participants had to determine which alternatives contained more dots on average. To account for this dissociation, we developed a sequential sampling rank-dependent utility model, which showed that participants in the FGT attended more to larger potential payoffs than participants in the perceptual task despite being given equivalent information. We discuss the implications of these findings in terms of computational models of preferential choice and a more complete understanding of experience-based decision making. PMID:24549141

  7. PUBLISHER'S NOTE: Rapid Communications Rapid Communications

    NASA Astrophysics Data System (ADS)

    Miller, Tom

    2009-09-01

    As part of a general review of Superconductor Science and Technology, we have been examining the scope for Rapid Communications (RAPs). We recognize these articles make up an important part of the journal representing the latest state-of-the-art research in superconductivity. To reflect this, we have devised a new scope for this article type: 'Rapid Communications. The journal offers open access to outstanding short articles (no longer than 5 journal pages or 4500 words including figures) reporting new and timely developments in superconductivity and its applications. These articles should report very substantial new advances in superconductivity to the readers of Superconductor Science and Technology, but are not expected to meet any requirement of 'general interest'. RAPs will be processed quickly (average receipt to online publication for RAPs is around 60 days) and are permanently free to read in the electronic journal. Authors submitting a RAP should provide reasons why the work is urgent and requires rapid publication. Each RAP will be assessed for suitability by our Reviews and Rapid Communications Editor before full peer review takes place.' The essential points are: They should report very substantial new advances in superconductivity and its application; They must be no longer than 5 journal pages long (approx. 4500 words); Average publication time for a Rapid Communication is 60 days; They are free to read. As mentioned in the previous publisher's announcement (2009 Supercond. Sci. Technol. 22 010101), each submitted Rapid Communication must come with a letter justifying why it should be prioritized over regular papers and will be pre-assessed by our Reviews and Rapid Communications Editor. In addition, we will work with the authors of any Rapid Communication to promote and raise the visibility of the work presented in it. We will be making further changes to the journal in the near future and we write to you accordingly. Thank you for your kind

  8. Multiple alternative substrate kinetics.

    PubMed

    Anderson, Vernon E

    2015-11-01

    The specificity of enzymes for their respective substrates has been a focal point of enzyme kinetics since the initial characterization of metabolic chemistry. Various processes to quantify an enzyme's specificity using kinetics have been utilized over the decades. Fersht's definition of the ratio kcat/Km for two different substrates as the "specificity constant" (ref [7]), based on the premise that the important specificity existed when the substrates were competing in the same reaction, has become a consensus standard for enzymes obeying Michaelis-Menten kinetics. The expansion of the theory for the determination of the relative specificity constants for a very large number of competing substrates, e.g. those present in a combinatorial library, in a single reaction mixture has been developed in this contribution. The ratio of kcat/Km for isotopologs has also become a standard in mechanistic enzymology where kinetic isotope effects have been measured by the development of internal competition experiments with extreme precision. This contribution extends the theory of kinetic isotope effects to internal competition between three isotopologs present at non-tracer concentrations in the same reaction mix. This article is part of a special issue titled: Enzyme Transition States from Theory and Experiment.

  9. Rapid diagnosis of sepsis

    PubMed Central

    Bloos, Frank; Reinhart, Konrad

    2014-01-01

    Fast and appropriate therapy is the cornerstone in the therapy of sepsis. However, the discrimination of sepsis from non-infectious causes of inflammation may be difficult. Biomarkers have been suggested to aid physicians in this decision. There is currently no biochemical technique available which alone allows a rapid and reliable discrimination between sepsis and non-infectious inflammation. Procalcitonin (PCT) is currently the most investigated biomarker for this purpose. C-reactive protein and interleukin 6 perform inferior to PCT in most studies and their value in diagnosing sepsis is not defined. All biomarkers including PCT are also released after various non-infectious inflammatory impacts. This shortcoming needs to be taken into account when biomarkers are used to aid the physician in the diagnosis of sepsis. Polymerase chain reaction (PCR) based pathogen detection may improve time to adequate therapy but cannot rule out the presence of infection when negative. PMID:24335467

  10. Vibrational relaxation and isomerization kinetics of alcohols

    NASA Astrophysics Data System (ADS)

    Self-Medlin, Yehudi

    The vibrational dynamics of the O-H stretch was investigated for a series of alcohols in room temperature gas-phase and dilute solution. A set of alcohols with one stable conformer was measured to determine the intramolecular vibrational energy redistribution (IVR) timescales of basic alcohols for comparison of the isolated to solvated molecule dynamics. It was determined from these experiments the IVR rate of the O-H stretch is unaffected by the presence of solvent. Next, population transfer rates were measured from the initially excited O-H stretch through the molecule to the v = 1 acetylenic C-H bending mode of a series of alkynols. It was found that the IVR and population transfer rates were almost independent of molecule size, distance between the O-H and acetylene moiety, or branching size. However, the excited O-H stretch exhibits very little transfer to the C-H stretch or C-H bend overtone, indicating a mode-specific redistribution pathway. The data, as well as ab initio calculations, suggest non-statistical relaxation of the O-H stretch excited state population through a subset of C-H bending states. Determining the timescales of intramolecular relaxation and population transfer establishes a foundation for developing methods to enhance chemical reactions with lasers. A preliminary step towards this goal is the study of conformational isomerization. The IVR lifetime is the rate limiting step in vibrationally-induced isomerization kinetics. The conformational isomerization takes places so rapidly after IVR completion that it could not be detected with the available time resolution. However, excited state absorption signal was used as a molecular probe to measure the thermal isomerization created by collisions with solvent. The kinetic rate constants of the thermal isomerization were determined from the transient absorption spectra in combination with fixed time frequency scans of the entire absorption and bleach region. The experimentally determined values

  11. Relativistic Chiral Kinetic Theory

    NASA Astrophysics Data System (ADS)

    Stephanov, Mikhail

    2016-12-01

    This very brief review of the recent progress in chiral kinetic theory is based on the results of Refs. [J.-Y. Chen, D. T. Son, M. A. Stephanov, H.-U. Yee, Y. Yin, Lorentz Invariance in Chiral Kinetic Theory, Phys. Rev. Lett. 113 (18) (2014) 182302. doi:10.1103/PhysRevLett.113.182302; J.-Y. Chen, D. T. Son, M. A. Stephanov, Collisions in Chiral Kinetic Theory, Phys. Rev. Lett. 115 (2) (2015) 021601. doi: 10.1103/PhysRevLett.115.021601; M. A. Stephanov, H.-U. Yee, The no-drag frame for anomalous chiral fluid, Phys. Rev. Lett. 116 (12) (2016) 122302. doi: 10.1103/PhysRevLett.116.122302].

  12. Rapidly-deposited polydopamine coating via high temperature and vigorous stirring: formation, characterization and biofunctional evaluation.

    PubMed

    Zhou, Ping; Deng, Yi; Lyu, Beier; Zhang, Ranran; Zhang, Hai; Ma, Hongwei; Lyu, Yalin; Wei, Shicheng

    2014-01-01

    Polydopamine (PDA) coating provides a promising approach for immobilization of biomolecules onto almost all kinds of solid substrates. However, the deposition kinetics of PDA coating as a function of temperature and reaction method is not well elucidated. Since dopamine self-polymerization usually takes a long time, therefore, rapid-formation of PDA film becomes imperative for surface modification of biomaterials and medical devices. In the present study, a practical method for preparation of rapidly-deposited PDA coating was developed using a uniquely designed device, and the kinetics of dopamine self-polymerization was investigated by QCM sensor system. It was found that high temperature and vigorous stirring could dramatically speed up the formation of PDA film on QCM chip surface. Surface characterization, BSA binding study, cell viability assay and antibacterial test demonstrates that the polydopamine coating after polymerization for 30 min by our approach exhibits similar properties to those of 24 h counterpart. The method has a great potential for rapid-deposition of polydopamine films to modify biomaterial surfaces.

  13. Effect of Temperature and Sheet Temper on Isothermal Solidification Kinetics in Clad Aluminum Brazing Sheet

    NASA Astrophysics Data System (ADS)

    Benoit, Michael J.; Whitney, Mark A.; Wells, Mary A.; Winkler, Sooky

    2016-09-01

    Isothermal solidification (IS) is a phenomenon observed in clad aluminum brazing sheets, wherein the amount of liquid clad metal is reduced by penetration of the liquid clad into the core. The objective of the current investigation is to quantify the rate of IS through the use of a previously derived parameter, the Interface Rate Constant (IRC). The effect of peak temperature and initial sheet temper on IS kinetics were investigated. The results demonstrated that IS is due to the diffusion of silicon (Si) from the liquid clad layer into the solid core. Reduced amounts of liquid clad at long liquid duration times, a roughened sheet surface, and differences in resolidified clad layer morphology between sheet tempers were observed. Increased IS kinetics were predicted at higher temperatures by an IRC model as well as by experimentally determined IRC values; however, the magnitudes of these values are not in good agreement due to deficiencies in the model when applied to alloys. IS kinetics were found to be higher for sheets in the fully annealed condition when compared with work-hardened sheets, due to the influence of core grain boundaries providing high diffusivity pathways for Si diffusion, resulting in more rapid liquid clad penetration.

  14. Kinetic equilibria of very high- β plasmas

    NASA Astrophysics Data System (ADS)

    Steinhauer, Loren; TAE Team

    2015-11-01

    Plasma equilibria with many large ion orbits, such as an advanced beam-driven field-reversed configuration, are neither static (Grad-Shafranov) nor describable as a flowing, multi-fluid. A fully-kinetic treatment of the ions is essential for such high- β plasmas. A kinetic equilibrium is needed to properly support realistic stability and transport analyses, both of which are strongly affected by large-orbit ions. A hybrid equilibrium model has been developed with a fully-kinetic treatment of both thermal ions and a rapidly-rotating ``beam-ion'' component, such as produced by neutral beam injection, relevant to the C-2U experiments at TAE. It employs analytic Vlasov solutions in that the distribution depends only on the two constants of motion, the Hamiltonian (H) and the canonical angular momentum (Pθ) . Electrons are treated as a pressure-bearing fluid. Since realistic forms of f (H ,Pθ) are affected by collisions, f is limited to solutions of a simplified Fokker-Planck equation. Importantly, a kinetic end-loss condition applies to unconfined ions, using a particle sink at a rate consistent with Monte-Carlo-like simulations of end loss accounting for a strong end mirror.

