WorldWideScience

Sample records for single reaction model

  1. Ignition and growth modeling of detonation reaction zone experiments on single crystals of PETN and HMX

    Science.gov (United States)

    White, Bradley W.; Tarver, Craig M.

    2017-01-01

    It has long been known that detonating single crystals of solid explosives have much larger failure diameters than those of heterogeneous charges of the same explosive pressed or cast to 98 - 99% theoretical maximum density (TMD). In 1957, Holland et al. demonstrated that PETN single crystals have failure diameters of about 8 mm, whereas heterogeneous PETN charges have failure diameters of less than 0.5 mm. Recently, Fedorov et al. quantitatively determined nanosecond time resolved detonation reaction zone profiles of single crystals of PETN and HMX by measuring the interface particle velocity histories of the detonating crystals and LiF windows using a PDV system. The measured reaction zone time durations for PETN and HMX single crystal detonations were approximately 100 and 260 nanoseconds, respectively. These experiments provided the necessary data to develop Ignition and Growth (I&G) reactive flow model parameters for the single crystal detonation reaction zones. Using these parameters, the calculated unconfined failure diameter of a PETN single crystal was 7.5 +/- 0.5 mm, close to the 8 mm experimental value. The calculated failure diameter of an unconfined HMX single crystal was 15 +/- 1 mm. The unconfined failure diameter of an HMX single crystal has not yet been determined precisely, but Fedorov et al. detonated 14 mm diameter crystals confined by detonating a HMX-based plastic bonded explosive (PBX) without initially overdriving the HMX crystals.

  2. Modeling of the interplay between single-file diffusion and conversion reaction in mesoporous systems

    Energy Technology Data Exchange (ETDEWEB)

    Wang, Jing [Iowa State Univ., Ames, IA (United States)

    2013-01-11

    We analyze the spatiotemporal behavior of species concentrations in a diffusion-mediated conversion reaction which occurs at catalytic sites within linear pores of nanometer diameter. A strict single-file (no passing) constraint occurs in the diffusion within such narrow pores. Both transient and steady-state behavior is precisely characterized by kinetic Monte Carlo simulations of a spatially discrete lattice–gas model for this reaction–diffusion process considering various distributions of catalytic sites. Exact hierarchical master equations can also be developed for this model. Their analysis, after application of mean-field type truncation approximations, produces discrete reaction–diffusion type equations (mf-RDE). For slowly varying concentrations, we further develop coarse-grained continuum hydrodynamic reaction–diffusion equations (h-RDE) incorporating a precise treatment of single-file diffusion (SFD) in this multispecies system. Noting the shortcomings of mf-RDE and h-RDE, we then develop a generalized hydrodynamic (GH) formulation of appropriate gh-RDE which incorporates an unconventional description of chemical diffusion in mixed-component quasi-single-file systems based on a refined picture of tracer diffusion for finite-length pores. The gh-RDE elucidate the non-exponential decay of the steady-state reactant concentration into the pore and the non-mean-field scaling of the reactant penetration depth. Then an extended model of a catalytic conversion reaction within a functionalized nanoporous material is developed to assess the effect of varying the reaction product – pore interior interaction from attractive to repulsive. The analysis is performed utilizing the generalized hydrodynamic formulation of the reaction-diffusion equations which can reliably capture the complex interplay between reaction and restricted transport for both irreversible and reversible reactions.

  3. Improved single particle potential for transport model simulations of nuclear reactions induced by rare isotope beams

    International Nuclear Information System (INIS)

    Xu Chang; Li Baoan

    2010-01-01

    Taking into account more accurately the isospin dependence of nucleon-nucleon interactions in the in-medium many-body force term of the Gogny effective interaction, new expressions for the single-nucleon potential and the symmetry energy are derived. Effects of both the spin (isospin) and the density dependence of nuclear effective interactions on the symmetry potential and the symmetry energy are examined. It is shown that they both play a crucial role in determining the symmetry potential and the symmetry energy at suprasaturation densities. The improved single-nucleon potential will be useful for more accurate simulation of nuclear reactions induced by rare-isotope beams within transport models.

  4. Hydrogen Evolution Reaction in Alkaline Solution: From Theory, Single Crystal Models, to Practical Electrocatalysts.

    Science.gov (United States)

    Zheng, Yao; Jiao, Yan; Qiao, Shizhang; Vasileff, Anthony

    2017-12-01

    The hydrogen evolution reaction (HER) is a fundamental process in electrocatalysis and plays an important role in energy conversion for the development of hydrogen-based energy sources. However, the considerably slow rate of the HER in alkaline conditions has hindered advances in water splitting techniques for high-purity hydrogen production. Differing from well documented acidic HER, the mechanistic aspects of alkaline HER are yet to be settled. Herein, we present a critical appraisal of alkaline HER electrocatalysis, with a special emphasis on the connection between fundamental surface electrochemistry on single crystal models and the derived molecular design principle for real-world electrocatalysts. By presenting some typical examples across theoretical calculations, surface characterization, and electrochemical experiments, we try to address some key ongoing debates to deliver a better understanding of alkaline HER at the atomic level. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  5. A nonlocal and periodic reaction-diffusion-advection model of a single phytoplankton species.

    Science.gov (United States)

    Peng, Rui; Zhao, Xiao-Qiang

    2016-02-01

    In this article, we are concerned with a nonlocal reaction-diffusion-advection model which describes the evolution of a single phytoplankton species in a eutrophic vertical water column where the species relies solely on light for its metabolism. The new feature of our modeling equation lies in that the incident light intensity and the death rate are assumed to be time periodic with a common period. We first establish a threshold type result on the global dynamics of this model in terms of the basic reproduction number R0. Then we derive various characterizations of R0 with respect to the vertical turbulent diffusion rate, the sinking or buoyant rate and the water column depth, respectively, which in turn give rather precise conditions to determine whether the phytoplankton persist or become extinct. Our theoretical results not only extend the existing ones for the time-independent case, but also reveal new interesting effects of the modeling parameters and the time-periodic heterogeneous environment on persistence and extinction of the phytoplankton species, and thereby suggest important implications for phytoplankton growth control.

  6. Modelling Tethered Enzymatic Reactions

    Science.gov (United States)

    Solis Salas, Citlali; Goyette, Jesse; Coker-Gordon, Nicola; Bridge, Marcus; Isaacson, Samuel; Allard, Jun; Maini, Philip; Dushek, Omer

    Enzymatic reactions are key to cell functioning, and whilst much work has been done in protein interaction in cases where diffusion is possible, interactions of tethered proteins are poorly understood. Yet, because of the large role cell membranes play in enzymatic reactions, several reactions may take place where one of the proteins is bound to a fixed point in space. We develop a model to characterize tethered signalling between the phosphatase SHP-1 interacting with a tethered, phosphorylated protein. We compare our model to experimental data obtained using surface plasmon resonance (SPR). We show that a single SPR experiment recovers 5 independent biophysical/biochemical constants. We also compare the results between a three dimensional model and a two dimensional model. The work gives the opportunity to use known techniques to learn more about signalling processes, and new insights into how enzyme tethering alters cellular signalling. With support from the Mexican Council for Science and Technology (CONACyT), the Public Education Secretariat (SEP), and the Mexican National Autonomous University's Foundation (Fundacion UNAM).

  7. Exploring single electrode reactions in polymer electrolyte fuel cells

    Energy Technology Data Exchange (ETDEWEB)

    Kuhn, H.; Wokaun, A.; Scherer, G.G. [Paul Scherrer Institute, Electrochemistry Laboratory, 5232 Villigen (Switzerland)

    2007-01-20

    Utilising a pseudo-reference electrode in polymer electrolyte fuel cells allows for the separation of anodic and cathodic contributions to the entire cell impedance. Modelling the impedance responses by using equivalent circuits inhibits the investigation of kinetic parameters of the basic electrochemical reactions, which take place at single electrode-electrolyte interfaces. Therefore, we evaluate single electrode impedance measurements by a kinetic model, which is based on specific reaction pathways, either for the oxygen reduction reaction (ORR) or the hydrogen oxidation reaction (HOR). As a consequence, it is possible to obtain kinetic parameters for the specific reaction of interest. Furthermore, the information gained from the single electrode impedance measurements and the kinetic model can give insight into single reactions steps. In particular, the ORR has to include a chemical step in the reaction pathway. (author)

  8. Application of noncatalytic gas-solid reactions for a single pellet of changing size to the modeling of fluidized-bed combustion of coal char containing sulfur

    Energy Technology Data Exchange (ETDEWEB)

    Rehmat, A.; Saxena, S.C.; Land, R.H.

    1980-09-01

    A mechanistic model is developed for coal char combustion, with sulfur retention by limestone or dolomite sorbent, in a gas fluidized bed employing noncatalytic single pellet gas-solid reactions. The shrinking core model is employed to describe the kinetics of chemical reactions taking place on a single pellet; changes in pellet size as the reaction proceeds are considered. The solids are assumed to be in back-mix condition whereas the gas flow is regarded to be in plug flow. Most char combustion occurs near the gas distributor plate (at the bottom of the bed), where the bubbles are small and consequently the mass transfer rate is high. For such a case, the analysis is considerably simplified by ignoring the bubble phase since it plays an insignificant role in the overall rate of carbon conversion. Bubble-free operation is also encounterd in the turbulent regime, where the gas flow is quite high and classical bubbles do not exist. Formulation of the model includes setting up heat and mass balance equations pertaining to a single particle (1) exposed to a varying reactant concentration along the height of the bed and (2) whose size changes during reaction. These equations are then solved numerically to account for particles of all sizes in the bed in obtaining the overall carbon conversion efficiency and resultant sulfur retention. In particular, the influence on sorbent requirement of several fluid-bed variables such as oxygen concentration profile, particle size, reaction rate for sulfation reaction, and suflur adsorption efficiency are examined.

  9. Low dose endotoxin priming is accountable for coagulation abnormalities and organ damage observed in the Shwartzman reaction. A comparison between a single-dose endotoxemia model and a double-hit endotoxin-induced Shwartzman reaction

    Directory of Open Access Journals (Sweden)

    Cate Hugo

    2006-08-01

    Full Text Available Abstract The clinical response of sepsis to a systemic inflammatory infection may be complicated by disseminated intravascular coagulation or DIC. In order to experimentally study the syndrome of DIC, we aimed for a severe sepsis model complicated by disseminated coagulation. Most -simplified- experimental models describing coagulation abnormalities as a consequence of sepsis are based on single dose endotoxemia. The so called-Shwartzman reaction contrarily, is elicited by a low dose endotoxin priming followed by an LPS challenge and is characterized by pathological manifestations that represent the syndrome of DIC. In order to investigate whether the Shwartzman reaction is superior to a single endotoxin challenge as a model for sepsis-induced DIC and to determine what the pathological effect is of an encounter of low endotoxin prior to an LPS challenge, we undertook the present study. In this study we demonstrate that low-dose endotoxin priming prior to an LPS challenge in the Shwartzman reaction is accountable for micro-vascular thrombosis in lung and liver and subsequent (multi- organ failure, not observed after a single-dose endotoxin challenge, which indicates that the Shwartzman reaction is well suited-model to study sepsis-induced DIC adversities. Remarkably, only minor differences in the innate immune response were established between the single-dose endotoxin challenge and the Shwartzman reaction.

  10. Kinetic modelling of hydrocracking catalytic reactions by the single events theory; Modelisation cinetique des reactions catalytiques d`hydrocraquage par la theorie des evenements constitutifs

    Energy Technology Data Exchange (ETDEWEB)

    Schweitzer, J.M.