  15. Ammonium Removal from Aqueous Solutions by Clinoptilolite: Determination of Isotherm and Thermodynamic Parameters and Comparison of Kinetics by the Double Exponential Model and Conventional Kinetic Models

    PubMed Central

    Tosun, İsmail

    2012-01-01

    The adsorption isotherm, the adsorption kinetics, and the thermodynamic parameters of ammonium removal from aqueous solution by using clinoptilolite in aqueous solution was investigated in this study. Experimental data obtained from batch equilibrium tests have been analyzed by four two-parameter (Freundlich, Langmuir, Tempkin and Dubinin-Radushkevich (D-R)) and four three-parameter (Redlich-Peterson (R-P), Sips, Toth and Khan) isotherm models. D-R and R-P isotherms were the models that best fitted to experimental data over the other two- and three-parameter models applied. The adsorption energy (E) from the D-R isotherm was found to be approximately 7 kJ/mol for the ammonium-clinoptilolite system, thereby indicating that ammonium is adsorbed on clinoptilolite by physisorption. Kinetic parameters were determined by analyzing the nth-order kinetic model, the modified second-order model and the double exponential model, and each model resulted in a coefficient of determination (R2) of above 0.989 with an average relative error lower than 5%. A Double Exponential Model (DEM) showed that the adsorption process develops in two stages as rapid and slow phase. Changes in standard free energy (∆G°), enthalpy (∆H°) and entropy (∆S°) of ammonium-clinoptilolite system were estimated by using the thermodynamic equilibrium coefficients. PMID:22690177

  16. Ammonium removal from aqueous solutions by clinoptilolite: determination of isotherm and thermodynamic parameters and comparison of kinetics by the double exponential model and conventional kinetic models.

    PubMed

    Tosun, Ismail

    2012-03-01

    The adsorption isotherm, the adsorption kinetics, and the thermodynamic parameters of ammonium removal from aqueous solution by using clinoptilolite in aqueous solution was investigated in this study. Experimental data obtained from batch equilibrium tests have been analyzed by four two-parameter (Freundlich, Langmuir, Tempkin and Dubinin-Radushkevich (D-R)) and four three-parameter (Redlich-Peterson (R-P), Sips, Toth and Khan) isotherm models. D-R and R-P isotherms were the models that best fitted to experimental data over the other two- and three-parameter models applied. The adsorption energy (E) from the D-R isotherm was found to be approximately 7 kJ/mol for the ammonium-clinoptilolite system, thereby indicating that ammonium is adsorbed on clinoptilolite by physisorption. Kinetic parameters were determined by analyzing the nth-order kinetic model, the modified second-order model and the double exponential model, and each model resulted in a coefficient of determination (R(2)) of above 0.989 with an average relative error lower than 5%. A Double Exponential Model (DEM) showed that the adsorption process develops in two stages as rapid and slow phase. Changes in standard free energy (∆G°), enthalpy (∆H°) and entropy (∆S°) of ammonium-clinoptilolite system were estimated by using the thermodynamic equilibrium coefficients.

  17. The Kinetics of Phase Transformation in Welds

    SciTech Connect

    Elmer, J W; Wong, J; Palmer, T

    2002-02-06

    that existed in the HAZ during welding. The TRXRD technique uses an x-ray beam positioned at one location, where XRD patterns are collected as a stationary ''spot'' weld rapidly heats and cools the base metal. Data can be collected from either the HAZ to observe solid-state phase transformations or from the FZ to observe solidification and subsequent solid-state phase transformations. Higher heating and cooling rates are produced in the spot welds than in the moving welds, requiring time resolution in the milli-second regime for TRXRD to record the rapid microstructural changes that occur. Numerical weld modeling is being performed to: (1) extract the important phase transformation kinetic information from the experimental data, (2) investigate mechanisms of phase transformations under non-isothermal welding conditions, and (3) develop models for predicting weld microstructural evolution. The core of our numerical weld modeling program is a 3-dimensional coupled heat and fluid flow code developed by the Penn State University. Additional modeling is being performed at Oak Ridge National Laboratory where Thermocalc is being used to understand phase equilibria in complex alloy systems, and where a diffusion-based model considering paraequilibrium is being developed to predict phase transformations in steels.

  18. Rapid self-healing hydrogels

    PubMed Central

    Phadke, Ameya; Zhang, Chao; Arman, Bedri; Hsu, Cheng-Chih; Mashelkar, Raghunath A.; Lele, Ashish K.; Tauber, Michael J.; Arya, Gaurav; Varghese, Shyni

    2012-01-01

    Synthetic materials that are capable of autonomous healing upon damage are being developed at a rapid pace because of their many potential applications. Despite these advancements, achieving self-healing in permanently cross-linked hydrogels has remained elusive because of the presence of water and irreversible cross-links. Here, we demonstrate that permanently cross-linked hydrogels can be engineered to exhibit self-healing in an aqueous environment. We achieve this feature by arming the hydrogel network with flexible-pendant side chains carrying an optimal balance of hydrophilic and hydrophobic moieties that allows the side chains to mediate hydrogen bonds across the hydrogel interfaces with minimal steric hindrance and hydrophobic collapse. The self-healing reported here is rapid, occurring within seconds of the insertion of a crack into the hydrogel or juxtaposition of two separate hydrogel pieces. The healing is reversible and can be switched on and off via changes in pH, allowing external control over the healing process. Moreover, the hydrogels can sustain multiple cycles of healing and separation without compromising their mechanical properties and healing kinetics. Beyond revealing how secondary interactions could be harnessed to introduce new functions to chemically cross-linked polymeric systems, we also demonstrate various potential applications of such easy-to-synthesize, smart, self-healing hydrogels. PMID:22392977

  19. Anthocyanin kinetics are dependent on anthocyanin structure

    Technology Transfer Automated Retrieval System (TEKTRAN)

    The kinetics of anthocyanin metabolism was investigated in a human feeding trial. Volunteers (n=12) consumed purple carrots containing five different anthocyanin forms: cyanidin-3-(2”-xylose-6”-glucose-galactoside), cyanidin-3-(2”-xylose-galactoside), cyanidin-3-(2”-xylose-6”-sinapoyl-glucose-galac...

  20. Ultracold chemistry and its reaction kinetics

    NASA Astrophysics Data System (ADS)

    Richter, Florian; Becker, Daniel; Bény, Cédric; Schulze, Torben A.; Ospelkaus, Silke; Osborne, Tobias J.

    2015-05-01

    We study the reaction kinetics of chemical processes occurring in the ultracold regime and systematically investigate their dynamics. Quantum entanglement is found to play a key role in driving an ultracold reaction towards a dynamical equilibrium. In case of multiple concurrent reactions Hamiltonian chaos dominates the phase space dynamics in the mean field approximation.

  1. Adsorption Kinetics in Nanoscale Porous Coordination Polymers

    SciTech Connect

    Nune, Satish K.; Thallapally, Praveen K.; McGrail, Benard Peter; Annapureddy, Harsha V. R.; Dang, Liem X.; Mei, Donghai; Karri, Naveen; Alvine, Kyle J.; Olszta, Matthew J.; Arey, Bruce W.; Dohnalkova, Alice

    2015-10-07

    Nanoscale porous coordination polymers were synthesized using simple wet chemical method. The effect of various polymer surfactants on colloidal stability and shape selectivity was investigated. Our results suggest that the nanoparticles exhibited significantly improved adsorption kinetics compared to bulk crystals due to decreased diffusion path lengths and preferred crystal plane interaction.

  2. Barrierless growth of precursor-free, ultrafast laser-fragmented noble metal nanoparticles by colloidal atom clusters - A kinetic in situ study.

    PubMed

    Jendrzej, Sandra; Gökce, Bilal; Amendola, Vincenzo; Barcikowski, Stephan

    2016-02-01

    Unintended post-synthesis growth of noble metal colloids caused by excess amounts of reactants or highly reactive atom clusters represents a fundamental problem in colloidal chemistry, affecting product stability or purity. Hence, quantified kinetics could allow defining nanoparticle size determination in dependence of the time. Here, we investigate in situ the growth kinetics of ps pulsed laser-fragmented platinum nanoparticles in presence of naked atom clusters in water without any influence of reducing agents or surfactants. The nanoparticle growth is investigated for platinum covering a time scale of minutes to 50days after nanoparticle generation, it is also supplemented by results obtained from gold and palladium. Since a minimum atom cluster concentration is exceeded, a significant growth is determined by time resolved UV/Vis spectroscopy, analytical disc centrifugation, zeta potential measurement and transmission electron microscopy. We suggest a decrease of atom cluster concentration over time, since nanoparticles grow at the expense of atom clusters. The growth mechanism during early phase (<1day) of laser-synthesized colloid is kinetically modeled by rapid barrierless coalescence. The prolonged slow nanoparticle growth is kinetically modeled by a combination of coalescence and Lifshitz-Slyozov-Wagner kinetic for Ostwald ripening, validated experimentally by the temperature dependence of Pt nanoparticle size and growth quenching by Iodide anions.

  3. The Kinetic Chain in Overhand Pitching

    PubMed Central

    Seroyer, Shane T.; Nho, Shane J.; Bach, Bernard R.; Bush-Joseph, Charles A.; Nicholson, Gregory P.; Romeo, Anthony A.

    2010-01-01

    The overhead throwing motion is a coordinated effort of muscle units from the entire body, culminating with explosive motion of the upper extremity. The throwing motion occurs at a rapid pace, making analysis difficult in real time. Electromyographic studies and high-speed video recordings have provided invaluable details regarding the involved musculature, the sequence of muscle involvement, and associated kinematic variables. The goal of the present article is to provide an overview of the kinetic chain—that is, a detailed description of the muscular coordination during each phase of pitching—and to describe specific types of pitches. An enhanced understanding of the components of the kinetic chain and the phases of the throwing motion can provide important information for rehabilitation, performance enhancement, and injury prevention. PMID:23015931

  4. Kinetic tetrazolium microtiter assay

    NASA Technical Reports Server (NTRS)

    Pierson, Duane L. (Inventor); Stowe, Raymond P. (Inventor); Koeing, David W. (Inventor)

    1992-01-01

    A method for conducting an in vitro cell assay using a tetrazolium indicator is disclosed. The indicator includes a nonionic detergent which solubilizes a tetrazolium reduction product in vitro and has low toxicity for the cells. The incubation of test cells in the presence of zolium bromide and octoxynol (TRITON X-100) permits kinetics of the cell metabolism to be determined.

  5. Kinetics and Catalysis Demonstrations.

    ERIC Educational Resources Information Center

    Falconer, John L.; Britten, Jerald A.

    1984-01-01

    Eleven videotaped kinetics and catalysis demonstrations are described. Demonstrations include the clock reaction, oscillating reaction, hydrogen oxidation in air, hydrogen-oxygen explosion, acid-base properties of solids, high- and low-temperature zeolite reactivity, copper catalysis of ammonia oxidation and sodium peroxide decomposition, ammonia…

  6. Oxidative desulfurization: kinetic modelling.

    PubMed

    Dhir, S; Uppaluri, R; Purkait, M K

    2009-01-30

    Increasing environmental legislations coupled with enhanced production of petroleum products demand, the deployment of novel technologies to remove organic sulfur efficiently. This work represents the kinetic modeling of ODS using H(2)O(2) over tungsten-containing layered double hydroxide (LDH) using the experimental data provided by Hulea et al. [V. Hulea, A.L. Maciuca, F. Fajula, E. Dumitriu, Catalytic oxidation of thiophenes and thioethers with hydrogen peroxide in the presence of W-containing layered double hydroxides, Appl. Catal. A: Gen. 313 (2) (2006) 200-207]. The kinetic modeling approach in this work initially targets the scope of the generation of a superstructure of micro-kinetic reaction schemes and models assuming Langmuir-Hinshelwood (LH) and Eley-Rideal (ER) mechanisms. Subsequently, the screening and selection of above models is initially based on profile-based elimination of incompetent schemes followed by non-linear regression search performed using the Levenberg-Marquardt algorithm (LMA) for the chosen models. The above analysis inferred that Eley-Rideal mechanism describes the kinetic behavior of ODS process using tungsten-containing LDH, with adsorption of reactant and intermediate product only taking place on the catalyst surface. Finally, an economic index is presented that scopes the economic aspects of the novel catalytic technology with the parameters obtained during regression analysis to conclude that the cost factor for the catalyst is 0.0062-0.04759 US $ per barrel.