    1998-11-23

    Kinetic modelling of petroleum hydrocracking is particularly difficult given the complexity of the feedstocks. There are two distinct classes of kinetics models: lumped empirical models and detailed molecular models. The productivity of lumped empirical models is generally not very accurate, and the number of kinetic parameters increases rapidly with the number of lumps. A promising new methodology is the use of kinetic modelling based on the single events theory. Due to the molecular approach, a finite and limited number of kinetic parameters can describe the kinetic behaviour of the hydrocracking of heavy feedstock. The parameters are independent of the feedstock. However, the available analytical methods are not able to identify the products on the molecular level. This can be accounted for by means of an posteriori lamping technique, which incorporates the detailed knowledge of the elementary step network. Thus, the lumped kinetic parameters are directly calculated from the fundamental kinetic coefficients and the single event model is reduced to a re-lumped molecular model. Until now, the ability of the method to extrapolate to higher carbon numbers had not been demonstrated. In addition, no study had been published for three phase (gas-liquid-solid) systems and a complex feedstock. The objective of this work is to validate the `single events` method using a paraffinic feedstock. First of all, a series of experiments was conducted on a model compound (hexadecane) in order to estimate the fundamental kinetic parameters for acyclic molecules. To validate the single event approach, these estimated kinetic coefficients were used to simulate hydrocracking of a paraffinic mixture ranging from C11 to C18. The simulation results were then compared to the results obtained from the hydrocracking experiments. The comparison allowed to validate the model for acyclic molecules and to demonstrate that the model is applicable to compounds with higher carbon numbers. (author

  11. Free-Propagator Reweighting Integrator for Single-Particle Dynamics in Reaction-Diffusion Models of Heterogeneous Protein-Protein Interaction Systems

    Directory of Open Access Journals (Sweden)

    Margaret E. Johnson

    2014-09-01

    Full Text Available We present a new algorithm for simulating reaction-diffusion equations at single-particle resolution. Our algorithm is designed to be both accurate and simple to implement, and to be applicable to large and heterogeneous systems, including those arising in systems biology applications. We combine the use of the exact Green’s function for a pair of reacting particles with the approximate free-diffusion propagator for position updates to particles. Trajectory reweighting in our free-propagator reweighting (FPR method recovers the exact association rates for a pair of interacting particles at all times. FPR simulations of many-body systems accurately reproduce the theoretically known dynamic behavior for a variety of different reaction types. FPR does not suffer from the loss of efficiency common to other path-reweighting schemes, first, because corrections apply only in the immediate vicinity of reacting particles and, second, because by construction the average weight factor equals one upon leaving this reaction zone. FPR applications include the modeling of pathways and networks of protein-driven processes where reaction rates can vary widely and thousands of proteins may participate in the formation of large assemblies. With a limited amount of bookkeeping necessary to ensure proper association rates for each reactant pair, FPR can account for changes to reaction rates or diffusion constants as a result of reaction events. Importantly, FPR can also be extended to physical descriptions of protein interactions with long-range forces, as we demonstrate here for Coulombic interactions.

  12. Modeling of Reaction Calorimeter

    OpenAIRE

    Farzad, Reza

    2014-01-01

    The purpose of this project was to model the reaction calorimeter in order to calculate the heat of absorption which is the most important parameter in this work. Reaction calorimeter is an apparatus which is used in measuring the heat of absorption of CO2 as well as the total pressure in vapor phase based on vapor-liquid equilibrium state. Mixture of monoethanolamine (MEA) and water was used as a solvent to absorb the CO2.Project was divided in to three parts in order to make the programming...

  13. A model of reaction field in gas-injected arc-in-water method to synthesize single-walled carbon nanohorns: Influence of water temperature

    International Nuclear Information System (INIS)

    Poonjarernsilp, Chantamanee; Sano, Noriaki; Tamon, Hajime; Charinpanitkul, Tawatchai

    2009-01-01

    The method to synthesize single-walled carbon nanohorns (SWCNHs) using gas-injected arc in water (GI-AIW) has been experimentally studied. GI-AIW is known as one of the cost-effective methods to obtain SWCNHs. It was revealed that the yield of SWCNHs significantly decreases with the increase in water temperature although the purity of SWCNHs is not dependent on the temperature change. Then the model of relevant reactions in the GI-AIW system was proposed by accounting the emission of carbon vapor, formation of SWCNHs, and diffusion of water vapor in three zones inside the cathode hole (arc plasma zone, quenching zone, and downstream zone). The side reaction between H 2 O and C produces H 2 gas and consumes a certain amount of carbon vapor, resulting in the hindered SWCNH formation. Moreover the observation of the optical spectra emitting from the arc plasma zone strongly supported that the H 2 generating reaction does not occur at arc plasma zone since N 2 flow can purge H 2 O out. The model proposed in this study can precisely explain the correlation between H 2 gas production and water temperature.

  14. Kinetic Study on Peptide-Bound Pyrraline Formation and Elimination in the Maillard Reaction Using Single- and Multiple-Response Models.

    Science.gov (United States)

    Liang, Zhili; Li, Lin; Qi, Haiping; Zhang, Zhenbo Xu Xia; Li, Bing

    2016-10-01

    Pyrraline, an advanced glycation end product (AGE), is related to some chronic diseases and can be employed as an indicator for heat damage in food processing. In this study, the impact of changing the reactant concentration and ratio on the kinetic parameters describing peptide-bound pyrraline (pep-pyr) formation and elimination was evaluated in the Lys-Gly/glucose model systems, with microwave heating treatment ranging from 120 to 200 °C. The maximum pep-pyr concentration increased as follows: 200 °C ˂ 180 °C ˂ 160 °C ˂ 120 °C ˂ 140 °C. First, the pep-pyr formation and elimination was modeled by using a single-response modelling. The formation rate constant (k F ) of pep-pyr was independent of the initial concentration of the reactants and ratios. However, the elimination rate constant of pep-pyr (k E ) increased with increasing reactant concentrations. Second, a multiresponse modelling was performed to illustrate the pathways of pep-pyr formation and elimination. Two adapted models can fit to the experimental data with the goodness-of-fit ranging from 0.663 to 0.920. Glucose-to-fructose isomerization rather than glucose-to-mannose epimerization was detected in an equimolar model system and the model system with an excess of any of the reactants. The caramelization reaction was negligible in the equimolar systems and the model systems with an excess of peptide. The reaction rate constant of glucose-to-fructose isomerization was independent of the initial reactant ratios. It was more difficult for pep-pyr elimination in the model system with an excess of peptide than that in the other 2 model systems (the equimolar system and the system with an excess of glucose), whereas a reverse result in pep-pyr formation was obtained. © 2016 Institute of Food Technologists®.

  15. Reaction Gradients Viewed Inside Single Photoactive Particles

    Science.gov (United States)

    Alpert, P.; Corral Arroyo, P.; Dou, J.; Kreiger, U.; Luo, B.; Peter, T.; Ammann, M.

    2017-12-01

    In terms of chemical selectivity and spatial resolution, a technique known as scanning transmission X-ray microscopy coupled to near-edge X-ray absorption fine structure spectroscopy (STXM/NEXAFS) is unmatched and will remain so for years into the future. We present a recent development coupling STXM/NEXAFS to a custom-built photochemical environmental reactor in which aerosol particles reside allowing for in situ chemical imaging. A laboratory investigation of metal-organic complex photochemistry was conducted. Transition metals are of great importance to atmospheric chemistry and aerosol photochemical aging due to their ability to catalyze oxidation reactions. Aerosol particles composed of mixtures of citric acid and iron citrate were probed for their organic carbon composition and iron oxidation state under atmospherically relevant conditions. At 40% relative humidity, oxygen diffusion and reaction was severely limited. Fe was reoxidized in the first 200 nm of the particle surface leaving reduced iron in the core. Similar gradients were observed at 60% RH, however waiting approximately 2 hours in the dark resulted in a recovery of the initial Fe(III) concentration. We draw two main conclusions from our findings. Frist, the oxidation gradients must have been the result of anoxic conditions at the interior of aerosol particles. This was predicted using a newly developed model for molecular diffusion through multiple layers with a reaction framework describing the photochemical processing of the metal organic matrix. Second, the lifetime of organic radicals in an anoxic diffusion limited organic matrix must be considerably long ( hours) to completely reoxidize iron as they wait for molecular oxygen. Long radical lifetimes in viscous organic aerosol in turn, could create high radical concentrations or favor radical-radical reactions in particles typically not considered when oxygen is plentiful. Our results impact predictions of aerosol physiochemical properties, e

  16. Large scale collective modeling the final 'freeze out' stages of energetic heavy ion reactions and calculation of single particle measurables from these models

    International Nuclear Information System (INIS)

    Nyiri, Agnes

    2005-01-01

    -relativistic heavy ion reactions is an important hadronic observable sensitive to the early stages of system evolution. The flow analysis involves the particles, which have already been frozen out. Therefore, to perform realistic flow computations from the Multi Module Model we need a complete freeze out description and a well identified freeze out surface. However, the freeze out module is still not ready. Although we have not yet been able to evaluate collective flow using the Multi Module Model, the method and code for the calculation of flow components has been worked out in an independent module. This module is completed and can be coupled to the previous modules when those are ready for use. In order to test the code, we have calculated directed and elliptic flow from a tilted, ellipsoidally expanding source using a simple, blast wave type of model. This model was developed directly for this aim based on Buda-Lund hydro models. Although, this oversimplified blast wave model is not suitable to reproduce the experimental data -which will be an important task in the future to check our Multi Module Model-, it has provided us with important information. We have found that the directed flow, is very sensitive to the correct identification of the reaction plane included the determination of the impact parameter vector, and can be misinterpreted by some experimental methods. We have shown that misidentification of the reaction plane may even set the directed flow to zero by construction. We have presented results of the rapidity dependence of the directed flow, v1, and elliptic flow, v2, furthermore, the transverse momentum dependence of v2. We have also investigated the dependence of the flow pattern on the initial geometry of the fireball by calculating flow components from two ellipsoidal sources with the same thermodynamical properties but different shape. The code determining the freeze out hypersurface should still be improved in order to avoid inaccuracies in the further

  17. Large scale collective modeling the final 'freeze out' stages of energetic heavy ion reactions and calculation of single particle measurables from these models

    Energy Technology Data Exchange (ETDEWEB)

    Nyiri, Agnes

    2005-07-01

    -relativistic heavy ion reactions is an important hadronic observable sensitive to the early stages of system evolution. The flow analysis involves the particles, which have already been frozen out. Therefore, to perform realistic flow computations from the Multi Module Model we need a complete freeze out description and a well identified freeze out surface. However, the freeze out module is still not ready. Although we have not yet been able to evaluate collective flow using the Multi Module Model, the method and code for the calculation of flow components has been worked out in an independent module. This module is completed and can be coupled to the previous modules when those are ready for use. In order to test the code, we have calculated directed and elliptic flow from a tilted, ellipsoidally expanding source using a simple, blast wave type of model. This model was developed directly for this aim based on Buda-Lund hydro models. Although, this oversimplified blast wave model is not suitable to reproduce the experimental data--which will be an important task in the future to check our Multi Module Model--it has provided us with important information. We have found that the directed flow, is very sensitive to the correct identification of the reaction plane included the determination of the impact parameter vector, and can be misinterpreted by some experimental methods. We have shown that misidentification of the reaction plane may even set the directed flow to zero by construction. We have presented results of the rapidity dependence of the directed flow, v1, and elliptic flow, v2, furthermore, the transverse momentum dependence of v2. We have also investigated the dependence of the flow pattern on the initial geometry of the fireball by calculating flow components from two ellipsoidal sources with the same thermodynamical properties but different shape. The code determining the freeze out hypersurface should still be improved in order to avoid inaccuracies in the further

  18. Action spectroscopy for single-molecule reactions - Experiments and theory

    Science.gov (United States)

    Kim, Y.; Motobayashi, K.; Frederiksen, T.; Ueba, H.; Kawai, M.