  7. Rapid CE-UV binding tests of environmentally hazardous compounds with polymer-modified magnetic nanoparticles.

    PubMed

    Iqbal, Zafar; Alsudir, Samar; Miah, Musharraf; Lai, Edward P C

    2011-08-01

    Hazardous compounds and bacteria in water have an adverse impact on human health and environmental ecology. Polydopamine (or polypyrrole)-coated magnetic nanoparticles and polymethacrylic acid-co-ethylene glycol dimethacrylate submicron particles were investigated for their fast binding kinetics with bisphenol A, proflavine, naphthalene acetic acid, and Escherichia coli. A new method was developed for the rapid determination of % binding by sequential injection of particles first and compounds (or E. coli) next into a fused-silica capillary for overlap binding during electrophoretic migration. Only nanolitre volumes of compounds and particles were sufficient to complete a rapid binding test. After heterogeneous binding, separation of the compounds from the particles was afforded by capillary electrophoresis. % binding was influenced by applied voltage but not current flow. In-capillary coating of particles affected the % binding of compounds.

  8. A Conserved Residue Cluster That Governs Kinetics of ATP-dependent Gating of Kir6.2 Potassium Channels.

    PubMed

    Zhang, Roger S; Wright, Jordan D; Pless, Stephan A; Nunez, John-Jose; Kim, Robin Y; Li, Jenny B W; Yang, Runying; Ahern, Christopher A; Kurata, Harley T

    2015-06-19

    ATP-sensitive potassium (KATP) channels are heteromultimeric complexes of an inwardly rectifying Kir channel (Kir6.x) and sulfonylurea receptors. Their regulation by intracellular ATP and ADP generates electrical signals in response to changes in cellular metabolism. We investigated channel elements that control the kinetics of ATP-dependent regulation of KATP (Kir6.2 + SUR1) channels using rapid concentration jumps. WT Kir6.2 channels re-open after rapid washout of ATP with a time constant of ∼60 ms. Extending similar kinetic measurements to numerous mutants revealed fairly modest effects on gating kinetics despite significant changes in ATP sensitivity and open probability. However, we identified a pair of highly conserved neighboring amino acids (Trp-68 and Lys-170) that control the rate of channel opening and inhibition in response to ATP. Paradoxically, mutations of Trp-68 or Lys-170 markedly slow the kinetics of channel opening (500 and 700 ms for W68L and K170N, respectively), while increasing channel open probability. Examining the functional effects of these residues using φ value analysis revealed a steep negative slope. This finding implies that these residues play a role in lowering the transition state energy barrier between open and closed channel states. Using unnatural amino acid incorporation, we demonstrate the requirement for a planar amino acid at Kir6.2 position 68 for normal channel gating, which is potentially necessary to localize the ϵ-amine of Lys-170 in the phosphatidylinositol 4,5-bisphosphate-binding site. Overall, our findings identify a discrete pair of highly conserved residues with an essential role for controlling gating kinetics of Kir channels.

  9. Regulation of neurotransmitter release kinetics by NSF.

    PubMed

    Schweizer, F E; Dresbach, T; DeBello, W M; O'Connor, V; Augustine, G J; Betz, H

    1998-02-20

    NSF (N-ethylmaleimide-sensitive factor) is an adenosine triphosphatase (ATPase) that contributes to a protein complex essential for membrane fusion. The synaptic function of this protein was investigated by injecting, into the giant presynaptic terminal of squid, peptides that inhibit the ATPase activity of NSF stimulated by the soluble NSF attachment protein (SNAP). These peptides reduced the amount and slowed the kinetics of neurotransmitter release as a result of actions that required vesicle turnover and occurred at a step subsequent to vesicle docking. These results define NSF as an essential participant in synaptic vesicle exocytosis that regulates the kinetics of neurotransmitter release and, thereby, the integrative properties of synapses.

  10. Kinetics of luminol sonochemiluminescence quenched by purines.

    PubMed

    Wang, Jian; Lai, Yongquan; Chen, Meili; Jiang, Zhou; Chen, Guonan

    2013-01-01

    A homogeneous chemiluminescence (CL) reaction was initiated by ultrasound irradiation. Luminol sonochemiluminescence (SCL) reaction kinetics were determined under pseudo-first-order conditions, and the reaction followed the model for simple rise-fall kinetics. In addition, SCL quenching reactions induced by purines were also investigated in which the interactions between luminol and purines were analysed using the Stern-Volmer (S-V) mechanism. The results implied that the high rate constant of luminol CL quenched by purines may be attributed to ground state interactions originating from hydrogen bonding.

  11. An investigation of the effect of surface impurities on the adsorption kinetics of hydrogen chemisorbed onto iron. Annual Status Report, 1 Jan. - 31 Dec. 1991. [titanium aluminides and beryllium

    SciTech Connect

    Shanabarger, M.R.

    1991-12-01

    The goal was to develop an understanding of heterogeneous kinetic processes for those molecular species which produce gaseous hydrogen degradation of the mechanical properties of metallic structural materials. Although hydrogen degradation of metallic materials is believed to result from dissolved protonic hydrogen, the heterogeneous hydrogen interface transport processes often dominate the kinetics of the degradation process. The initial step in the interface transport process is the dissociative chemisorption of the molecular species at the metal surface followed by hydrogen absorption into and transport through the bulk. Modern advanced aerospace applications often require the use of structural materials in high pressure hydrogen environments at temperatures which range from low cryogenic temperatures to very high temperatures (1300 K and greater). Materials proposed for these applications, such as the titanium aluminides, beta-titanium alloys, nickel- and cobalt-based superalloys, molybdenum-rhenium alloys, beryllium, and various beryllides, need to possess a high degree of immunity from hydrogen induced degradation of mechanical properties. In the present program, the interaction of hydrogen with the surfaces of alpha-2 (Ti3Al) titanium aluminide, gamma (TiAl) titanium aluminide, and beryllium were studied. The interaction of low pressure hydrogen with gamma titanium aluminide and beryllium was found to be relatively weak, in the sense that adsorption leads to a low surface concentration of dissociated hydrogen, i.e., the chemisorption process is reversible at room temperature (300 K) for gamma titanium aluminide and the sticking coefficient for chemisorption is extremely small for beryllium. Hydrogen was found to interact readily with alpha-2 titanium aluminide to form a stable surface hydride at 300 K.

  12. Investigation of mitigating effect of colon-specific prodrugs of boswellic acid on 2,4,6-trinitrobenzene sulfonic acid-induced colitis in Wistar rats: Design, kinetics and biological evaluation

    PubMed Central

    Sarkate, Ajinkya; Dhaneshwar, Suneela S

    2017-01-01

    AIM To develop a colon-targeting bioreversible delivery system for β-boswellic acid (BBA) and explore utility of its prodrugs in 2,4,6-trinitrobenzene sulfonic acid (TNBS)-induced colitis in rats. METHODS Synthesis of 4 co-drugs of BBA with essential amino acids was achieved by CDI coupling, followed by their spectral characterization. In vitro kinetics were studied by HPLC in aqueous buffers, homogenates of gastrointestinal tract and fecal matter. In vivo kinetic studies were performed in Wistar rat plasma, urine and feces. The prodrugs were screened in TNBS-induced colitis modeled Wistar rats. Statistical significance was assumed at P < 0.05, P < 0.01, P < 0.001 when compared with disease controls using one-way and two-way ANOVAs. RESULTS Prodrugs were stable in 0.05 mol/L HCl buffer (pH 1.2) and stomach homogenates. Negligible hydrolysis was observed in phosphate buffer and intestinal homogenates. Substantial release (55%-72% and 68%-86%) of BBA was achieved in rat fecal matter and homogenates of colon. In vivo studies of BBA with L-tryptophan (BT) authenticated colon-specific release of BBA. But, surprisingly substantial concentration of BBA was seen to reach the systemic circulation due to probable absorption through colonic mucosa. Site-specifically enhanced bioavailability of BBA could be achieved in colon, which resulted in demonstration of significant mitigating effect on TNBS-induced colitis in rats without inducing any adverse effects on stomach, liver and pancreas. Prodrug of BT was found to be 1.7% (P < 0.001) superior than sulfasalazine in reducing the inflammation to colon among all prodrugs tested. CONCLUSION The outcome of this study strongly suggests that these prodrugs might have dual applicability to inflammatory bowel disease and chronotherapy of rheumatoid arthritis. PMID:28275295

  13. Electron-transfer reactions of cobalt(III) complexes. 1. The kinetic investigation of the reduction of various surfactant cobalt(III) complexes by iron(II) in surface active ionic liquids.

    PubMed

    Nagaraj, Karuppiah; Senthil Murugan, Krishnan; Thangamuniyandi, Pilavadi; Sakthinathan, Subramanian

    2015-05-15

    The kinetics of outer sphere electron transfer reaction of surfactant cobalt(III) complex ions, cis-[Co(en)2(C12H25NH2)2](3+) (1), cis-[Co(dp)2(C12H25NH2)2](3+) (2), cis-[Co(trien)(C12H25NH2)2](3+) (3), cis-[Co(bpy)2(C12H25NH2)2](3+) (4) and cis-[Co(phen)2(C12H25NH2)2](3+) (5) (en: ethylenediamine, dp: diaminopropane, trien : triethylenetetramine, bpy: 2,2'-bipyridyl, phen: 1,10-phenanthroline and C12H25NH2 : dodecylamine) have been interrogated by Fe(2+) ion in ionic liquid (1-butyl-3-methylimidazoliumbromide) medium at different temperatures (298, 303, 308, 313, 318 and 323K) by the spectrophotometry method under pseudo first order conditions using an excess of the reductant. Experimentally the reactions were found to be of second order and the electron transfer as outer sphere. The second order rate constant for the electron transfer reaction in ionic liquids was found to increase with increase in the concentration of all these surfactant cobalt(III) complexes. Among these complexes (from en to phen ligand), complex containing the phenanthroline ligand rate is higher compared to other complexes. By assuming the outer sphere mechanism, the results have been explained based on the presence of aggregated structures containing cobalt(III) complexes at the surface of ionic liquids formed by the surfactant cobalt(III) complexes in the reaction medium. The activation parameters (enthalpy of activation ΔH(‡) and entropy of activation ΔS(‡)) of the reaction have been calculated which substantiate the kinetics of the reaction.

  14. A Stopped-Flow Kinetics Experiment for the Physical Chemistry Laboratory Using Noncorrosive Reagents

    ERIC Educational Resources Information Center

    Prigodich, Richard V.

    2014-01-01

    Stopped-flow kinetics techniques are important to the study of rapid chemical and biochemical reactions. Incorporation of a stopped-flow kinetics experiment into the physical chemistry laboratory curriculum would therefore be an instructive addition. However, the usual reactions studied in such exercises employ a corrosive reagent that can over…

  15. Crystal growth of intermetallic clathrates: Floating zone process and ultra rapid crystallization

    NASA Astrophysics Data System (ADS)

    Prokofiev, A.; Yan, X.; Ikeda, M.; Löffler, S.; Paschen, S.

    2014-09-01

    We studied the crystal growth process of type-I transition metal clathrates in two different regimes: a regime of moderate cooling rate, realized with the floating zone technique, and a regime of ultra rapid cooling, realized by the melt spinning technique. In the former regime, bulk Ba8AuxSi46-x and Ba8Cu4.8GaxGe41.2-x single crystals were grown. We investigated segregation effects of the constituting elements by measurements of the composition profiles along the growth direction. The compositional non-uniformity results in a spatial variation of the electrical resistivity which is discussed as well. Structural features of clathrates and their extremely low thermal conductivities imply specifics in growth behavior which manifest themselves most pronouncedly in a rapid crystallization process. Our melt spinning experiments on Ba8Au5Si41 and Ba8Ni3.5Si42.5 (and earlier on some other clathrates) have revealed surprisingly large grains of at least 1 μm. Because of the anomalously high growth rate of the clathrate phase the formation of impurity phases is considerably kinetically suppressed. We present our scanning and transmission electron microscopy investigations of melt spun samples and discuss structural, thermodynamic and kinetic aspects of the unusual clathrate nucleation and crystallization.

  16. Kinetics and thermodynamics of living copolymerization processes

    NASA Astrophysics Data System (ADS)

    Gaspard, Pierre

    2016-11-01

    Theoretical advances are reported on the kinetics and thermodynamics of free and template-directed living copolymerizations. Until recently, the kinetic theory of these processes had only been established in the fully irreversible regime, in which the attachment rates are only considered. However, the entropy production is infinite in this regime and the approach to thermodynamic equilibrium cannot be investigated. For this purpose, the detachment rates should also be included. Inspite of this complication, the kinetics can be exactly solved in the regimes of steady growth and depolymerization. In this way, analytical expressions are obtained for the mean growth velocity, the statistical properties of the copolymer sequences, as well as the thermodynamic entropy production. The results apply to DNA replication, transcription and translation, allowing us to understand important aspects of molecular evolution. This article is part of the themed issue 'Multiscale modelling at the physics-chemistry-biology interface'.

  17. A kinetic cross-field streaming instability

    NASA Technical Reports Server (NTRS)

    Wu, C. S.; Winske, D.; Papadopoulos, K.; Zhou, Y. M.; Tsai, S. T.; Guo, S. C.

    1983-01-01

    In a high-beta plasma the so-called modified-two-stream instability, which results from strongly magnetized electrons drifting relative to unmagnetized ions across a homogeneous magnetic field, is misnamed because the mode is highly kinetic, particularly when the relative streaming velocity exceeds the Alfven speed of the plasma. This kinetic cross-field streaming instability is investigated in detail, examining the effect of the electromagnetic terms and the stability boundaries in both low- and high-beta plasmas. An approximate dispersion relation showing the relation of this mode to the whistler is derived and solutions of it are compared with those obtained from the exact dispersion relation. The kinetic mode, unlike the usual modified-two-stream instability, is not stabilized by electromagnetic effects when the relative electron-ion drift speed exceeds the Alfven speed.

  18. LLNL Chemical Kinetics Modeling Group

    SciTech Connect

    Pitz, W J; Westbrook, C K; Mehl, M; Herbinet, O; Curran, H J; Silke, E J

    2008-09-24

    The LLNL chemical kinetics modeling group has been responsible for much progress in the development of chemical kinetic models for practical fuels. The group began its work in the early 1970s, developing chemical kinetic models for methane, ethane, ethanol and halogenated inhibitors. Most recently, it has been developing chemical kinetic models for large n-alkanes, cycloalkanes, hexenes, and large methyl esters. These component models are needed to represent gasoline, diesel, jet, and oil-sand-derived fuels.

  19. Infrared Absorption Spectroscopy and Chemical Kinetics of Free Radicals. Final Performance Report, August 1, 1985--July 31, 1994

    DOE R&D Accomplishments Database

    Curl, R. F.; Glass, G. P.

    1995-06-01

    This research was directed at the detection, monitoring, and study (by infrared absorption spectroscopy) of the chemical kinetic behavior of small free radical species thought to be important intermediates in combustion. The work typically progressed from the detection and analysis of the infrared spectrum of combustion radical to the utilization of the infrared spectrum thus obtained in the investigation of chemical kinetics of the radical species. The methodology employed was infrared kinetic spectroscopy. In this technique the radical is produced by UV flash photolysis using an excimer laser and then its transient infrared absorption is observed using a single frequency cw laser as the source of the infrared probe light. When the probe laser frequency is near the center of an absorption line of the radical produced by the flash, the transient infrared absorption rises rapidly and then decays as the radical reacts with the precursor or with substances introduced for the purpose of studying the reaction kinetics or with itself. The decay times observed in these studies varied from less than one microsecond to more than one millisecond. By choosing appropriate time windows after the flash and the average infrared detector signal in a window as data channels, the infrared spectrum of the radical may be obtained. By locking the infrared probe laser to the center of the absorption line and measuring the rate of decay of the transient infrared absorption signal as the chemical composition of the gas mixture is varied, the chemical kinetics of the radical may be investigated. In what follows the systems investigated and the results obtained are outlined.

  20. CO and O2 binding to pseudo-tetradentate ligand-copper(I) complexes with a variable N-donor moiety: kinetic/thermodynamic investigation reveals ligand-induced changes in reaction mechanism.

    PubMed

    Lucas, Heather R; Meyer, Gerald J; Karlin, Kenneth D

    2010-09-22

    The kinetics, thermodynamics, and coordination dynamics are reported for O(2) and CO 1:1 binding to a series of pseudo-tetradentate ligand-copper(I) complexes ((D)LCu(I)) to give Cu(I)/O(2) and Cu(I)/CO product species. Members of the (D)LCu(I) series possess an identical tridentate core structure where the cuprous ion binds to the bispicolylamine (L) fragment. (D)L also contains a fourth variable N-donor moiety {D = benzyl (Bz); pyridyl (Py); imidazolyl (Im); dimethylamino (NMe(2)); (tert-butylphenyl)pyridyl (TBP); quinolyl (Q)}. The structural characteristics of (D)LCu(I)-CO and (D)LCu(I) are detailed, with X-ray crystal structures reported for (TBP)LCu(I)-CO, (Bz)LCu(I)-CO, and (Q)LCu(I). Infrared studies (solution and solid-state) confirm that (D)LCu(I)-CO possess the same four-coordinate core structure in solution with the variable D moiety "dangling", i.e., not coordinated to the copper(I) ion. Other trends observed for the present series appear to derive from the degree to which the D-group interacts with the cuprous ion center. Electrochemical studies reveal close similarities of behavior for (Im)LCu(I) and (NMe(2))LCu(I) (as well as for (TBP)LCu(I) and (Q)LCu(I)), which relate to the O(2) binding kinetics and thermodynamics. Equilibrium CO binding data (K(CO), ΔH°, ΔS°) were obtained by conducting UV-visible spectrophotometric CO titrations, while CO binding kinetics and thermodynamics (k(CO), ΔH(double dagger), ΔS(double dagger)) were measured through variable-temperature (193-293 K) transient absorbance laser flash photolysis experiments, λ(ex) = 355 nm. Carbon monoxide dissociation rate constants (k(-CO)) and corresponding activation parameters (ΔH(double dagger), ΔS(double dagger)) have also been obtained. CO binding to (D)LCu(I) follows an associative mechanism, with the increased donation from D leading to higher k(CO) values. Unlike observations from previous work, the K(CO) values increased as the k(CO) and k(-CO) values declined; the

  1. An experimental model of COD abatement in MBBR based on biofilm growth dynamic and on substrates' removal kinetics.

    PubMed

    Siciliano, Alessio; De Rosa, Salvatore

    2016-08-01

    In this study, the performance of a lab-scale Moving Bed Biofilm Reactor (MBBR) under different operating conditions was analysed. Moreover, the dependence of the reaction rates both from the concentration and biodegradability of substrates and from the biofilm surface density, by means of several batch kinetic tests, was investigated. The reactor controls exhibited an increasing COD (Chemical Oxygen Demand) removal, reaching maximum yields (close to 90%) for influent loadings of up to12.5 gCOD/m(2)d. From this value, the pilot plant performance decreased to yields of only about 55% for influent loadings greater than 16 gCOD/m(2)d. In response to the influent loading increase, the biofilm surface density exhibited a logistic growing trend until reaching a maximum amount of total attached solids of about 9.5 g/m(2). The kinetic test results indicated that the COD removal rates for rapidly biodegradable, rapidly hydrolysable and slowly biodegradable substrates were not affected by the organic matter concentrations. Instead, first-order kinetics were detected with respect to biofilm surface density. The experimental results permitted the formulation of a mathematical model to predict the MBBR organic matter removal efficiency. The validity of the model was successfully tested in the lab-scale plant.

  2. Kinetic Tetrazolium Microtiter Assay

    NASA Technical Reports Server (NTRS)

    Pierson, Duane L.; Stowe, Raymond; Koenig, David

    1993-01-01

    Kinetic tetrazolium microtiter assay (KTMA) involves use of tetrazolium salts and Triton X-100 (or equivalent), nontoxic, in vitro color developer solubilizing colored metabolite formazan without injuring or killing metabolizing cells. Provides for continuous measurement of metabolism and makes possible to determine rate of action of antimicrobial agent in real time as well as determines effective inhibitory concentrations. Used to monitor growth after addition of stimulatory compounds. Provides for kinetic determination of efficacy of biocide, greatly increasing reliability and precision of results. Also used to determine relative effectiveness of antimicrobial agent as function of time. Capability of generating results on day of test extremely important in treatment of water and waste, disinfection of hospital rooms, and in pharmaceutical, agricultural, and food-processing industries. Assay also used in many aspects of cell biology.