    2015-05-01

    We review several representative experimental results of action spectroscopy (AS) of single molecules on metal surfaces using a scanning tunneling microscope (STM) by M. Kawai's group over last decade. The experimental procedures to observe STM-AS are described. A brief description of a low-temperature STM and experimental setup are followed by key experimental techniques of how to determine an onset bias voltage of a reaction and how to measure a current change associated with reactions and finally how to observe AS for single molecule reactions. The experimental results are presented for vibrationally mediated chemical transformation of trans-2-butene to 1.3-butadiene molecule and rotational motion of a single cis-2-butene molecule among four equivalent orientations on Pd(1 1 0). The AS obtained from the motion clearly detects more vibrational modes than inelastic electron tunneling spectroscopy with an STM. AS is demonstrated as a useful and novel single molecule vibrational spectroscopy. The AS for a lateral hopping of water dimer on Pt(1 1 1) is presented as an example of novelty. Several distinct vibrational modes are detected as the thresholds in the AS. The assignment of the vibrational modes determined from the analysis of the AS is made from a view of the adsorption geometry of hydrogen-bond donor or acceptor molecules in water dimer. A generic theory of STM-AS, i.e., a reaction rate or yield as a function of bias voltage, is presented using a single adsorbate resonance model for single molecule reactions induced by the inelastic tunneling current. Formulas for the reaction rate R (V) and Y (V) , i.e., reaction yield per electron Y (V) = eR (V) / I are derived. It provides a versatile framework to analyze any vibrationally mediated reactions of single adsorbates on metal surfaces. Numerical examples are presented to demonstrate generic features of the vibrational generation rate and Y (V) at different levels of approximations and to show how the effective

  19. Reaction path analysis of sodium-water reaction phenomena in support of chemical reaction model development

    International Nuclear Information System (INIS)

    Kikuchi, Shin; Ohshima, Hiroyuki; Hashimoto, Kenro

    2011-01-01

    Computational study of the sodium-water reaction at the gas (water) - liquid (sodium) interface has been carried out using ab initio (first-principle) method. A possible reaction channel has been identified for the stepwise OH bond dissociations of a single water molecule. The energetics including the binding energy of a water molecule to the sodium surface, the activation energies of the bond cleavages, and the reaction energies, have been evaluated, and the rate constants of the first and second OH bond-breakings have been compared. The results are used as the basis for constructing the chemical reaction model used in a multi-dimensional sodium-water reaction code, SERAPHIM, being developed by JAEA toward the safety assessment of the steam generator (SG) in a sodium-cooled fast reactor (SFR). (author)

  20. Reduction of chemical reaction models

    Science.gov (United States)

    Frenklach, Michael

    1991-01-01

    An attempt is made to reconcile the different terminologies pertaining to reduction of chemical reaction models. The approaches considered include global modeling, response modeling, detailed reduction, chemical lumping, and statistical lumping. The advantages and drawbacks of each of these methods are pointed out.

  1. Study of single nucleon transfer in α + 12C reaction

    International Nuclear Information System (INIS)

    Pandey, R.; Rana, T.K.; Dey, A.; Bhattacharya, C.; Kundu, S.; Banerjee, K.; Mukherjee, G.; Ghosh, T.K.; Meena, J.K.; Pai, H.; Gohil, M.; Bhattacharya, S.; Biswas, M.

    2011-01-01

    Nucleon transfer reactions are of great significance for understanding the nuclear structure both for direct reaction studies as well as for production of nuclear states. Transfer reactions are simplest to interpret when either the initial and final state of the target nucleus has spin zero and when the conditions are such that the transition from the initial and final states occurs to a good approximation in a single step. In this paper, the measurement of angular momentum distribution and calculation of the spectroscopic factor for one nucleon transfer reaction in α + 12 C reaction have been reported

  2. Single-Atom Catalysts of Precious Metals for Electrochemical Reactions.

    Science.gov (United States)

    Kim, Jiwhan; Kim, Hee-Eun; Lee, Hyunjoo

    2018-01-10

    Single-atom catalysts (SACs), in which metal atoms are dispersed on the support without forming nanoparticles, have been used for various heterogeneous reactions and most recently for electrochemical reactions. In this Minireview, recent examples of single-atom electrocatalysts used for the oxygen reduction reaction (ORR), hydrogen oxidation reaction (HOR), hydrogen evolution reaction (HER), formic acid oxidation reaction (FAOR), and methanol oxidation reaction (MOR) are introduced. Many density functional theory (DFT) simulations have predicted that SACs may be effective for CO 2 reduction to methane or methanol production while suppressing H 2 evolution, and those cases are introduced here as well. Single atoms, mainly Pt single atoms, have been deposited on TiN or TiC nanoparticles, defective graphene nanosheets, N-doped covalent triazine frameworks, graphitic carbon nitride, S-doped zeolite-templated carbon, and Sb-doped SnO 2 surfaces. Scanning transmission electron microscopy, extended X-ray absorption fine structure measurement, and in situ infrared spectroscopy have been used to detect the single-atom structure and confirm the absence of nanoparticles. SACs have shown high mass activity, minimizing the use of precious metal, and unique selectivity distinct from nanoparticle catalysts owing to the absence of ensemble sites. Additional features that SACs should possess for effective electrochemical applications were also suggested. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  3. Direct single-molecule dynamic detection of chemical reactions.

    Science.gov (United States)

    Guan, Jianxin; Jia, Chuancheng; Li, Yanwei; Liu, Zitong; Wang, Jinying; Yang, Zhongyue; Gu, Chunhui; Su, Dingkai; Houk, Kendall N; Zhang, Deqing; Guo, Xuefeng

    2018-02-01

    Single-molecule detection can reveal time trajectories and reaction pathways of individual intermediates/transition states in chemical reactions and biological processes, which is of fundamental importance to elucidate their intrinsic mechanisms. We present a reliable, label-free single-molecule approach that allows us to directly explore the dynamic process of basic chemical reactions at the single-event level by using stable graphene-molecule single-molecule junctions. These junctions are constructed by covalently connecting a single molecule with a 9-fluorenone center to nanogapped graphene electrodes. For the first time, real-time single-molecule electrical measurements unambiguously show reproducible large-amplitude two-level fluctuations that are highly dependent on solvent environments in a nucleophilic addition reaction of hydroxylamine to a carbonyl group. Both theoretical simulations and ensemble experiments prove that this observation originates from the reversible transition between the reactant and a new intermediate state within a time scale of a few microseconds. These investigations open up a new route that is able to be immediately applied to probe fast single-molecule physics or biophysics with high time resolution, making an important contribution to broad fields beyond reaction chemistry.

  4. QGSM development for spallation reactions modeling

    Directory of Open Access Journals (Sweden)

    Gudima K.K.

    2012-12-01

    Full Text Available The growing interest in spallation neutron sources, accelerator-driven systems, R&D of rare isotope beams, and development of external beam radiation therapy necessitated the improvement of nuclear reaction models for both stand-alone codes for the analysis of nuclear reactions and event generators within the Monte Carlo transport systems for calculations of interactions of high-energy particles with matter in a wide range of energy and in arbitrary 3D geometry of multicomponent targets. The exclusive approach to the description of nuclear reactions is the most effective for detailed calculation of inelastic interactions with atomic nuclei. It provides the correct description of particle production, single- and double-differential spectra, recoil, and fission product yields. This approach has been realized in the Quark Gluon String Model (QGSM for nuclear reactions induced by photons, hadrons, and high energy heavy ions. In this article, improved versions of the QGSM model and a corresponding code have been developed tested and bench marked against experimental data for neutron production in spallation reactions on thin and thick targets in the energy range from a few MeV to several GeV/nucleon.

  5. QGSM development for spallation reactions modeling

    Science.gov (United States)

    Baznat, M. I.; Chigrinov, S. E.; Gudima, K. K.

    2012-12-01

    The growing interest in spallation neutron sources, accelerator-driven systems, R&D of rare isotope beams, and development of external beam radiation therapy necessitated the improvement of nuclear reaction models for both stand-alone codes for the analysis of nuclear reactions and event generators within the Monte Carlo transport systems for calculations of interactions of high-energy particles with matter in a wide range of energy and in arbitrary 3D geometry of multicomponent targets. The exclusive approach to the description of nuclear reactions is the most effective for detailed calculation of inelastic interactions with atomic nuclei. It provides the correct description of particle production, single- and double-differential spectra, recoil, and fission product yields. This approach has been realized in the Quark Gluon String Model (QGSM) for nuclear reactions induced by photons, hadrons, and high energy heavy ions. In this article, improved versions of the QGSM model and a corresponding code have been developed tested and bench marked against experimental data for neutron production in spallation reactions on thin and thick targets in the energy range from a few MeV to several GeV/nucleon.

  6. Modelling Students' Visualisation of Chemical Reaction

    Science.gov (United States)

    Cheng, Maurice M. W.; Gilbert, John K.

    2017-01-01

    This paper proposes a model-based notion of "submicro representations of chemical reactions". Based on three structural models of matter (the simple particle model, the atomic model and the free electron model of metals), we suggest there are two major models of reaction in school chemistry curricula: (a) reactions that are simple…

  7. Single-molecule chemical reaction reveals molecular reaction kinetics and dynamics.

    Science.gov (United States)

    Zhang, Yuwei; Song, Ping; Fu, Qiang; Ruan, Mingbo; Xu, Weilin

    2014-06-25

    Understanding the microscopic elementary process of chemical reactions, especially in condensed phase, is highly desirable for improvement of efficiencies in industrial chemical processes. Here we show an approach to gaining new insights into elementary reactions in condensed phase by combining quantum chemical calculations with a single-molecule analysis. Elementary chemical reactions in liquid-phase, revealed from quantum chemical calculations, are studied by tracking the fluorescence of single dye molecules undergoing a reversible redox process. Statistical analyses of single-molecule trajectories reveal molecular reaction kinetics and dynamics of elementary reactions. The reactivity dynamic fluctuations of single molecules are evidenced and probably arise from either or both of the low-frequency approach of the molecule to the internal surface of the SiO2 nanosphere or the molecule diffusion-induced memory effect. This new approach could be applied to other chemical reactions in liquid phase to gain more insight into their molecular reaction kinetics and the dynamics of elementary steps.

  8. High-pressure catalytic reactions over single-crystal metal surfaces

    Science.gov (United States)

    Rodriguez, JoséA.; Wayne Goodman, D.

    1991-11-01

    Studies dealing with high-pressure catalytic reactions over single-crystal surfaces are reviewed. The coupling of an apparatus for the measurement of reaction kinetics at elevated pressures with an ultrahigh vacuum system for surface analysis allows detailed study of structure sensitivity, the effects of promoters and inhibitors on catalytic activity, and, in certain cases, identification of reaction intermediates by post-reaction surface analysis. Examples are provided which demonstrate the relevance of single-crystal studies for modeling the behaviour of high-surface-area supported catalysts. Studies of CO methanation and CO oxidation over single-crystal surfaces provide convincing evidence that these reactions are structure insensitive. For structure-sensitive reactions (ammonia synthesis, alkane hydrogenolysis, alkane isomerization, water-gas shift reaction, etc.) model single-crystal studies allow correlations to be established between surface structure and catalytic activity. The effects of both electronegative (S and P) and electropositive (alkali metals) impurities upon the catalytic activity of metal single crystals for ammonia synthesis, CO methanation, alkane hydrogenolysis, ethylene epoxidation and water-gas shift are discussed. The roles of "ensemble" and "ligand" effects in bimetallic catalysts are examined in light of data obtained using surfaces prepared by vapor-depositing one metal onto a crystal face of a dissimilar metal.

  9. High performance platinum single atom electrocatalyst for oxygen reduction reaction

    Science.gov (United States)

    Liu, Jing; Jiao, Menggai; Lu, Lanlu; Barkholtz, Heather M.; Li, Yuping; Wang, Ying; Jiang, Luhua; Wu, Zhijian; Liu, Di-Jia; Zhuang, Lin; Ma, Chao; Zeng, Jie; Zhang, Bingsen; Su, Dangsheng; Song, Ping; Xing, Wei; Xu, Weilin; Wang, Ying; Jiang, Zheng; Sun, Gongquan

    2017-07-01

    For the large-scale sustainable implementation of polymer electrolyte membrane fuel cells in vehicles, high-performance electrocatalysts with low platinum consumption are desirable for use as cathode material during the oxygen reduction reaction in fuel cells. Here we report a carbon black-supported cost-effective, efficient and durable platinum single-atom electrocatalyst with carbon monoxide/methanol tolerance for the cathodic oxygen reduction reaction. The acidic single-cell with such a catalyst as cathode delivers high performance, with power density up to 680 mW cm-2 at 80 °C with a low platinum loading of 0.09 mgPt cm-2, corresponding to a platinum utilization of 0.13 gPt kW-1 in the fuel cell. Good fuel cell durability is also observed. Theoretical calculations reveal that the main effective sites on such platinum single-atom electrocatalysts are single-pyridinic-nitrogen-atom-anchored single-platinum-atom centres, which are tolerant to carbon monoxide/methanol, but highly active for the oxygen reduction reaction.

  10. Multiresponse modelling of the caramelisation reaction

    OpenAIRE

    Quintas, Mafalda; Guimarães, Carla; Baylina, João; Brandão, Teresa R. S.; Silva, Cristina L.M.

    2007-01-01

    Multiresponse modelling is a powerful tool for studying complex kinetics of reactions occurring in food products. This modelling technique uses information of reactants and products involved, allowing insightful kinetic parameters estimation and helping in clarifying reaction mechanisms. One example of a complex reaction that occurs in food processing is the caramelisation reaction. Caramelisation is the common name for a group of reactions observed when carbohydrates are exposed to high temp...