  3. Kinetic Proofreading of Cytoskeletal Structures

    NASA Astrophysics Data System (ADS)

    Swanson, Douglas; Wingreen, Ned

    2010-03-01

    Cytoskeletal polymer dynamics play a role in cellular processes as varied as reproduction, locomotion, and intracellular transport. Microtubules are cytoskeletal biopolymers that grow by accumulating tubulin subunits bound to guanosine triphosphate (GTP). The subunits hydrolyze GTP to guanosine diphosphate (GDP), causing a conformational change in the protein that destabilizes the microtubule. GDP-bound subunits tend to depolymerize, leading to stochastic microtubule disassembly in a process known as dynamic instability. Over time polymerization and depolymerization come to steady state, leading to a local steady-state concentration of tubulin subunits. This may be viewed as a kind of ``kinetic proofreading,'' in which the system consumes energy actively to ``proofread'' the steady-state subunit concentration. We suggest that the same mechanism could also ``proofread'' between different cytoskeletal structures. For example, we show that a small free-energy difference between two polymer orientations, combined with dynamic instability, can strongly drive the system towards the lower free-energy state. This might help to explain the long-time stability of many cytoskeletal structures despite the short-time rapid turnover of the individual subunits.

  4. Kinetic Theory of Gases

    NASA Astrophysics Data System (ADS)

    Murdin, P.

    2000-11-01

    The theory, developed in the nineteenth century, notably by Rudolf Clausius (1822-88) and James Clerk Maxwell (1831-79), that the properties of a gas (temperature, pressure, etc) could be described in terms of the motions (and kinetic energy) of the molecules comprising the gases. The theory has wide implications in astrophysics. In particular, the perfect gas law, which relates the pressure, vol...

  5. Homogeneous nucleation kinetics

    NASA Technical Reports Server (NTRS)

    Rasmussen, D. H.; Appleby, M. R.; Leedom, G. L.; Babu, S. V.; Naumann, R. J.

    1983-01-01

    Homogeneous nucleation kinetics are rederived in a manner fundamentally similar to the approach of classical nucleation theory with the following modifications and improvements. First, the cluster is a parent phase cluster and does not require energization to the parent state. Second, the thermodynamic potential used to describe phase stability is a continuous function along the pathway of phase decomposition. Third, the kinetics of clustering corresponds directly to the diffusional flux of monomers through the cluster distribution and are formally similar to classical theory with the resulting kinetic equation modified by two terms in the preexponential factor. These terms correct for the influence of a supersaturation dependent clustering within the parent phase and for the influence of an asymmetrical cluster concentration as a function of cluster size at the critical cluster size. Fourth, the supersaturation dependence of the nucleation rate is of the same form as that given by classical nucleation theory. This supersaturation dependence must however be interpreted in terms of a size dependent surface tension. Finally, there are two scaling laws which describe supersaturation to either constant nucleation rate or to the thermodynamically determined physical spinodal.

  6. Equilibrium and kinetics study on hexavalent chromium adsorption onto diethylene triamine grafted glycidyl methacrylate based copolymers.

    PubMed

    Maksin, Danijela D; Nastasović, Aleksandra B; Milutinović-Nikolić, Aleksandra D; Suručić, Ljiljana T; Sandić, Zvjezdana P; Hercigonja, Radmila V; Onjia, Antonije E

    2012-03-30

    Two porous and one non-porous crosslinked poly(glycidyl methacrylate-co-ethylene glycol dimethacrylate) [abbreviated PGME] were prepared by suspension copolymerization and functionalized with diethylene triamine [abbreviated PGME-deta]. Samples were characterized by elemental analysis, mercury porosimetry, scanning electron microscopy with energy-dispersive X-ray spectroscopy, and transmission electron microscopy. Kinetics of Cr(VI) sorption by PGME-deta were investigated in batch static experiments, in the temperature range 25-70°C. Sorption was rapid, with the uptake capacity higher than 80% after 30 min. Sorption behavior and rate-controlling mechanisms were analyzed using five kinetic models (pseudo-first order, pseudo-second order, Elovich, intraparticle diffusion and Bangham model). Kinetic studies showed that Cr(VI) adsorption adhered to the pseudo-second-order model, with definite influence of pore diffusion. Equilibrium data was tested with Langmuir, Freundlich and Tempkin adsorption isotherm models. Langmuir model was the most suitable indicating homogeneous distribution of active sites on PGME-deta and monolayer sorption. The maximum adsorption capacity from the Langmuir model, Q(max), at pH 1.8 and 25°C was 143 mg g(-1) for PGME2-deta (sample with the highest amino group concentration) while at 70°C Q(max) reached the high value of 198 mg g(-1). Thermodynamic parameters revealed spontaneous and endothermic nature of Cr(VI) adsorption onto PGME-deta.

  7. Dissolution Kinetics of Alumina Calcine

    SciTech Connect

    Batcheller, Thomas Aquinas

    2001-09-01

    Dissolution kinetics of alumina type non-radioactive calcine was investigated as part of ongoing research that addresses permanent disposal of Idaho High Level Waste (HLW). Calcine waste was produced from the processing of nuclear fuel at the Idaho Nuclear Technology and Engineering Center (INTEC). Acidic radioactive raffinates were solidified at ~500°C in a fluidized bed reactor to form the dry granular calcine material. Several Waste Management alternatives for the calcine are presented in the Idaho High Level Waste Draft EIS. The Separations Alternative addresses the processing of the calcine so that the HLW is ready for removal to a national geological repository by the year 2035. Calcine dissolution is the key front-end unit operation for the separations alternative.

  8. Desorption kinetics of benzene in a sandy soil in the presence of powdered activated carbon.

    PubMed

    Choi, J-W; Kim, S-B; Kim, D-J

    2007-02-01

    Desorption kinetics of benzene was investigated with a modified biphasic desorption model in a sandy soil with five different powdered activated carbon (PAC) contents (0, 1, 2, 5, 10% w/w) as sorbents. Sorption experiments followed by series dilution desorption were conducted for each sorbent. Desorption of benzene was successively performed at two stages using deionized water and hexane. Modeling was performed on both desorption isotherm and desorption rate for water-induced desorption to elucidate the presence of sorption-desorption hysteresis and biphasic desorption and if present to quantify the desorption-resistant fraction (q (irr)) and labile fraction (F) of desorption site responsible for rapid process. Desorption isotherms revealed that sorption-desorption exhibited a severe hysteresis with a significant fraction of benzene being irreversibly adsorbed onto both pure sand and PAC, and that desorption-resistant fraction (q (irr)) increased with PAC content. Desorption kinetic modeling showed that desorption of benzene was biphasic with much higher (4-40 times) rate constant for rapid process (k (1)) than that for slow process (k (2)), and that the difference in the rate constant increased with PAC content. The labile fraction (F) of desorption site showed a decreasing tendency with PAC. The experimental results would provide valuable information on remediation methods for soils and groundwater contaminated with BTEX.

  9. Degradation Kinetics and Mechanism of Lithospermic Acid under Low Oxygen Condition Using Quantitative 1H NMR with HPLC-MS

    PubMed Central

    Pan, Jianyang; Gong, Xingchu; Qu, Haibin

    2016-01-01

    A novel quantitative 1H NMR (Q-NMR) combined with HPLC-MS method has been proposed for investigating the degradation process of traditional Chinese medicine (TCM) components. Through this method, in-situ monitoring of dynamics degradation process of lithospermic acid (LA), one of the popular polyphenolic acids in TCM, was realized under low oxygen condition. Additionally, this methodology was proved to be simple, rapid and specific. Degradation kinetic runs have been carried out to systematically investigate the effects of two key environmental factors, initial pH values and temperatures. Eight main degradation products of LA were detected, seven of which were tentatively structural elucidated with the help of both NMR and LC-MS in this work and salvianolic acid A (Sal A) was the primary degradation product of LA. A possible degradation pathway of LA was proposed, subsequently. The results showed that the degradation of LA followed pseudo-first-order kinetics. The apparent degradation kinetic constants increased as the initial pH value of the phosphate buffer increased. Under the given conditions, the rate constants of overall degradation as a function of temperature obeyed the Arrhenius equation. Our results proved that the Q-NMR combined with HPLC-MS method can be one of the most promising techniques for investigating degradation process of active components in TCM. PMID:27776128

  10. Kinetics of biosorption of hazardous metals by green soil supplement

    NASA Astrophysics Data System (ADS)

    Bagla, Hemlata; Khilnani, Roshan

    2016-04-01

    The process of metal retention by soil may include ion exchange, adsorption and precipitation. These reaction mechanisms have been defined through fitting the data into different equilibrium and kinetic models. The natural organic matter in soil consists of various fractions like macro-organic material, plant residues, soil biomass and stable humus. Most of the organic matter is dominated with large amount of humic substances. Humic fractions in soil are known to have indirect and direct effects on plant growth and crop production. Humic substances increase the cation exchange capacity, providing a strong buffer capacity to resist sudden drastic chemical changes in soil which enhance soil fertility and environmental quality. The cation-humic interactions exert control on the reactivity of the cation, influencing its bioavailability in the soil system. The investigation of metal concentrations adsorbed with time can be useful to estimate the metal bioavailability in soil. Understanding how metals interact and compete for adsorption sites is of great interest to those involved in environmental remediation. Cow Dung is bio-organic, complex, polymorphic fecal matter of the bovine species, enriched with 'Humic acid' (HA), 'Fulvic Acid', etc. The HA in Cow Dung has been successfully extracted using neutralization reaction and its presence was confirmed by comparison with FTIR spectra of standard HA (IHSS). Since, dry Cow dung powder (DCP) is being added as a soil supplement to enhance the quality of soil, it is important to understand the kinetics associated with it. This work reports kinetic studies of various toxic and hazardous elements such as Cr(III), Cr(VI), Sr(II), Cd(II), Hg(II) and Co(II) adsorption by dry Cow dung powder. Kinetic experiments demonstrated rapid metal uptake. The Kinetic biosorption data were obtained by Batch experiments to explore the rate of biosorption by DCP at optimum parameters and varying the time of reaction from 1-30 min. The dynamics

  11. FNAS/Rapid Spectral Inversion Methods

    NASA Technical Reports Server (NTRS)

    Poularikas, Alexander

    1997-01-01

    The purpose of this investigation was to study methods and ways for rapid inversion programs involving the correlated k-method, and to study the infrared observations of Saturn from the Cassini orbiter.

  12. Protein folded states are kinetic hubs

    PubMed Central

    Bowman, Gregory R.; Pande, Vijay S.