  11. Reaction kinetics of oxygen on single-phase alloys, oxidation of nickel and niobium alloys

    International Nuclear Information System (INIS)

    Lalauze, Rene

    1973-01-01

    This research thesis first addresses the reaction kinetics of oxygen on alloys. It presents some generalities on heterogeneous reactions (conventional theory, theory of jumps), discusses the core reaction (with the influence of pressure), discusses the influence of metal self-diffusion on metal oxidation kinetics (equilibrium conditions at the interface, hybrid diffusion regime), reports the application of the hybrid diffusion model to the study of selective oxidation of alloys (Wagner model, hybrid diffusion model) and the study of the oxidation kinetics of an alloy forming a solid solution of two oxides. The second part reports the investigation of the oxidation of single phase nickel and niobium alloys (phase α, β and γ)

  12. Single Item Inventory Models

    NARCIS (Netherlands)

    E.M. Bazsa-Oldenkamp; P. den Iseger

    2001-01-01

    textabstractThis paper extends a fundamental result about single-item inventory systems. This approach allows more general performance measures, demand processes and order policies, and leads to easier analysis and implementation, than prior research. We obtain closed form expressions for the

  13. Modelling Chemical Reasoning to Predict and Invent Reactions.

    Science.gov (United States)

    Segler, Marwin H S; Waller, Mark P

    2017-05-02

    The ability to reason beyond established knowledge allows organic chemists to solve synthetic problems and invent novel transformations. Herein, we propose a model that mimics chemical reasoning, and formalises reaction prediction as finding missing links in a knowledge graph. We have constructed a knowledge graph containing 14.4 million molecules and 8.2 million binary reactions, which represents the bulk of all chemical reactions ever published in the scientific literature. Our model outperforms a rule-based expert system in the reaction prediction task for 180 000 randomly selected binary reactions. The data-driven model generalises even beyond known reaction types, and is thus capable of effectively (re-)discovering novel transformations (even including transition metal-catalysed reactions). Our model enables computers to infer hypotheses about reactivity and reactions by only considering the intrinsic local structure of the graph and because each single reaction prediction is typically achieved in a sub-second time frame, the model can be used as a high-throughput generator of reaction hypotheses for reaction discovery. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  14. Mass transfer with complex reversible chemical reactions I. Single reversible chemical reaction

    NARCIS (Netherlands)

    Versteeg, Geert; Kuipers, J.A.M.; van Beckum, F.P.H.; van Swaaij, Willibrordus Petrus Maria

    1989-01-01

    An improved numerical technique was used in order to develop an absorption model with which it is possible to calculate rapidly absorption rates for the phenomenon of mass transfer accompanied by a complex reversible chemical reaction. This model can be applied for the calculation of the mass

  15. Single-molecule chemical reactions on DNA origami

    DEFF Research Database (Denmark)

    Voigt, Niels Vinther; Tørring, Thomas; Rotaru, Alexandru

    2010-01-01

    DNA nanotechnology and particularly DNA origami, in which long, single-stranded DNA molecules are folded into predetermined shapes, can be used to form complex self-assembled nanostructures. Although DNA itself has limited chemical, optical or electronic functionality, DNA nanostructures can serve...... on a DNA origami scaffold by atomic force microscopy. The high yields and chemoselectivities of successive cleavage and bond-forming reactions observed in these experiments demonstrate the feasibility of post-assembly chemical modification of DNA nanostructures and their potential use as locally...

  16. Single-collision studies of energy transfer and chemical reaction

    Energy Technology Data Exchange (ETDEWEB)

    Valentini, J.J. [Columbia Univ., New York, NY (United States)

    1993-12-01

    The research focus in this group is state-to-state dynamics of reaction and energy transfer in collisions of free radicals such as H, OH, and CH{sub 3} with H{sub 2}, alkanes, alcohols and other hydrogen-containing molecules. The motivation for the work is the desire to provide a detailed understanding of the chemical dynamics of prototype reactions that are important in the production and utilization of energy sources, most importantly in combustion. The work is primarily experimental, but with an important and growing theoretical/computational component. The focus of this research program is now on reactions in which at least one of the reactants and one of the products is polyatomic. The objective is to determine how the high dimensionality of the reactants and products differentiates such reactions from atom + diatom reactions of the same kinematics and energetics. The experiments use highly time-resolved laser spectroscopic methods to prepare reactant states and analyze the states of the products on a single-collision time scale. The primary spectroscopic tool for product state analysis is coherent anti-Stokes Raman scattering (CARS) spectroscopy. CARS is used because of its generality and because the extraction of quantum state populations from CARS spectra is straightforward. The combination of the generality and easy analysis of CARS makes possible absolute cross section measurements (both state-to-state and total), a particularly valuable capability for characterizing reactive and inelastic collisions. Reactant free radicals are produced by laser photolysis of appropriate precursors. For reactant vibrational excitation stimulated Raman techniques are being developed and implemented.

  17. Entity models for trigger-reaction documents

    NARCIS (Netherlands)

    Khalid, M.A.; Marx, M.; Makkes, M.X.

    2008-01-01

    We define the notion of an entity model for a special kind of document popular on the web: an article followed by a list of reactions on that article, usually by many authors, usually inverse chronologically ordered. We call these documents trigger-reactions pairs. The entity model describes which

  18. Sodium-concrete reaction model development

    International Nuclear Information System (INIS)

    Nguyen, D.H.; Muhlestein, L.D.; Postma, A.K.

    1982-07-01

    Major observations have been formulated after reviewing test results for over 100 sodium-concrete reaction tests. The observations form the basis for developing a mechanistic model to predict the transient behavior of sodium-concrete reactions. The major observations are listed. Mechanisms associated with sodium and water transport to the reaction zone are identified, and represented by appropriate mathematical expressions. The model attempts to explain large-scale, long-term (100 h) test results were sodium-concrete reactions terminated even in the presence of unreacted sodium and concrete

  19. Constituent models and large transverse momentum reactions

    International Nuclear Information System (INIS)

    Brodsky, S.J.

    1975-01-01

    The discussion of constituent models and large transverse momentum reactions includes the structure of hard scattering models, dimensional counting rules for large transverse momentum reactions, dimensional counting and exclusive processes, the deuteron form factor, applications to inclusive reactions, predictions for meson and photon beams, the charge-cubed test for the e/sup +-/p → e/sup +-/γX asymmetry, the quasi-elastic peak in inclusive hadronic reactions, correlations, and the multiplicity bump at large transverse momentum. Also covered are the partition method for bound state calculations, proofs of dimensional counting, minimal neutralization and quark--quark scattering, the development of the constituent interchange model, and the A dependence of high transverse momentum reactions

  20. Multicomponent modelling of Portland cement hydration reactions

    NARCIS (Netherlands)

    Ukrainczyk, N.; Koenders, E.A.B.; Van Breugel, K.

    2012-01-01

    The prospect of cement and concrete technologies depends on more in depth understanding of cement hydration reactions. Hydration reaction models simulate the development of the microstructures that can finally be used to estimate the cement based material properties that influence performance and

  1. Modeling of turbulent chemical reaction

    Science.gov (United States)

    Chen, J.-Y.

    1995-01-01

    Viewgraphs are presented on modeling turbulent reacting flows, regimes of turbulent combustion, regimes of premixed and regimes of non-premixed turbulent combustion, chemical closure models, flamelet model, conditional moment closure (CMC), NO(x) emissions from turbulent H2 jet flames, probability density function (PDF), departures from chemical equilibrium, mixing models for PDF methods, comparison of predicted and measured H2O mass fractions in turbulent nonpremixed jet flames, experimental evidence of preferential diffusion in turbulent jet flames, and computation of turbulent reacting flows.

  2. Kinetics interpretation model of isothermal martensite reactions

    International Nuclear Information System (INIS)

    Guimaraes, J.R.C.

    1976-01-01

    It was discussed details associated to the interpretation of kinetics of martencite heterogeneous nucleation in isothermal reactions. It was proposed a model which allows compute the variation of concentration of preferencial sites nucleation with a volumetric martencite fraction [pt

  3. DSMC Modeling of Flows with Recombination Reactions

    Science.gov (United States)

    2017-06-23

    Reactions S. Gimelshein, I. Wysong Air Force Research Laboratory (AFMC) AFRL/RQRC 10 E. Saturn Blvd. Edwards AFB, CA 93524-7680 Air Force Research...dimensional flows, modeling is usually con- ducted for Knudsen numbers Kn > 0.001, where the impact of recombination reactions is almost always minor, so...prac- tical applicability of the DSMC method. These methods have already been tested for reacting air flows.20 Today, modeling of gas flows at

  4. Review of statistical models for nuclear reactions

    International Nuclear Information System (INIS)

    Igarasi, Sin-iti

    1991-01-01

    Statistical model calculations have been widely performed for nuclear data evaluations. These were based on the models of Hauser-Feshbach, Weisskopf-Ewing and their modifications. Since the 1940s, non-compound nuclear phenomena have been observed, and stimulated many nuclear physicists to study compound and non-compound nuclear reaction mechanisms. Concerning compound nuclear reactions, they investigated problems on the basis of fundamental properties of S-matrix, statistical distributions of resonance pole parameters, random matrix elements of the nuclear Hamiltonian, and so forth. They have presented many sophisticated results. But old statistical models have been still useful, because these models were simple and easily utilizable. In this report, these old and new models will be briefly reviewed with a purpose of application to nuclear data evaluation, and examine applicability of the new models. (author)

  5. Thermodynamically Feasible Kinetic Models of Reaction Networks

    OpenAIRE

    Ederer, Michael; Gilles, Ernst Dieter

    2007-01-01

    The dynamics of biological reaction networks are strongly constrained by thermodynamics. An holistic understanding of their behavior and regulation requires mathematical models that observe these constraints. However, kinetic models may easily violate the constraints imposed by the principle of detailed balance, if no special care is taken. Detailed balance demands that in thermodynamic equilibrium all fluxes vanish. We introduce a thermodynamic-kinetic modeling (TKM) formalism that adapts th...

  6. Nonlinear control of the Salnikov model reaction

    DEFF Research Database (Denmark)

    Recke, Bodil; Jørgensen, Sten Bay

    1999-01-01

    This paper explores different nonlinear control schemes, applied to a simple model reaction. The model is the Salnikov model, consisting of two ordinary differential equations. The control strategies investigated are I/O-linearisation, Exact linearisation, exact linearisation combined with LQR...... and Control Lyapunov Functions (CLF's). The results show that based on the lowest possible cost function and shortest settling time, the exact linearisation performs marginally better than the other methods....

  7. Multicriterial evaluation of spallation reaction models

    International Nuclear Information System (INIS)

    Andrianov, A.A.; Gritsyuk, S.V.; Korovin, Yu.A.; Kuptsov, I.S.

    2013-01-01

    Results of evaluation of predicting ability of spallation reaction models as applied to high-energy protons interaction based on methods of discrete decision analysis are presented. It is shown that results obtained using different methods are well consistent. Recommendations are given on the use of discrete decision analysis methods for providing constants to be employed in calculations of future nuclear power facility [ru

  8. Tuning Catalytic Performance through a Single or Sequential Post-Synthesis Reaction(s) in a Gas Phase

    Energy Technology Data Exchange (ETDEWEB)

    Shan, Junjun [Department; Department; Zhang, Shiran [Department; Department; Choksi, Tej [Department; Nguyen, Luan [Department; Department; Bonifacio, Cecile S. [Department; Li, Yuanyuan [Department; Zhu, Wei [Department; Department; College; Tang, Yu [Department; Department; Zhang, Yawen [College; Yang, Judith C. [Department; Greeley, Jeffrey [Department; Frenkel, Anatoly I. [Department; Tao, Franklin [Department; Department

    2016-12-05

    Catalytic performance of a bimetallic catalyst is determined by geometric structure and electronic state of the surface or even the near-surface region of the catalyst. Here we report that single and sequential postsynthesis reactions of an as-synthesized bimetallic nanoparticle catalyst in one or more gas phases can tailor surface chemistry and structure of the catalyst in a gas phase, by which catalytic performance of this bimetallic catalyst can be tuned. Pt–Cu regular nanocube (Pt–Cu RNC) and concave nanocube (Pt–Cu CNC) are chosen as models of bimetallic catalysts. Surface chemistry and catalyst structure under different reaction conditions and during catalysis were explored in gas phase of one or two reactants with ambient-pressure X-ray photoelectron spectroscopy (AP-XPS) and extended X-ray absorption fine structure (EXAFS) spectroscopy. The newly formed surface structures of Pt–Cu RNC and Pt–Cu CNC catalysts strongly depend on the reactive gas(es) used in the postsynthesis reaction(s). A reaction of Pt–Cu RNC-as synthesized with H2 at 200 °C generates a near-surface alloy consisting of a Pt skin layer, a Cu-rich subsurface, and a Pt-rich deep layer. This near-surface alloy of Pt–Cu RNC-as synthesized-H2 exhibits a much higher catalytic activity in CO oxidation in terms of a low activation barrier of 39 ± 4 kJ/mol in contrast to 128 ± 7 kJ/mol of Pt–Cu RNC-as synthesized. Here the significant decrease of activation barrier demonstrates a method to tune catalytic performances of as-synthesized bimetallic catalysts. A further reaction of Pt–Cu RNC-as synthesized-H2 with CO forms a Pt–Cu alloy surface, which exhibits quite different catalytic performance in CO oxidation. It suggests the capability of generating a different surface by using another gas. The capability of tuning surface chemistry and structure of bimetallic catalysts was also demonstrated in restructuring of Pt–Cu CNC-as synthesized.