    2010-01-01

    Understanding molecular kinetics, and particularly protein folding, is a classic grand challenge in molecular biophysics. Network models, such as Markov state models (MSMs), are one potential solution to this problem. MSMs have recently yielded quantitative agreement with experimentally derived structures and folding rates for specific systems, leaving them positioned to potentially provide a deeper understanding of molecular kinetics that can lead to experimentally testable hypotheses. Here we use existing MSMs for the villin headpiece and NTL9, which were constructed from atomistic simulations, to accomplish this goal. In addition, we provide simpler, humanly comprehensible networks that capture the essence of molecular kinetics and reproduce qualitative phenomena like the apparent two-state folding often seen in experiments. Together, these models show that protein dynamics are dominated by stochastic jumps between numerous metastable states and that proteins have heterogeneous unfolded states (many unfolded basins that interconvert more rapidly with the native state than with one another) yet often still appear two-state. Most importantly, we find that protein native states are hubs that can be reached quickly from any other state. However, metastability and a web of nonnative states slow the average folding rate. Experimental tests for these findings and their implications for other fields, like protein design, are also discussed. PMID:20534497

  13. Kinetics and mechanism of autohydrolysis of hardwoods.

    PubMed

    Chen, Xiaowen; Lawoko, Martin; Heiningen, Adriaan van

    2010-10-01

    Autohydrolysis using water is a promising method to extract hemicelluloses from wood prior to pulping in order to make co-products such as ethanol and acetic acid besides pulp. Many studies have been carried out on the kinetics and mechanism of autohydrolysis using batch reactors. The present study was performed in a continuous mixed flow reactor where the wood chips are retained in a basket inside the reactor. This reactor is well suited to determine intrinsic kinetics of hemicellulose dissolution because the dissolved products are rapidly removed from the reactor, thus minimizing further hydrolysis and degradation of the hemicelluloses in solution. The xylan removal rate follows an S-shaped behavior. GPC analysis of the continuously removed extract shows that the dissolved xylan oligomers have a DP smaller than about 25. Lignin-free xylan oligomers and cellulose oligomers are the major components dissolved in the initial stage of autohydrolysis, while xylan covalently bound to lignin (i.e. an LCC) is the major component removed during the later stage of autohydrolysis. The molecular weight of the dissolved components decreases with time in the second stage. The kinetics of xylan removal are explained in terms of a mechanism based on recent knowledge of the ultrastructure of the cell fibre wall.

  14. Caged Naloxone Reveals Opioid Signaling Deactivation Kinetics

    PubMed Central

    Banghart, Matthew R.; Shah, Ruchir C.; Lavis, Luke D.

    2013-01-01

    The spatiotemporal dynamics of opioid signaling in the brain remain poorly defined. Photoactivatable opioid ligands provide a means to quantitatively measure these dynamics and their underlying mechanisms in brain tissue. Although activation kinetics can be assessed using caged agonists, deactivation kinetics are obscured by slow clearance of agonist in tissue. To reveal deactivation kinetics of opioid signaling we developed a caged competitive antagonist that can be quickly photoreleased in sufficient concentrations to render agonist dissociation effectively irreversible. Carboxynitroveratryl-naloxone (CNV-NLX), a caged analog of the competitive opioid antagonist NLX, was readily synthesized from commercially available NLX in good yield and found to be devoid of antagonist activity at heterologously expressed opioid receptors. Photolysis in slices of rat locus coeruleus produced a rapid inhibition of the ionic currents evoked by multiple agonists of the μ-opioid receptor (MOR), but not of α-adrenergic receptors, which activate the same pool of ion channels. Using the high-affinity peptide agonist dermorphin, we established conditions under which light-driven deactivation rates are independent of agonist concentration and thus intrinsic to the agonist-receptor complex. Under these conditions, some MOR agonists yielded deactivation rates that are limited by G protein signaling, whereas others appeared limited by agonist dissociation. Therefore, the choice of agonist determines which feature of receptor signaling is unmasked by CNV-NLX photolysis. PMID:23960100

  15. Computational model for Halorhodopsin photocurrent kinetics

    NASA Astrophysics Data System (ADS)

    Bravo, Jaime; Stefanescu, Roxana; Talathi, Sachin

    2013-03-01

    Optogenetics is a rapidly developing novel optical stimulation technique that employs light activated ion channels to excite (using channelrhodopsin (ChR)) or suppress (using halorhodopsin (HR)) impulse activity in neurons with high temporal and spatial resolution. This technique holds enormous potential to externally control activity states in neuronal networks. The channel kinetics of ChR and HR are well understood and amenable for mathematical modeling. Significant progress has been made in recent years to develop models for ChR channel kinetics. To date however, there is no model to mimic photocurrents produced by HR. Here, we report the first model developed for HR photocurrents based on a four-state model of the HR photocurrent kinetics. The model provides an excellent fit (root-mean-square error of 3.1862x10-4, to an empirical profile of experimentally measured HR photocurrents. In combination, mathematical models for ChR and HR photocurrents can provide effective means to design test light based control systems to regulate neural activity, which in turn may have implications for the development of novel light based stimulation paradigms for brain disease control. I would like to thank the University of Florida and the Physics Research Experience for Undergraduates (REU) program, funded through NSF DMR-1156737. This research was also supported through start-up funds provided to Dr. Sachin Talathi

  16. An investigation of the formation of chlorate and perchlorate during electrolysis using Pt/Ti electrodes: the effects of pH and reactive oxygen species and the results of kinetic studies.

    PubMed

    Jung, Yeon Jung; Baek, Ko Woon; Oh, Byung Soo; Kang, Joon-Wun

    2010-10-01

    The characteristics of chlorate (ClO(3)(-)) and perchlorate (ClO(4)(-)) formation were studied during the electrolysis of water containing chloride ions (Cl(-)). The experiments were performed using an undivided Pt/Ti plate electrode under different pH conditions (pH 3.6, 5.5, 7.2, 8.0 and 9.0). ClO(3)(-) and ClO(4)(-) were formed during electrolysis in proportion to the Cl(-) concentration. The generation rates of ClO(3)(-) and ClO(4)(-) under acidic conditions (pH 3.6 and 5.5) were lower than in basic pH conditions (pH 7.2, 8.0 and 9.0). However, the pH of the solution did not influence the conversion of ClO(3)(-) to ClO(4)(-). The effects of intermediately formed oxidants on the production of ClO(3)(-) and ClO(4)(-) were observed using sodium thiosulfate (Na(2)S(2)O(3)) as the active chlorine scavenger and tertiary butyl alcohol (t-BuOH) as the hydroxyl radical (OH) scavenger. The results revealed that electrolysis reactions that involved active chlorine contributed dominantly to ClO(3)(-) production. The direct oxidation reaction rate of Cl(-) to ClO(3)(-) was 13%. The OH species that were intermediately formed during electrolysis were also found to significantly affect ClO(3)(-) and ClO(4)(-) production. The key formation pathways of ClO(3)(-) and ClO(4)(-) were studied using kinetic model development.

  17. The kinetics of root gravitropism: dual motors and sensors

    NASA Technical Reports Server (NTRS)

    Wolverton, Chris; Ishikawa, Hideo; Evans, Michael L.

    2002-01-01

    The Cholodny-Went theory of tropisms has served as a framework for investigation of root gravitropism for nearly three quarters of a century. Recent investigations using modern techniques have generated findings consistent with the classical theory, including confirmation of asymmetrical distribution of polar auxin transport carriers, molecular evidence for auxin asymmetry following gravistimulation, and generation of auxin response mutants with predictable lesions in gravitropism. Other results indicate that the classical model is inadequate to account for key features of root gravitropism. Initiation of curvature, for example, occurs outside the region of most rapid elongation and is driven by differential acceleration rather than differential inhibition of elongation. The evidence indicates that there are two motors driving root gravitropism, one of which appears not to be auxin regulated. We have recently developed technology that is capable of maintaining a constant angle of gravistimulation at any selected target region of a root while continuously monitoring growth and curvature kinetics. This review elaborates on the advantages of this new technology for analyzing gravitropism and describes applications of the technology that reveal (1) the existence of at least two phases to gravitropic motor output, even under conditions of constant stimulus input and (2) the existence of gravity sensing outside of the root cap. We propose a revised model of root gravitropism including dual sensors and dual motors interacting to accomplish root gravitropism, with only one of the systems linked to the classical Cholodny-Went theory.

  18. Kinetic modelling of runaway electrons in dynamic scenarios

    NASA Astrophysics Data System (ADS)

    Stahl, A.; Embréus, O.; Papp, G.; Landreman, M.; Fülöp, T.

    2016-11-01

    Improved understanding of runaway-electron formation and decay processes are of prime interest for the safe operation of large tokamaks, and the dynamics of the runaway electrons during dynamical scenarios such as disruptions are of particular concern. In this paper, we present kinetic modelling of scenarios with time-dependent plasma parameters; in particular, we investigate hot-tail runaway generation during a rapid drop in plasma temperature. With the goal of studying runaway-electron generation with a self-consistent electric-field evolution, we also discuss the implementation of a collision operator that conserves momentum and energy and demonstrate its properties. An operator for avalanche runaway-electron generation, which takes the energy dependence of the scattering cross section and the runaway distribution into account, is investigated. We show that the simplified avalanche model of Rosenbluth and Putvinskii (1997 Nucl. Fusion 37 1355) can give inaccurate results for the avalanche growth rate (either lower or higher) for many parameters, especially when the average runaway energy is modest, such as during the initial phase of the avalanche multiplication. The developments presented pave the way for improved modelling of runaway-electron dynamics during disruptions or other dynamic events.

  19. Rapid removal of copper with magnetic poly-acrylic weak acid resin: quantitative role of bead radius on ion exchange.

    PubMed

    Fu, Lichun; Shuang, Chendong; Liu, Fuqiang; Li, Aimin; Li, Yan; Zhou, Yang; Song, Haiou

    2014-05-15

    A novel magnetic weak acid resin NDMC was self-synthesized for the removal of Cu(2+) from aqueous solutions. NDMC showed superior properties on the removal of Cu(2+) compared to commercial resins C106 and IRC-748, which was deeply investigated by adsorption isotherms and kinetic tests. The equilibrium adsorption amount of Cu(2+) onto NDMC (267.2mg/g) was almost twice as large as that onto IRC-748 (120.0mg/g). The adsorption kinetics of Cu(2+) onto the three resins fitted well with the pseudo-second-order equation. The initial adsorption rate h of NDMC was about 4 times that of C106 and nearly 8 times that of IRC-748 at the initial concentration of 500mg/L. External surface area was determined to be the key factor in rate-controlling by further analyzing the adsorption thermodynamics, kinetics parameters and physicochemical properties of the resins. NDMC resin with the smallest bead radius possessed the largest external surface and therefore exhibited the fastest kinetics. The adsorption amount of Cu(2+) onto NDMC was not influenced as the concentration of Na(+) increased from 1.0 to 10.0mM/L. Dilute HCl solution could effectively desorb Cu(2+). NDMC demonstrated high stability during 10 adsorption/desorption cycles, showing great potential in the rapid removal of Cu(2+) from wastewater.

  20. The ilmenite/titano-magnetite assemblage - Kinetics of re-equilibration

    NASA Technical Reports Server (NTRS)

    Hammond, P. A.; Taylor, L. A.

    1982-01-01

    The petrogenesis of igneous and metamorphic rocks is a function of several parameters. Of these, temperature and pressure are of particular importance. Information concerning these two parameters is obtained through the use of mineral indicators. One such commonly used geothermometer/oxybarometer is that involving ilmenite/titano-magnetite. Anomalously low temperatures have been reported in cases in which the geothermometer/oxybarometer was employed. The studies suggest that low temperatures result from slow cooling rates which allows the Fe-Ti oxides to re-equilibrate. The current investigation is mainly concerned with the kinetics of the reduction of ilmenite-hematite solid solution, since this is the slower and, consequently, rate-controlling step in the re-equilibration process. The reaction rates determined for the reduction of ilmenites in the investigation are geologically rapid and must be considered when applying the considered geothermometer/oxybarometer.

  1. Portable Diagnostics and Rapid Germination

    SciTech Connect

    Dunn, Zachary Spencer

    2016-12-01

    In the Bioenergy and Defense Department of Sandia National Laboratories, characterization of the BaDx (Bacillus anthracis diagnostic cartridge) was performed and rapid germination chemistry was investigated. BaDx was tested with complex sample matrixes inoculated with Bacillus anthracis, and the trials proved that BaDx will detect Bacillus anthracis in a variety of the medium, such as dirt, serum, blood, milk, and horse fluids. The dimensions of the device were altered to accommodate an E. coli or Listeria lateral flow immunoassay, and using a laser printer, BaDx devices were manufactured to identify E. coli and Listeria. Initial testing with E. coli versions of BaDx indicate that the device will be viable as a portable diagnostic cartridge. The device would be more effective with faster bacteria germination; hence studies were performed the use of rapid germination chemistry. Trials with calcium dipicolinic acid displayed increased cell germination, as shown by control studies using a microplate reader. Upon lyophilization the rapid germination chemistry failed to change growth patterns, indicating that the calcium dipicolinic acid was not solubilized under the conditions tested. Although incompatible with the portable diagnostic device, the experiments proved that the rapid germination chemistry was effective in increasing cell germination.

  2. Equilibrium collapse and the kinetic 'foldability' of proteins.

    PubMed

    Millet, Ian S; Townsley, Lara E; Chiti, Fabrizio; Doniach, Sebastian; Plaxco, Kevin W

    2002-01-08

    An important element of protein folding theory has been the identification of equilibrium parameters that might uniquely distinguish rapidly folding polypeptide sequences from those that fold slowly. One such parameter, termed sigma, is a dimensionless, equilibrium measure of the coincidence of chain compaction and folding that is predicted to be an important determinant of relative folding kinetics. To test this prediction and improve our understanding of the putative relationship between nonspecific compaction of the unfolded state and protein folding kinetics, we have used small-angle X-ray scattering and circular dichroism spectroscopy to measure the sigma of five well-characterized proteins. Consistent with theoretical predictions, we find that near-perfect coincidence of the unfolded state contraction and folding (sigma approximately 0) is associated with the rapid kinetics of these naturally occurring proteins. We do not, however, observe any significant correlation between sigma and either the relative folding rates of these proteins or the presence or absence of well-populated kinetic intermediates. Thus, while sigma approximately 0 may be a necessary condition to ensure rapid folding, differences in sigma do not account for the wide range of rates and mechanisms with which naturally occurring proteins fold.

  3. Optimizing solubility: kinetic versus thermodynamic solubility temptations and risks.

    PubMed

    Saal, Christoph; Petereit, Anna Christine

    2012-10-09

    The aim of this study was to assess the usefulness of kinetic and thermodynamic solubility data in guiding medicinal chemistry during lead optimization. The solubility of 465 research compounds was measured using a kinetic and a thermodynamic solubility assay. In the thermodynamic assay, polarized-light microscopy was used to investigate whether the result referred to the crystalline or to the amorphous compound. From the comparison of kinetic and thermodynamic solubility data it was noted that kinetic solubility measurements frequently yielded results which show considerably higher solubility compared to thermodynamic solubility. This observation is ascribed to the fact that a kinetic solubility assay typically delivers results which refer to the amorphous compound. In contrast, results from thermodynamic solubility determinations more frequently refer to a crystalline phase. Accordingly, thermodynamic solubility data--especially when used together with an assessment of the solid state form--are deemed to be more useful in guiding solubility optimization for research compounds.

  4. Chemical kinetics modeling

    SciTech Connect

    Westbrook, C.K.; Pitz, W.J.

    1993-12-01

    This project emphasizes numerical modeling of chemical kinetics of combustion, including applications in both practical combustion systems and in controlled laboratory experiments. Elementary reaction rate parameters are combined into mechanisms which then describe the overall reaction of the fuels being studied. Detailed sensitivity analyses are used to identify those reaction rates and product species distributions to which the results are most sensitive and therefore warrant the greatest attention from other experimental and theoretical research programs. Experimental data from a variety of environments are combined together to validate the reaction mechanisms, including results from laminar flames, shock tubes, flow systems, detonations, and even internal combustion engines.

  5. Analysis of Crystallization Kinetics

    NASA Technical Reports Server (NTRS)

    Kelton, Kenneth F.

    1997-01-01

    A realistic computer model for polymorphic crystallization (i.e., initial and final phases with identical compositions), which includes time-dependent nucleation and cluster-size-dependent growth rates, is developed and tested by fits to experimental data. Model calculations are used to assess the validity of two of the more common approaches for the analysis of crystallization data. The effects of particle size on transformation kinetics, important for the crystallization of many systems of limited dimension including thin films, fine powders, and nanoparticles, are examined.

  6. Aquatic photochemical kinetics of benzotriazole and structurally related compounds.

    PubMed

    Janssen, Elisabeth M L; Marron, Emily; McNeill, Kristopher

    2015-05-01

    Benzotriazole corrosion inhibitors are not completely removed during wastewater treatment and are frequently detected in surface waters. Here, the photochemical kinetics of benzotriazoles and structurally related compounds were assessed for natural aqueous environments. The direct photochemical half-lives during exposure to simulated sunlight ranged from 1.3 to 1.8 days for benzotriazole and its derivatives (4-methyl-, 5-methyl-, 4-hydroxy-substituted benzotriazoles). Benzotriazole is more resistant to direct photodegradation than indazole (0.28 days) and indole (0.09 days), while benzimidazole showed no significant decay. Hydroxyl radicals (1.6 × 10(-16) M) and singlet oxygen (2.5 × 10(-13) M) are formed during simulated sunlight exposure in the presence of dissolved organic matter (13 mgC L(-1)). All tested compounds reacted rapidly with hydroxyl radicals near the diffusion-controlled limit (8.3 to 12 × 10(9) M(-1) s(-1)). Only 4-hydroxybenzotriazole and indole showed significant reactivity towards singlet oxygen and their photochemical half-lives in the presence of organic matter were shorter (0.1 days for both) than for benzotriazole and its methylated derivatives (1.4-1.5 days). The photochemical half-lives determined here are relatively long and support the persistence of benzotriazoles in the environment. At the same time, these results suggest that photochemical transformation can be supplementary to microbial degradation. While the presented study focused on environmental photodegradation kinetics, the relevance of transformation products remains to be investigated.

  7. Rapid Airplane Parametric Input Design (RAPID)

    NASA Technical Reports Server (NTRS)

    Smith, Robert E.

    1995-01-01

    RAPID is a methodology and software system to define a class of airplane configurations and directly evaluate surface grids, volume grids, and grid sensitivity on and about the configurations. A distinguishing characteristic which separates RAPID from other airplane surface modellers is that the output grids and grid sensitivity are directly applicable in CFD analysis. A small set of design parameters and grid control parameters govern the process which is incorporated into interactive software for 'real time' visual analysis and into batch software for the application of optimization technology. The computed surface grids and volume grids are suitable for a wide range of Computational Fluid Dynamics (CFD) simulation. The general airplane configuration has wing, fuselage, horizontal tail, and vertical tail components. The double-delta wing and tail components are manifested by solving a fourth order partial differential equation (PDE) subject to Dirichlet and Neumann boundary conditions. The design parameters are incorporated into the boundary conditions and therefore govern the shapes of the surfaces. The PDE solution yields a smooth transition between boundaries. Surface grids suitable for CFD calculation are created by establishing an H-type topology about the configuration and incorporating grid spacing functions in the PDE equation for the lifting components and the fuselage definition equations. User specified grid parameters govern the location and degree of grid concentration. A two-block volume grid about a configuration is calculated using the Control Point Form (CPF) technique. The interactive software, which runs on Silicon Graphics IRIS workstations, allows design parameters to be continuously varied and the resulting surface grid to be observed in real time. The batch software computes both the surface and volume grids and also computes the sensitivity of the output grid with respect to the input design parameters by applying the precompiler tool

  8. Rapidly progressive Alzheimer disease.

    PubMed

    Schmidt, Christian; Wolff, Martin; Weitz, Michael; Bartlau, Thomas; Korth, Carsten; Zerr, Inga

    2011-09-01

    Different rates of progression have been observed among patients with Alzheimer disease. Risk factors that accelerate deterioration have been identified and some are being discussed, such as genetics, comorbidity, and the early appearance of Alzheimer disease motor signs. Progressive forms of Alzheimer disease have been reported with rapid cognitive decline and disease duration of only a few years. This short review aims to provide an overview of the current knowledge of rapidly progressive Alzheimer disease. Furthermore, we suggest that rapid, in this context, should be defined as a Mini-Mental State Examination score decrease of 6 points per year.

  9. Rapidly Progressive Dementia

    PubMed Central

    Geschwind, Michael D.; Shu, Huidy; Haman, Aissa; Sejvar, James J.; Miller, Bruce L.

    2009-01-01

    In contrast with more common dementing conditions that typically develop over years, rapidly progressive dementias can develop subacutely over months, weeks, or even days and be quickly fatal. Because many rapidly progressive dementias are treatable, it is paramount to evaluate and diagnose these patients quickly. This review summarizes recent advances in the understanding of the major categories of RPD and outlines efficient approaches to the diagnosis of the various neurodegenerative, toxic-metabolic, infectious, autoimmune, neoplastic, and other conditions that may progress rapidly. PMID:18668637

  10. Rapid transbilayer movement of spin-labeled steroids in human erythrocytes and in liposomes.

    PubMed Central

    Müller, Peter; Herrmann, Andreas

    2002-01-01

    The transbilayer movement and distribution of spin-labeled analogs of the steroids androstane (SLA) and cholestane (SLC) were investigated in the human erythrocyte and in liposomes. Membranes were labeled with SLA or SLC, and the analogs in the outer leaflet were selectively reduced at 4C using 6-O-phenylascorbic acid. As shown previously, 6-O-phenylascorbic acid reduces rapidly nitroxides exposed on the outer leaflet, but its permeation of membranes is comparatively slow and thus does not interfere with the assay. From the reduction kinetics, we infer that transbilayer movement of SLA in erythrocytes is rapid at 4C with a half-time of approximately 4.3 min and that the probe distributes almost symmetrically between both halves of the plasma membrane. We have no indication that a protein-mediated transport is involved in the rapid transbilayer movement of SLA because 1) pretreatment of erythrocytes with N-ethyl maleimide affected neither flip-flop nor transbilayer distribution of SLA and 2) flip-flop of SLA was also rapid in pure lipid membranes. The transbilayer dynamics of SLC in erythrocyte membranes could not be resolved by our assay. Thus, the rate of SLC flip-flop must be on the order of, or even faster than, that of probe reduction rate on the exoplasmic leaflet (half-time approximately 0.5 min). The results are discussed with regard to the transbilayer dynamics of cholesterol. PMID:11867457