  9. Reaction-diffusion pulses: a combustion model

    International Nuclear Information System (INIS)

    Campos, Daniel; Llebot, Josep Enric; Fort, Joaquim

    2004-01-01

    We focus on a reaction-diffusion approach proposed recently for experiments on combustion processes, where the heat released by combustion follows first-order reaction kinetics. This case allows us to perform an exhaustive analytical study. Specifically, we obtain the exact expressions for the speed of the thermal pulses, their maximum temperature and the condition of self-sustenance. Finally, we propose two generalizations of the model, namely, the case of several reactants burning together, and that of time-delayed heat conduction. We find an excellent agreement between our analytical results and simulations

  10. Single-molecule stochastic times in a reversible bimolecular reaction.

    Science.gov (United States)

    Keller, Peter; Valleriani, Angelo

    2012-08-28

    In this work, we consider the reversible reaction between reactants of species A and B to form the product C. We consider this reaction as a prototype of many pseudobiomolecular reactions in biology, such as for instance molecular motors. We derive the exact probability density for the stochastic waiting time that a molecule of species A needs until the reaction with a molecule of species B takes place. We perform this computation taking fully into account the stochastic fluctuations in the number of molecules of species B. We show that at low numbers of participating molecules, the exact probability density differs from the exponential density derived by assuming the law of mass action. Finally, we discuss the condition of detailed balance in the exact stochastic and in the approximate treatment.

  11. Reaction Wheel Disturbance Model Extraction Software - RWDMES

    Science.gov (United States)

    Blaurock, Carl

    2009-01-01

    The RWDMES is a tool for modeling the disturbances imparted on spacecraft by spinning reaction wheels. Reaction wheels are usually the largest disturbance source on a precision pointing spacecraft, and can be the dominating source of pointing error. Accurate knowledge of the disturbance environment is critical to accurate prediction of the pointing performance. In the past, it has been difficult to extract an accurate wheel disturbance model since the forcing mechanisms are difficult to model physically, and the forcing amplitudes are filtered by the dynamics of the reaction wheel. RWDMES captures the wheel-induced disturbances using a hybrid physical/empirical model that is extracted directly from measured forcing data. The empirical models capture the tonal forces that occur at harmonics of the spin rate, and the broadband forces that arise from random effects. The empirical forcing functions are filtered by a physical model of the wheel structure that includes spin-rate-dependent moments (gyroscopic terms). The resulting hybrid model creates a highly accurate prediction of wheel-induced forces. It accounts for variation in disturbance frequency, as well as the shifts in structural amplification by the whirl modes, as the spin rate changes. This software provides a point-and-click environment for producing accurate models with minimal user effort. Where conventional approaches may take weeks to produce a model of variable quality, RWDMES can create a demonstrably high accuracy model in two hours. The software consists of a graphical user interface (GUI) that enables the user to specify all analysis parameters, to evaluate analysis results and to iteratively refine the model. Underlying algorithms automatically extract disturbance harmonics, initialize and tune harmonic models, and initialize and tune broadband noise models. The component steps are described in the RWDMES user s guide and include: converting time domain data to waterfall PSDs (power spectral

  12. Quasifree (p , 2 p ) Reactions on Oxygen Isotopes: Observation of Isospin Independence of the Reduced Single-Particle Strength

    Science.gov (United States)

    Atar, L.; Paschalis, S.; Barbieri, C.; Bertulani, C. A.; Díaz Fernández, P.; Holl, M.; Najafi, M. A.; Panin, V.; Alvarez-Pol, H.; Aumann, T.; Avdeichikov, V.; Beceiro-Novo, S.; Bemmerer, D.; Benlliure, J.; Boillos, J. M.; Boretzky, K.; Borge, M. J. G.; Caamaño, M.; Caesar, C.; Casarejos, E.; Catford, W.; Cederkall, J.; Chartier, M.; Chulkov, L.; Cortina-Gil, D.; Cravo, E.; Crespo, R.; Dillmann, I.; Elekes, Z.; Enders, J.; Ershova, O.; Estrade, A.; Farinon, F.; Fraile, L. M.; Freer, M.; Galaviz Redondo, D.; Geissel, H.; Gernhäuser, R.; Golubev, P.; Göbel, K.; Hagdahl, J.; Heftrich, T.; Heil, M.; Heine, M.; Heinz, A.; Henriques, A.; Hufnagel, A.; Ignatov, A.; Johansson, H. T.; Jonson, B.; Kahlbow, J.; Kalantar-Nayestanaki, N.; Kanungo, R.; Kelic-Heil, A.; Knyazev, A.; Kröll, T.; Kurz, N.; Labiche, M.; Langer, C.; Le Bleis, T.; Lemmon, R.; Lindberg, S.; Machado, J.; Marganiec-Gałązka, J.; Movsesyan, A.; Nacher, E.; Nikolskii, E. Y.; Nilsson, T.; Nociforo, C.; Perea, A.; Petri, M.; Pietri, S.; Plag, R.; Reifarth, R.; Ribeiro, G.; Rigollet, C.; Rossi, D. M.; Röder, M.; Savran, D.; Scheit, H.; Simon, H.; Sorlin, O.; Syndikus, I.; Taylor, J. T.; Tengblad, O.; Thies, R.; Togano, Y.; Vandebrouck, M.; Velho, P.; Volkov, V.; Wagner, A.; Wamers, F.; Weick, H.; Wheldon, C.; Wilson, G. L.; Winfield, J. S.; Woods, P.; Yakorev, D.; Zhukov, M.; Zilges, A.; Zuber, K.; R3B Collaboration

    2018-01-01

    Quasifree one-proton knockout reactions have been employed in inverse kinematics for a systematic study of the structure of stable and exotic oxygen isotopes at the R3B /LAND setup with incident beam energies in the range of 300 - 450 MeV /u . The oxygen isotopic chain offers a large variation of separation energies that allows for a quantitative understanding of single-particle strength with changing isospin asymmetry. Quasifree knockout reactions provide a complementary approach to intermediate-energy one-nucleon removal reactions. Inclusive cross sections for quasifree knockout reactions of the type O A (p ,2 p )N-1A have been determined and compared to calculations based on the eikonal reaction theory. The reduction factors for the single-particle strength with respect to the independent-particle model were obtained and compared to state-of-the-art ab initio predictions. The results do not show any significant dependence on proton-neutron asymmetry.

  13. Cohabitation reaction-diffusion model for virus focal infections

    Science.gov (United States)

    Amor, Daniel R.; Fort, Joaquim

    2014-12-01

    The propagation of virus infection fronts has been typically modeled using a set of classical (noncohabitation) reaction-diffusion equations for interacting species. However, for some single-species systems it has been recently shown that noncohabitation reaction-diffusion equations may lead to unrealistic descriptions. We argue that previous virus infection models also have this limitation, because they assume that a virion can simultaneously reproduce inside a cell and diffuse away from it. For this reason, we build a several-species cohabitation model that does not have this limitation. Furthermore, we perform a sensitivity analysis for the most relevant parameters of the model, and we compare the predicted infection speed with observed data for two different strains of the T7 virus.

  14. Single-particle and collective states in transfer reactions

    International Nuclear Information System (INIS)

    Lhenry, I.; Suomijaervi, T.; Giai, N. van

    1993-01-01

    The possibility to excite collective states in transfer reactions induced by heavy ions is studied. Collective states are described within the Random Phase Approximation (RPA) and the collectivity is defined according to the number of configurations contributing to a given state. The particle transfer is described within the Distorted Wave Born Approximation (DWBA). Calculations are performed for two different stripping reactions: 207 Pb( 20 Ne, 19 Ne) 208 Pb and 59 Co( 20 Ne, 19 F) 60 Ni at 48 MeV/nucleon for which experimental data are available. The calculation shows that a sizeable fraction of collective strength can be excited in these reactions. The comparison with experiment shows that this parameter-free calculation qualitatively explains the data. (author) 19 refs.; 10 figs

  15. Kinetics of Single-Enzyme Reactions on Vesicles: Role of Substrate Aggregation

    Science.gov (United States)

    Zhdanov, Vladimir P.

    2015-03-01

    Enzymatic reactions occurring in vivo on lipid membranes can be influenced by various factors including macromolecular crowding in general and substrate aggregation in particular. In academic studies, the role of these factors can experimentally be clarified by tracking single-enzyme kinetics occurring on individual lipid vesicles. To extend the conceptual basis for such experiments, we analyze herein the corresponding kinetics mathematically with emphasis on the role of substrate aggregation. In general, the aggregation may occur on different length scales. Small aggregates may e.g. contain a few proteins or peptides while large aggregates may be mesoscopic as in the case of lipid domains which can be formed in the membranes composed of different lipids. We present a kinetic model describing comprehensively the effect of aggregation of the former type on the dependence of the reaction rate on substrate membrane concentration. The results obtained with physically reasonable parameters indicate that the aggregation-related deviations from the conventional Michaelis-Menten kinetics may be appreciable. Special Issue Comments: This theoretical article is focused on single-enzyme reactions occurring in parallel with substrate aggregation on individual vesicles. This subject is related to a few Special Issue articles concerning enzyme dynamics6,7 and function8 and mathematical aspects of stochastic kinetics.9

  16. Modeling of calcination of single kaolinitic clay particle

    DEFF Research Database (Denmark)

    Gebremariam, Abraham Teklay; Yin, Chungen; Rosendahl, Lasse

    The present work aims at modeling of the calcination (dehydroxylation) process of clay particles, specifically kaolinite, and its thermal transformation. For such purpose, 1D single particle calcination model was developed based on the concept of shrinking core model to assess the dehydroxylation...... distribution within the clay particle and simultaneous density changes due to the reaction kinetics. Accordingly, a particular residence time was noticed as a point where kaolinitic clay particles attain optimum conversion to metakaolinite which is pozzolanic....

  17. Cowpea Reaction to Single and Mixed Viral Infection with Blackeye ...

    African Journals Online (AJOL)

    The results of the experiment showed that mixed inoculation with the two viruses, induced greater susceptibility to the viral pathogens in the plants, compared to single virus inoculations. The study also indicated that, early viral infection at 2 WAP, was more pathogenic and resulted in higher yield losses compared with ...

  18. Photochemical reactions of various model protocell systems

    Science.gov (United States)

    Folsome, C. E.

    1986-01-01

    Models for the emergence of cellular life on the primitive Earth, and for physical environments of that era have been studied that embody these assumptions: (1) pregenetic cellular forms were phase-bounded systems primarily photosynthetic in nature, and (2) the early Earth environment was anoxic (lacking appreciable amounts of free hydrogen). It was found that organic structures can also be formed under anoxic conditions (N2, CO3=, H2O) by protracted longwavelength UV radiation. Apparently these structures form initially as organic layers upon CaCO3 crystalloids. The question remains as to whether the UV photosynthetic ability of such phase bounded structures is a curiosity, or a general property of phase bounded systems which is of direct interest to the emergence of cellular life. The question of the requirement and sailient features of a phase boundary for UV photosynthetic abilities was addressed by searching for similar general physical properties which might be manifest in a variety of other simple protocell-like structures. Since it has been shown that laboratory protocell models can effect the UV photosynthesis of low molecular weight compounds, this reaction is being used as an assay to survey other types of structures for similar UV photosynthetic reactions. Various kinds of structures surveyed are: (1) proteinoids; (2) liposomes; (3) reconstituted cell membrane spheroids; (4) coacervates; and (5) model protocells formed under anoxic conditions.