  11. Slide-and-exchange mechanism for rapid and selective transport through the nuclear pore complex

    PubMed Central

    Raveh, Barak; Karp, Jerome M.; Sparks, Samuel; Rout, Michael P.; Sali, Andrej; Cowburn, David

    2016-01-01

    Nucleocytoplasmic transport is mediated by the interaction of transport factors (TFs) with disordered phenylalanine-glycine (FG) repeats that fill the central channel of the nuclear pore complex (NPC). However, the mechanism by which TFs rapidly diffuse through multiple FG repeats without compromising NPC selectivity is not yet fully understood. In this study, we build on our recent NMR investigations showing that FG repeats are highly dynamic, flexible, and rapidly exchanging among TF interaction sites. We use unbiased long timescale all-atom simulations on the Anton supercomputer, combined with extensive enhanced sampling simulations and NMR experiments, to characterize the thermodynamic and kinetic properties of FG repeats and their interaction with a model transport factor. Both the simulations and experimental data indicate that FG repeats are highly dynamic random coils, lack intrachain interactions, and exhibit significant entropically driven resistance to spatial confinement. We show that the FG motifs reversibly slide in and out of multiple TF interaction sites, transitioning rapidly between a strongly interacting state and a weakly interacting state, rather than undergoing a much slower transition between strongly interacting and completely noninteracting (unbound) states. In the weakly interacting state, FG motifs can be more easily displaced by other competing FG motifs, providing a simple mechanism for rapid exchange of TF/FG motif contacts during transport. This slide-and-exchange mechanism highlights the direct role of the disorder within FG repeats in nucleocytoplasmic transport, and resolves the apparent conflict between the selectivity and speed of transport. PMID:27091992

  12. Low Gravity Rapid Thermal Analysis of Glass

    NASA Technical Reports Server (NTRS)

    Tucker, Dennis S.; Ethridge, Edwin C.; Smith, Guy A.

    2004-01-01

    It has been observed by two research groups that ZrF4-BaF2-LaF3-AlF3-NaF (ZBLAN) glass crystallization is suppressed in microgravity. The mechanism for this phenomenon is unknown at the present time. In order to better understand the mechanism, an experiment was performed on NASA's KC135 reduced gravity aircraft to obtain quantitative crystallization data. An apparatus was designed and constructed for performing rapid thermal analysis of milligram quantities of ZBLAN glass. The apparatus employs an ellipsoidal furnace allowing for rapid heating and cooling. Using this apparatus nucleation and crystallization kinetic data was obtained leading to the construction of time-temperature-transformation curves for ZBLAN in microgravity and unit gravity.

  13. Deconstruction Rapid Assessment Tool

    EPA Pesticide Factsheets

    Deconstruction Rapid Assessment Tool (EPA 905-F-15-001) instructions, form and spreadsheet for assessing and triaging structures being considered for deconstruction. Promote environmental stewardship and economic revitalization through deconstruction.

  14. RAPID and DDS

    NASA Technical Reports Server (NTRS)

    Utz, Hans Heinrich

    2011-01-01

    This talk gives an overview of the the Robot Applications Programmers Interface Delegate (RAPID) as well as the distributed systems middleware Data Distribution Service (DDS). DDS is an open software standard, RAPID is cleared for open-source release under NOSA. RAPID specifies data-structures and semantics for high-level telemetry published by NASA robotic software. These data-structures are supported by multiple robotic platforms at Johnson Space Center (JSC), Jet Propulsion Laboratory (JPL) and Ames Research Center (ARC), providing high-level interoperability between those platforms. DDS is used as the middleware for data transfer. The feature set of the middleware heavily influences the design decision made in the RAPID specification. So it is appropriate to discuss both in this introductory talk.

  15. Hydropower RAPID Toolkit

    SciTech Connect

    2016-12-01

    This fact sheet provides a brief overview of the U.S. Department of Energy (DOE) Hydropower Regulatory and Permitting Information Desktop (RAPID) Toolkit including its capabilities, features, and benefits.

  16. Algorithms, modelling and VO₂ kinetics.

    PubMed

    Capelli, Carlo; Carlo, Capelli; Cautero, Michela; Michela, Cautero; Pogliaghi, Silvia; Silvia, Pogliaghi

    2011-03-01

    This article summarises the pros and cons of different algorithms developed for estimating breath-by-breath (B-by-B) alveolar O(2) transfer (VO 2A) in humans. VO 2A is the difference between O(2) uptake at the mouth and changes in alveolar O(2) stores (∆ VO(2s)), which for any given breath, are equal to the alveolar volume change at constant FAO2/FAiO2 ∆VAi plus the O(2) alveolar fraction change at constant volume [V Ai-1(F Ai - F Ai-1) O2, where V (Ai-1) is the alveolar volume at the beginning of a breath. Therefore, VO 2A can be determined B-by-B provided that V (Ai-1) is: (a) set equal to the subject's functional residual capacity (algorithm of Auchincloss, A) or to zero; (b) measured (optoelectronic plethysmography, OEP); (c) selected according to a procedure that minimises B-by-B variability (algorithm of Busso and Robbins, BR). Alternatively, the respiratory cycle can be redefined as the time between equal FO(2) in two subsequent breaths (algorithm of Grønlund, G), making any assumption of V (Ai-1) unnecessary. All the above methods allow an unbiased estimate of VO2 at steady state, albeit with different precision. Yet the algorithms "per se" affect the parameters describing the B-by-B kinetics during exercise transitions. Among these approaches, BR and G, by increasing the signal-to-noise ratio of the measurements, reduce the number of exercise repetitions necessary to study VO2 kinetics, compared to A approach. OEP and G (though technically challenging and conceptually still debated), thanks to their ability to track ∆VO(2s) changes during the early phase of exercise transitions, appear rather promising for investigating B-by-B gas exchange.

  17. Temporal sampling requirements for the tracer kinetics modeling of breast disease.

    PubMed

    Henderson, E; Rutt, B K; Lee, T Y

    1998-11-01

    The physiological parameters measured in the tracer kinetics modeling of data from a dynamic contrast-enhanced magnetic resonance (MR) breast exam (blood flow-extraction fraction product [FE], volume of the extracellular extravascular space [Ve], and blood volume [Vb]) may enable non-invasive diagnosis of breast cancer. One of the factors that compromises the accuracy and precision of the parameter estimates, and therefore their diagnostic potential, is the temporal resolution of the MR scans used to measure contrast agent (gadolinium-diethylenetriamine pentaacetic acid [Gd-DTPA]) concentration in an artery (arterial input function [AIF]) and in the tissue (tissue residue function [TRF]). Using computer simulations, we have examined, for several AIF widths, the errors introduced into estimates of tracer kinetic parameters in breast tissue due to insufficient temporal sampling. Temporal sampling errors can be viewed as uncertainties and biases in the parameter estimates introduced by the uncertainty in the relative alignments of the AIF, TRF, and sampling grid. These effects arise from the model's inherent sensitivity to error in either the AIF or TRF, which is dependent on the values of the tracer kinetic parameters and increases with AIF width. Based on the results of the simulations, to ensure that the error in FE and Ve will be under 10% of their true values, we recommend a rapid bolus injection of contrast agent (approximately 10 s), that the AIF be sampled every second, and that the TRF be sampled every 16 s or less. An accurate measurement of Vb requires that the TRF be sampled at least every 4 s. The results of these investigations can be used to set minimum dynamic imaging rates for tracer kinetics modeling of the breast.

  18. Kinetics and mechanism of styrene epoxidation by chlorite: role of chlorine dioxide.

    PubMed

    Leigh, Jessica K; Rajput, Jonathan; Richardson, David E

    2014-07-07

    An investigation of the kinetics and mechanism for epoxidation of styrene and para-substituted styrenes by chlorite at 25 °C in the pH range of 5-6 is described. The proposed mechanism in water and water/acetonitrile includes seven oxidation states of chlorine (-I, 0, I, II, III, IV, and V) to account for the observed kinetics and product distributions. The model provides an unusually detailed quantitative mechanism for the complex reactions that occur in mixtures of chlorine species and organic substrates, particularly when the strong oxidant chlorite is employed. Kinetic control of the reaction is achieved by the addition of chlorine dioxide to the reaction mixture, thereby eliminating a substantial induction period observed when chlorite is used alone. The epoxidation agent is identified as chlorine dioxide, which is continually formed by the reaction of chlorite with hypochlorous acid that results from ClO produced by the epoxidation reaction. The overall stoichiometry is the result of two competing chain reactions in which the reactive intermediate ClO reacts with either chlorine dioxide or chlorite ion to produce hypochlorous acid and chlorate or chloride, respectively. At high chlorite ion concentrations, HOCl is rapidly eliminated by reaction with chlorite, minimizing side reactions between HOCl and Cl2 with the starting material. Epoxide selectivity (>90% under optimal conditions) is accurately predicted by the kinetic model. The model rate constant for direct reaction of styrene with ClO2(aq) to produce epoxide is (1.16 ± 0.07) × 10(-2) M(-1) s(-1) for 60:40 water/acetonitrile with 0.20 M acetate buffer. Rate constants for para substituted styrenes (R = -SO3(-), -OMe, -Me, -Cl, -H, and -NO2) with ClO2 were determined. The results support the radical addition/elimination mechanism originally proposed by Kolar and Lindgren to account for the formation of styrene oxide in the reaction of styrene with chlorine dioxide.

  19. Kinetic properties of fractal stellar media

    NASA Astrophysics Data System (ADS)

    Chumak, O. V.; Rastorguev, A. S.

    2017-01-01

    Kinetic processes in fractal stellar media are analysed in terms of the approach developed in our earlier paper involving a generalization of the nearest neighbour and random force distributions to fractal media. Diffusion is investigated in the approximation of scale-dependent conditional density based on an analysis of the solutions of the corresponding Langevin equations. It is shown that kinetic parameters (time-scales, coefficients of dynamic friction, diffusion, etc.) for fractal stellar media can differ significantly both qualitatively and quantitatively from the corresponding parameters for a quasi-uniform random media with limited fluctuations. The most important difference is that in the fractal case, kinetic parameters depend on spatial scalelength and fractal dimension of the medium studied. A generalized kinetic equation for stellar media (fundamental equation of stellar dynamics) is derived in the Fokker-Planck approximation with the allowance for the fractal properties of the spatial stellar density distribution. Also derived are its limit forms that can be used to describe small departures of fractal gravitating medium from equilibrium.

  20. Growth and dissolution kinetics of tetragonal lysozyme

    NASA Technical Reports Server (NTRS)

    Monaco, L. A.; Rosenberger, F.

    1993-01-01

    The growth and dissolution kinetics of lysozyme in a 25 ml solution bridge inside a closed growth cell was investigated. It was found that, under all growth conditions, the growth habit forming (110) and (101) faces grew through layer spreading with different growth rate dependence on supersaturation/temperature. On the other hand, (100) faces which formed only at low temperatures underwent a thermal roughening transition around 12 C.