  19. Reaction-diffusion models of decontamination

    DEFF Research Database (Denmark)

    Hjorth, Poul G.

    A contaminant, which also contains a polymer is in the form of droplets on a solid surface. It is to be removed by the action of a decontaminant, which is applied in aqueous solution. The contaminant is only sparingly soluble in water, so the reaction mechanism is that it slowly dissolves...... in the aqueous solution and then is oxidized by the decontaminant. The polymer is insoluble in water, and so builds up near the interface, where its presence can impede the transport of contaminant. In these circumstances, Dstl wish to have mathematical models that give an understanding of the process, and can...

  20. Single-molecule detection of dihydroazulene photo-thermal reaction using break junction technique

    Science.gov (United States)

    Huang, Cancan; Jevric, Martyn; Borges, Anders; Olsen, Stine T.; Hamill, Joseph M.; Zheng, Jue-Ting; Yang, Yang; Rudnev, Alexander; Baghernejad, Masoud; Broekmann, Peter; Petersen, Anne Ugleholdt; Wandlowski, Thomas; Mikkelsen, Kurt V.; Solomon, Gemma C.; Brøndsted Nielsen, Mogens; Hong, Wenjing

    2017-05-01

    Charge transport by tunnelling is one of the most ubiquitous elementary processes in nature. Small structural changes in a molecular junction can lead to significant difference in the single-molecule electronic properties, offering a tremendous opportunity to examine a reaction on the single-molecule scale by monitoring the conductance changes. Here, we explore the potential of the single-molecule break junction technique in the detection of photo-thermal reaction processes of a photochromic dihydroazulene/vinylheptafulvene system. Statistical analysis of the break junction experiments provides a quantitative approach for probing the reaction kinetics and reversibility, including the occurrence of isomerization during the reaction. The product ratios observed when switching the system in the junction does not follow those observed in solution studies (both experiment and theory), suggesting that the junction environment was perturbing the process significantly. This study opens the possibility of using nano-structured environments like molecular junctions to tailor product ratios in chemical reactions.

  1. Catalytic effect of a single water molecule on the OH + CH2NH reaction.

    Science.gov (United States)

    Akbar Ali, Mohamad; M, Balaganesh; Lin, K C

    2018-02-07

    In recent work, there has been considerable speculation about the atmospheric reaction of methylenimine (CH 2 NH), because this compound is highly reactive, soluble in water, and sticky, thus posing severe experimental challenges. In this work, we have revisited the kinetics of the OH + CH 2 NH reaction assisted by a single water molecule. The potential energy surfaces (PESs) for the water-assisted OH + CH 2 NH reaction were calculated using the CCSD(T)//BH&HLYP/aug-cc-pVTZ levels of theory. The rate coefficients for the bimolecular reaction pathways CH 2 NHH 2 O + OH and CH 2 NH + H 2 OHO were computed using canonical variational transition state theory (CVT) with small curvature tunneling correction. The reaction without water has four elementary reaction pathways, depending on how the hydroxyl radical approaches CH 2 NH. In all cases, the reaction begins with the formation of a single pre-reactive complex before producing abstraction and addition products. When water is added, the products of the reaction do not change, and the reaction becomes quite complex, yielding four different pre-reactive complexes and eight reaction pathways. The calculated rate coefficient for the OH + CH 2 NH (water-free) reaction at 300 K is 1.7 × 10 -11 cm 3 molecule -1 s -1 and for OH + CH 2 NH (water-assisted), it is 5.1 × 10 -14 cm 3 molecule -1 s -1 . This result is similar to the isoelectronic analogous reaction OH + CH 2 O (water-assisted). In general, the effective rate coefficients of the water-assisted reaction are 2∼3 orders of magnitude smaller than water-free. Our results show that the water-assisted OH + CH 2 NH reaction cannot accelerate the reaction because the dominated water-assisted process depends parametrically on water concentration. As a result, the overall reaction rate coefficients are smaller.

  2. Modelling of structural effects on chemical reactions in turbulent flows

    Energy Technology Data Exchange (ETDEWEB)

    Gammelsaeter, H.R.

    1997-12-31

    Turbulence-chemistry interactions are analysed using algebraic moment closure for the chemical reaction term. The coupling between turbulence and chemical length and time scales generate a complex interaction process. This interaction process is called structural effects in this work. The structural effects are shown to take place on all scales between the largest scale of turbulence and the scales of the molecular motions. The set of equations describing turbulent correlations involved in turbulent reacting flows are derived. Interactions are shown schematically using interaction charts. Algebraic equations for the turbulent correlations in the reaction rate are given using the interaction charts to include the most significant couplings. In the frame of fundamental combustion physics, the structural effects appearing on the small scales of turbulence are proposed modelled using a discrete spectrum of turbulent scales. The well-known problem of averaging the Arrhenius law, the specific reaction rate, is proposed solved using a presumed single variable probability density function and a sub scale model for the reaction volume. Although some uncertainties are expected, the principles are addressed. Fast chemistry modelling is shown to be consistent in the frame of algebraic moment closure when the turbulence-chemistry interaction is accounted for in the turbulent diffusion. The modelling proposed in this thesis is compared with experimental data for an laboratory methane flame and advanced probability density function modelling. The results show promising features. Finally it is shown a comparison with full scale measurements for an industrial burner. All features of the burner are captured with the model. 41 refs., 33 figs.

  3. Comparison of DSMC Reaction Models with QCT Reaction Rates for Nitrogen

    Science.gov (United States)

    2016-07-17

    include area code) N/A Standard Form 298 (Rev. 8-98) Prescribed by ANSI Std. 239.18 Comparison of DSMC Reaction Models with QCT Reaction Rates ...controls vibration coupling A is adjusted to match thermal reaction rate Simplest to implement, not tied to any other model Distribution A: Approved for...General trend: reaction rate increases with v • TCE, QK: lack of vibrational favoring results in much lower slope as compared to the benchmark QCT • VFD: φ

  4. Nuclear reaction matrix calculations with a shell-model Q

    International Nuclear Information System (INIS)

    Barrett, B.R.; McCarthy, R.J.

    1976-01-01

    Das Barrett-Hewitt-McCarthy (BHM) method for calculating the nuclear reaction matrix G is used to compute shell-model matrix elements for A = 18 nuclei. The energy denominators in intermediate states containing one unoccupied single-particle (s.p.) state and one valence s.p. state are treated correctly, in contrast to previous calculations. These corrections are not important for valence-shell matrix elements but are found to lead to relatively large changes in cross-shell matrix elements involved in core-polarization diagrams. (orig.) [de

  5. Modeling of Reaction Processes Controlled by Diffusion

    International Nuclear Information System (INIS)

    Revelli, Jorge

    2003-01-01

    Stochastic modeling is quite powerful in science and technology.The technics derived from this process have been used with great success in laser theory, biological systems and chemical reactions.Besides, they provide a theoretical framework for the analysis of experimental results on the field of particle's diffusion in ordered and disordered materials.In this work we analyze transport processes in one-dimensional fluctuating media, which are media that change their state in time.This fact induces changes in the movements of the particles giving rise to different phenomena and dynamics that will be described and analyzed in this work.We present some random walk models to describe these fluctuating media.These models include state transitions governed by different dynamical processes.We also analyze the trapping problem in a lattice by means of a simple model which predicts a resonance-like phenomenon.Also we study effective diffusion processes over surfaces due to random walks in the bulk.We consider different boundary conditions and transitions movements.We derive expressions that describe diffusion behaviors constrained to bulk restrictions and the dynamic of the particles.Finally it is important to mention that the theoretical results obtained from the models proposed in this work are compared with Monte Carlo simulations.We find, in general, excellent agreements between the theory and the simulations

  6. Circumnutation modeled by reaction-diffusion equations

    Energy Technology Data Exchange (ETDEWEB)

    Lubkin, S.R.

    1992-01-01

    In studies of biological oscillators, plants are only rarely examined. The authors study a common sub-diurnal oscillation of plants, called circumnutation. Based on experimental evidence that the oscillations consist of a turgor wave traveling around a growing plant part, circumnutation is modeled by a nonlinear reaction-diffusion system with cylindrical geometry. Because of its simplicity, and because biological oscillations are so common, an oscillatory [lambda]-[omega] reaction-diffusion system is chosen for the model. The authors study behavior of traveling waves in [lambda]-[omega] systems. The authors show the existence of Hopf bifurcations and the stability of the limit cycles born at the Hopf bifurcation for some parameter values. Using a Lindstedt-type perturbation scheme, the authors construct periodic solutions of the [lambda]-[omega] system near a Hopf bifurcation and show that the periodic solutions superimposed on the original traveling wave have the effect of altering its overall frequency and amplitude. Circumnutating plants generally display a strong directional preference to their oscillations, which is species-dependent. Circumnutation is modeled by a [lambda]-[omega] system on an annulus of variable width, which does not possess reflection symmetry about any axis. The annulus represents a region of high potassium concentration in the cross-section of the stem. The asymmetry of the annulus represents the anatomical asymmetry of the plant. Traveling waves are constructed on this variable-width annulus by a perturbation scheme, and perturbing the width of the annulus alters the amplitude and frequency of traveling waves on the domain by a small (order [epsilon][sup 2]) amount. The speed, frequency, and stability are unaffected by the direction of travel of the wave on the annulus. This indicates that the [lambda]-[omega] system on a variable-width domain cannot account for directional preferences of traveling waves in biological systems.

  7. Single-Site Palladium(II) Catalyst for Oxidative Heck Reaction: Catalytic Performance and Kinetic Investigations

    Energy Technology Data Exchange (ETDEWEB)

    Duan, Hui; Li, Mengyang; Zhang, Guanghui; Gallagher, James R.; Huang, Zhiliang; Sun, Yu; Luo, Zhong; Chen, Hongzhong; Miller, Jeffrey T.; Zou, Ruqiang; Lei, Aiwen; Zhao, Yanli

    2015-01-01

    ABSTRACT: The development of organometallic single-site catalysts (SSCs) has inspired the designs of new heterogeneous catalysts with high efficiency. Nevertheless, the application of SSCs in certain modern organic reactions, such as C-C bond formation reactions, has still been less investigated. In this study, a single-site Pd(II) catalyst was developed, where 2,2'-bipyridine-grafted periodic mesoporous organosilica (PMO) was employed as the support of a Pd(II) complex. The overall performance of the single-site Pd(II) catalyst in the oxidative Heck reaction was then investigated. The investigation results show that the catalyst displays over 99% selectivity for the product formation with high reaction yield. Kinetic profiles further confirm its high catalytic efficiency, showing that the rate constant is nearly 40 times higher than that for the free Pd(II) salt. X-ray absorption spectroscopy reveals that the catalyst has remarkable lifetime and recyclability.

  8. Single-molecule detection of dihydroazulene photo-thermal reaction using break junction technique

    DEFF Research Database (Denmark)

    Huang, Cancan; Jevric, Martyn; Borges, Anders Christian

    2017-01-01

    a quantitative approach for probing the reaction kinetics and reversibility, including the occurrence of isomerization during the reaction. The product ratios observed when switching the system in the junction does not follow those observed in solution studies (both experiment and theory), suggesting......Charge transport by tunnelling is one of the most ubiquitous elementary processes in nature. Small structural changes in a molecular junction can lead to significant difference in the single-molecule electronic properties, offering a tremendous opportunity to examine a reaction on the single......-molecule scale by monitoring the conductance changes. Here, we explore the potential of the single-molecule break junction technique in the detection of photo-thermal reaction processes of a photochromic dihydroazulene/vinylheptafulvene system. Statistical analysis of the break junction experiments provides...

  9. Investigation and Modelling of Diesel Hydrotreating Reactions

    DEFF Research Database (Denmark)

    Boesen, Rasmus Risum

    This project consists of a series of studies, that are related to hydrotreating of diesel. Hy- drotreating is an important refinery process, in which the oil stream is upgraded to meet the required environmental specifications and physical properties. Although hydrotreating is a ma- ture technology...... it has received increased attention within the last decade due to tightened legislations regarding the sulfur content, e.g. the demand for Ultra Low Sulfur Diesel (ULSD) with a maximum sulfur content of as low as 10 ppm S has increased. The process is complex, as the performance of a hydrotreating...... due to a stronger adsorption on hydrogenation sites. Since feeds used in the hydrotreating process, usually gas-oils, are complex mixtures with a large number of compounds, analysis of the reactions of individual compounds can be difficult. In this work a model-diesel feed consisting of 13 different...

  10. Model Experiment of Thermal Runaway Reactions Using the Aluminum-Hydrochloric Acid Reaction

    Science.gov (United States)

    Kitabayashi, Suguru; Nakano, Masayoshi; Nishikawa, Kazuyuki; Koga, Nobuyoshi

    2016-01-01

    A laboratory exercise for the education of students about thermal runaway reactions based on the reaction between aluminum and hydrochloric acid as a model reaction is proposed. In the introductory part of the exercise, the induction period and subsequent thermal runaway behavior are evaluated via a simple observation of hydrogen gas evolution and…

  11. Trend to equilibrium for a reaction-diffusion system modelling reversible enzyme reaction

    OpenAIRE

    Elias, Jan

    2016-01-01

    20 pages; A spatio-temporal evolution of chemicals appearing in a reversible enzyme reaction and modelled by a four component reaction-diffusion system with the reaction terms obtained by the law of mass action is considered. The large time behaviour of the system is studied by means of entropy methods.

  12. Trend to Equilibrium for a Reaction-Diffusion System Modelling Reversible Enzyme Reaction.

    Science.gov (United States)

    Eliaš, Ján

    2018-01-01

    A spatio-temporal evolution of chemicals appearing in a reversible enzyme reaction and modelled by a four-component reaction-diffusion system with the reaction terms obtained by the law of mass action is considered. The large time behaviour of the system is studied by means of entropy methods.

  13. Atomic-level insights in optimizing reaction paths for hydroformylation reaction over Rh/CoO single-atom catalyst.

    Science.gov (United States)

    Wang, Liangbing; Zhang, Wenbo; Wang, Shenpeng; Gao, Zehua; Luo, Zhiheng; Wang, Xu; Zeng, Rui; Li, Aowen; Li, Hongliang; Wang, Menglin; Zheng, Xusheng; Zhu, Junfa; Zhang, Wenhua; Ma, Chao; Si, Rui; Zeng, Jie

    2016-12-22

    Rh-based heterogeneous catalysts generally have limited selectivity relative to their homogeneous counterparts in hydroformylation reactions despite of the convenience of catalyst separation in heterogeneous catalysis. Here, we develop CoO-supported Rh single-atom catalysts (Rh/CoO) with remarkable activity and selectivity towards propene hydroformylation. By increasing Rh mass loading, isolated Rh atoms switch to aggregated clusters of different atomicity. During the hydroformylation, Rh/CoO achieves the optimal selectivity of 94.4% for butyraldehyde and the highest turnover frequency number of 2,065 h -1 among the obtained atomic-scale Rh-based catalysts. Mechanistic studies reveal that a structural reconstruction of Rh single atoms in Rh/CoO occurs during the catalytic process, facilitating the adsorption and activation of reactants. In kinetic view, linear products are determined as the dominating products by analysing reaction paths deriving from the two most stable co-adsorbed configurations. As a bridge of homogeneous and heterogeneous catalysis, single-atom catalysts can be potentially applied in other industrial reactions.

  14. Kinetic modelling of the Maillard reaction between proteins and sugars

    NARCIS (Netherlands)

    Brands, C.M.J.

    2002-01-01

    Keywords: Maillard reaction, sugar isomerisation, kinetics, multiresponse modelling, brown colour formation, lysine damage, mutagenicity, casein, monosaccharides, disaccharides, aldoses, ketoses

    The aim of this thesis was to determine the kinetics of the Maillard reaction between

  15. Diffusion-controlled reactions modeling in Geant4-DNA

    International Nuclear Information System (INIS)

    Karamitros, M.; Luan, S.; Bernal, M.A.; Allison, J.; Baldacchino, G.; Davidkova, M.; Francis, Z.; Friedland, W.; Ivantchenko, V.; Ivantchenko, A.; Mantero, A.; Nieminem, P.; Santin, G.; Tran, H.N.; Stepan, V.; Incerti, S.

    2014-01-01

    Context Under irradiation, a biological system undergoes a cascade of chemical reactions that can lead to an alteration of its normal operation. There are different types of radiation and many competing reactions. As a result the kinetics of chemical species is extremely complex. The simulation becomes then a powerful tool which, by describing the basic principles of chemical reactions, can reveal the dynamics of the macroscopic system. To understand the dynamics of biological systems under radiation, since the 80s there have been on-going efforts carried out by several research groups to establish a mechanistic model that consists in describing all the physical, chemical and biological phenomena following the irradiation of single cells. This approach is generally divided into a succession of stages that follow each other in time: (1) the physical stage, where the ionizing particles interact directly with the biological material; (2) the physico-chemical stage, where the targeted molecules release their energy by dissociating, creating new chemical species; (3) the chemical stage, where the new chemical species interact with each other or with the biomolecules; (4) the biological stage, where the repairing mechanisms of the cell come into play. This article focuses on the modeling of the chemical stage. Method This article presents a general method of speeding-up chemical reaction simulations in fluids based on the Smoluchowski equation and Monte-Carlo methods, where all molecules are explicitly simulated and the solvent is treated as a continuum. The model describes diffusion-controlled reactions. This method has been implemented in Geant4-DNA. The keys to the new algorithm include: (1) the combination of a method to compute time steps dynamically with a Brownian bridge process to account for chemical reactions, which avoids costly fixed time step simulations; (2) a k–d tree data structure for quickly locating, for a given molecule, its closest reactants. The

  16. Study of Reaction Forces in a Single Sided Linear Induction Motor (SLIM)

    Science.gov (United States)

    1974-01-01

    SLIM reaction forces were measured on a laboratory model having aluminum and aluminum-iron secondaries and the results were correlated with the theoretical forces derived for different idealized SLIM models. The first part of the report discusses wav...

  17. Single-Atom Catalyst of Platinum Supported on Titanium Nitride for Selective Electrochemical Reactions.

    Science.gov (United States)

    Yang, Sungeun; Kim, Jiwhan; Tak, Young Joo; Soon, Aloysius; Lee, Hyunjoo

    2016-02-05

    As a catalyst, single-atom platinum may provide an ideal structure for platinum minimization. Herein, a single-atom catalyst of platinum supported on titanium nitride nanoparticles were successfully prepared with the aid of chlorine ligands. Unlike platinum nanoparticles, the single-atom active sites predominantly produced hydrogen peroxide in the electrochemical oxygen reduction with the highest mass activity reported so far. The electrocatalytic oxidation of small organic molecules, such as formic acid and methanol, also exhibited unique selectivity on the single-atom platinum catalyst. A lack of platinum ensemble sites changed the reaction pathway for the oxygen-reduction reaction toward a two-electron pathway and formic acid oxidation toward direct dehydrogenation, and also induced no activity for the methanol oxidation. This work demonstrates that single-atom platinum can be an efficient electrocatalyst with high mass activity and unique selectivity. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  18. Mathematical Model of Synthesis Catalyst with Local Reaction Centers

    Directory of Open Access Journals (Sweden)

    I. V. Derevich

    2017-01-01

    Full Text Available The article considers a catalyst granule with a porous ceramic passive substrate and point active centers on which an exothermic synthesis reaction occurs. A rate of the chemical reaction depends on the temperature according to the Arrhenius law. Heat is removed from the pellet surface in products of synthesis due to heat transfer. In our work we first proposed a model for calculating the steady-state temperature of a catalyst pellet with local reaction centers. Calculation of active centers temperature is based on the idea of self-consistent field (mean-field theory. At first, it is considered that powers of the reaction heat release at the centers are known. On the basis of the found analytical solution, which describes temperature distribution inside the granule, the average temperature of the reaction centers is calculated, which then is inserted in the formula for heat release. The resulting system of transcendental algebraic equations is transformed into a system of ordinary differential equations of relaxation type and solved numerically to achieve a steady-state value. As a practical application, the article considers a Fischer-Tropsch synthesis catalyst granule with active cobalt metallic micro-particles. Cobalt micro-particles are the centers of the exothermic reaction of hydrocarbons macromolecular synthesis. Synthesis occurs as a result of absorption of the components of the synthesis gas on metallic cobalt. The temperature distribution inside the granule for a single local center and reaction centers located on the same granule diameter is found. It was found that there is a critical temperature of reactor exceeding of which leads to significant local overheating of the centers - thermal explosion. The temperature distribution with the local reaction centers is qualitatively different from the granule temperature, calculated in the homogeneous approximation. It is shown that, in contrast to the homogeneous approximation, the

  19. Using Multiorder Time-Correlation Functions (TCFs) To Elucidate Biomolecular Reaction Pathways from Microsecond Single-Molecule Fluorescence Experiments.

    Science.gov (United States)

    Phelps, Carey; Israels, Brett; Marsh, Morgan C; von Hippel, Peter H; Marcus, Andrew H

    2016-12-29

    Recent advances in single-molecule fluorescence imaging have made it possible to perform measurements on microsecond time scales. Such experiments have the potential to reveal detailed information about the conformational changes in biological macromolecules, including the reaction pathways and dynamics of the rearrangements involved in processes, such as sequence-specific DNA "breathing" and the assembly of protein-nucleic acid complexes. Because microsecond-resolved single-molecule trajectories often involve "sparse" data, that is, they contain relatively few data points per unit time, they cannot be easily analyzed using the standard protocols that were developed for single-molecule experiments carried out with tens-of-millisecond time resolution and high "data density." Here, we describe a generalized approach, based on time-correlation functions, to obtain kinetic information from microsecond-resolved single-molecule fluorescence measurements. This approach can be used to identify short-lived intermediates that lie on reaction pathways connecting relatively long-lived reactant and product states. As a concrete illustration of the potential of this methodology for analyzing specific macromolecular systems, we accompany the theoretical presentation with the description of a specific biologically relevant example drawn from studies of reaction mechanisms of the assembly of the single-stranded DNA binding protein of the T4 bacteriophage replication complex onto a model DNA replication fork.

  20. Electronic state selectivity in dication-molecule single electron transfer reactions: NO(2+) + NO.

    Science.gov (United States)

    Parkes, Michael A; Lockyear, Jessica F; Schröder, Detlef; Roithová, Jana; Price, Stephen D

    2011-11-07

    The single-electron transfer reaction between NO(2+) and NO, which initially forms a pair of NO(+) ions, has been studied using a position-sensitive coincidence technique. The reactivity in this class of collision system, which involves the interaction of a dication with its neutral precursor, provides a sensitive test of recent ideas concerning electronic state selectivity in dicationic single-electron transfer reactions. In stark contrast to the recently observed single-electron transfer reactivity in the analogous CO(2)(2+)/CO(2) and O(2)(2+)/O(2) collision systems, electron transfer between NO(2+) and NO generates two product NO(+) ions which behave in an identical manner, whether the ions are formed from NO(2+) or NO. This observed behaviour is in excellent accord with the recently proposed rationalization of the state selectivity in dication-molecule SET reactions using simple propensity rules involving one-electron transitions. This journal is © the Owner Societies 2011

  1. Single-molecule imaging of platinum ligand exchange reaction reveals reactivity distribution.

    Science.gov (United States)

    Esfandiari, N Melody; Wang, Yong; Bass, Jonathan Y; Cornell, Trevor P; Otte, Douglas A L; Cheng, Ming H; Hemminger, John C; McIntire, Theresa M; Mandelshtam, Vladimir A; Blum, Suzanne A

    2010-11-03

    Single-molecule fluorescence microscopy provided information about the real-time distribution of chemical reactivity on silicon oxide supports at the solution-surface interface, at a level of detail which would be unavailable from a traditional ensemble technique or from a technique that imaged the static physical properties of the surface. Chemical reactions on the surface were found to be uncorrelated; that is, the chemical reaction of one metal complex did not influence the location of a future chemical reaction of another metal complex.

  2. Single-Molecule Sensing with Nanopore Confinement: from Chemical Reactions to Biological Interactions.

    Science.gov (United States)

    Lin, Yao; Ying, Yi-Lun; Gao, Rui; Long, Yi-Tao

    2018-03-25

    The nanopore can generate an electrochemical confinement for single-molecule sensing which help understand the fundamental chemical principle in nanoscale dimensions. By observing the generated ionic current, individual bond-making and bond-breaking steps, single biomolecule dynamic conformational changes and electron transfer processes that occur within pore can be monitored with high temporal and current resolution. These single-molecule studies in nanopore confinement are revealing information about the fundamental chemical and biological processes that cannot be extracted from ensemble measurements. In this concept, we introduce and discuss the electrochemical confinement effects on single-molecule covalent reactions, conformational dynamics of individual molecules and host-guest interactions in protein nanopores. Then, we extend the concept of nanopore confinement effects to confine electrochemical redox reactions in solid-state nanopores for developing new sensing mechanisms. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  3. Fast and quantitative differentiation of single-base mismatched DNA by initial reaction rate of catalytic hairpin assembly.

    Science.gov (United States)

    Li, Chenxi; Li, Yixin; Xu, Xiao; Wang, Xinyi; Chen, Yang; Yang, Xiaoda; Liu, Feng; Li, Na

    2014-10-15

    The widely used catalytic hairpin assembly (CHA) amplification strategy generally needs several hours to accomplish one measurement based on the prevailingly used maximum intensity detection mode, making it less practical for assays where high throughput or speed is desired. To make the best use of the kinetic specificity of toehold domain for circuit reaction initiation, we developed a mathematical model and proposed an initial reaction rate detection mode to quantitatively differentiate the single-base mismatch. Using the kinetic mode, assay time can be reduced substantially to 10 min for one measurement with the comparable sensitivity and single-base mismatch differentiating ability as were obtained by the maximum intensity detection mode. This initial reaction rate based approach not only provided a fast and quantitative differentiation of single-base mismatch, but also helped in-depth understanding of the CHA system, which will be beneficial to the design of highly sensitive and specific toehold-mediated hybridization reactions. Copyright © 2014 Elsevier B.V. All rights reserved.

  4. Disturbances in reaction wheels; from measurement to modelling

    NARCIS (Netherlands)

    Le, M.P.; Ellenbroek, Marcellinus Hermannus Maria; Seiler, R; van Put, P.; Cottaar, E.J.E.

    2014-01-01

    Disturbances in reaction wheels have been long a crucial aspect for many scientific observation missions. An accurate and reliable disturbance model to understand and evaluate the influence of reaction wheel disturbances to the spacecraft is critically needed. Several reaction wheel disturbance

  5. A computational study of pyrolysis reactions of lignin model compounds

    Science.gov (United States)

    Thomas Elder

    2010-01-01

    Enthalpies of reaction for the initial steps in the pyrolysis of lignin have been evaluated at the CBS-4m level of theory using fully substituted b-O-4 dilignols. Values for competing unimolecular decomposition reactions are consistent with results previously published for phenethyl phenyl ether models, but with lowered selectivity. Chain propagating reactions of free...

  6. Reaction Kinetics Model of Polymerization in the Absence of ...

    African Journals Online (AJOL)

    This paper is on reaction kinetics models for approximating diffuse propagation reaction fronts in one-dimensional gasless combustion type models. This study is carried out in the context of free-radical frontal polymerization (FP) via a propagating, self sustaining reacting front in the absence of material diffusion. The model ...

  7. Reaction Wheel Disturbance Model Extraction Software Project

    Data.gov (United States)

    National Aeronautics and Space Administration — Reaction wheel mechanical noise is one of the largest sources of disturbance forcing on space-based observatories. Such noise arises from mass imbalance, bearing...

  8. Reaction Wheel Disturbance Model Extraction Software Project

    Data.gov (United States)

    National Aeronautics and Space Administration — Reaction wheel disturbances are some of the largest sources of noise on sensitive telescopes. Such wheel-induced mechanical noises are not well characterized....

  9. Supramolecular Systems and Chemical Reactions in Single-Molecule Break Junctions.

    Science.gov (United States)

    Li, Xiaohui; Hu, Duan; Tan, Zhibing; Bai, Jie; Xiao, Zongyuan; Yang, Yang; Shi, Jia; Hong, Wenjing

    2017-04-01

    The major challenges of molecular electronics are the understanding and manipulation of the electron transport through the single-molecule junction. With the single-molecule break junction techniques, including scanning tunneling microscope break junction technique and mechanically controllable break junction technique, the charge transport through various single-molecule and supramolecular junctions has been studied during the dynamic fabrication and continuous characterization of molecular junctions. This review starts from the charge transport characterization of supramolecular junctions through a variety of noncovalent interactions, such as hydrogen bond, π-π interaction, and electrostatic force. We further review the recent progress in constructing highly conductive molecular junctions via chemical reactions, the response of molecular junctions to external stimuli, as well as the application of break junction techniques in controlling and monitoring chemical reactions in situ. We suggest that beyond the measurement of single molecular conductance, the single-molecule break junction techniques provide a promising access to study molecular assembly and chemical reactions at the single-molecule scale.

  10. Including lateral interactions into microkinetic models of catalytic reactions

    DEFF Research Database (Denmark)

    Hellman, Anders; Honkala, Johanna Karoliina

    2007-01-01

    In many catalytic reactions lateral interactions between adsorbates are believed to have a strong influence on the reaction rates. We apply a microkinetic model to explore the effect of lateral interactions and how to efficiently take them into account in a simple catalytic reaction. Three differ...... different approximations are investigated: site, mean-field, and quasichemical approximations. The obtained results are compared to accurate Monte Carlo numbers. In the end, we apply the approximations to a real catalytic reaction, namely, ammonia synthesis....

  11. Reaction of single-standard DNA with hydroxyl radical generated by iron(II)-ethylenediaminetetraacetic acid

    International Nuclear Information System (INIS)

    Prigodich, R.V.; Martin, C.T.

    1990-01-01

    This study demonstrates that the reaction of Fe(II)-EDTA and hydrogen peroxide with the single-stranded nucleic acids d(pT) 70 and a 29-base sequence containing a mixture of bases results in substantial damage which is not directly detected by gel electrophoresis. Cleavage of the DNA sugar backbone is enhanced significantly after the samples are incubated at 90 degree C in the presence of piperidine. The latter reaction is used in traditional Maxam-Gilbert DNA sequencing to detect base damage, and the current results are consistent with reaction of the hydroxyl radical with the bases in single-stranded DNA (although reaction with sugar may also produce adducts that are uncleaved but labile to cleavage by piperidine). We the authors propose that hydroxyl radicals may react preferentially with the nucleic acid bases in ssDNA and that reaction of the sugars in dsDNA is dominant because the bases are sequestered within the double helix. These results have implications both for the study of single-stranded DNA binding protein binding sites and for the interpretation of experiments using the hydroxyl radical to probe DNA structure or to footprint double-stranded DNA binding protein binding sites

  12. Stability results for a reaction-diffusion system with a single measurement

    Energy Technology Data Exchange (ETDEWEB)

    Ramoul, Hichem [Centre universitaire de Khenchela, Route de Batna, BP 1252, Liberte, 40004 Khenchela (Algeria); Gaitan, Patricia [Laboratoire d' analyse, topologie, probabilites CNRS UMR 6632, Marseille (France) and Universite Aix-Marseille II (France); Cristofol, Michel [Laboratoire d' analyse, topologie, probabilites CNRS UMR 6632, Marseille, France and Universite Aix-Marseille III (France)

    2007-06-15

    For a two by two reaction-diffusion system on a bounded domain we give a simultaneous stability result for one coefficient and for the initial conditions. The key ingredient is a global Carleman-type estimate with a single observation acting on a subdomain.

  13. Effects of reaction-kinetic parameters on modeling reaction pathways in GaN MOVPE growth

    Science.gov (United States)

    Zhang, Hong; Zuo, Ran; Zhang, Guoyi

    2017-11-01

    In the modeling of the reaction-transport process in GaN MOVPE growth, the selections of kinetic parameters (activation energy Ea and pre-exponential factor A) for gas reactions are quite uncertain, which cause uncertainties in both gas reaction path and growth rate. In this study, numerical modeling of the reaction-transport process for GaN MOVPE growth in a vertical rotating disk reactor is conducted with varying kinetic parameters for main reaction paths. By comparisons of the molar concentrations of major Ga-containing species and the growth rates, the effects of kinetic parameters on gas reaction paths are determined. The results show that, depending on the values of the kinetic parameters, the gas reaction path may be dominated either by adduct/amide formation path, or by TMG pyrolysis path, or by both. Although the reaction path varies with different kinetic parameters, the predicted growth rates change only slightly because the total transport rate of Ga-containing species to the substrate changes slightly with reaction paths. This explains why previous authors using different chemical models predicted growth rates close to the experiment values. By varying the pre-exponential factor for the amide trimerization, it is found that the more trimers are formed, the lower the growth rates are than the experimental value, which indicates that trimers are poor growth precursors, because of thermal diffusion effect caused by high temperature gradient. The effective order for the contribution of major species to growth rate is found as: pyrolysis species > amides > trimers. The study also shows that radical reactions have little effect on gas reaction path because of the generation and depletion of H radicals in the chain reactions when NH2 is considered as the end species.

  14. Computational study of a model system of enzyme-mediated [4+2] cycloaddition reaction.

    Science.gov (United States)

    Gordeev, Evgeniy G; Ananikov, Valentine P

    2015-01-01

    A possible mechanistic pathway related to an enzyme-catalyzed [4+2] cycloaddition reaction was studied by theoretical calculations at density functional (B3LYP, O3LYP, M062X) and semiempirical levels (PM6-DH2, PM6) performed on a model system. The calculations were carried out for the key [4+2] cycloaddition step considering enzyme-catalyzed biosynthesis of Spinosyn A in a model reaction, where a reliable example of a biological Diels-Alder reaction was reported experimentally. In the present study it was demonstrated that the [4+2] cycloaddition reaction may benefit from moving along the energetically balanced reaction coordinate, which enabled the catalytic rate enhancement of the [4+2] cycloaddition pathway involving a single transition state. Modeling of such a system with coordination of three amino acids indicated a reliable decrease of activation energy by ~18.0 kcal/mol as compared to a non-catalytic transformation.

  15. Computational study of a model system of enzyme-mediated [4+2] cycloaddition reaction.

    Directory of Open Access Journals (Sweden)

    Evgeniy G Gordeev

    Full Text Available A possible mechanistic pathway related to an enzyme-catalyzed [4+2] cycloaddition reaction was studied by theoretical calculations at density functional (B3LYP, O3LYP, M062X and semiempirical levels (PM6-DH2, PM6 performed on a model system. The calculations were carried out for the key [4+2] cycloaddition step considering enzyme-catalyzed biosynthesis of Spinosyn A in a model reaction, where a reliable example of a biological Diels-Alder reaction was reported experimentally. In the present study it was demonstrated that the [4+2] cycloaddition reaction may benefit from moving along the energetically balanced reaction coordinate, which enabled the catalytic rate enhancement of the [4+2] cycloaddition pathway involving a single transition state. Modeling of such a system with coordination of three amino acids indicated a reliable decrease of activation energy by ~18.0 kcal/mol as compared to a non-catalytic transformation.

  16. High-throughput microfluidic single-cell digital polymerase chain reaction.

    Science.gov (United States)

    White, A K; Heyries, K A; Doolin, C; Vaninsberghe, M; Hansen, C L

    2013-08-06

    Here we present an integrated microfluidic device for the high-throughput digital polymerase chain reaction (dPCR) analysis of single cells. This device allows for the parallel processing of single cells and executes all steps of analysis, including cell capture, washing, lysis, reverse transcription, and dPCR analysis. The cDNA from each single cell is distributed into a dedicated dPCR array consisting of 1020 chambers, each having a volume of 25 pL, using surface-tension-based sample partitioning. The high density of this dPCR format (118,900 chambers/cm(2)) allows the analysis of 200 single cells per run, for a total of 204,000 PCR reactions using a device footprint of 10 cm(2). Experiments using RNA dilutions show this device achieves shot-noise-limited performance in quantifying single molecules, with a dynamic range of 10(4). We performed over 1200 single-cell measurements, demonstrating the use of this platform in the absolute quantification of both high- and low-abundance mRNA transcripts, as well as micro-RNAs that are not easily measured using alternative hybridization methods. We further apply the specificity and sensitivity of single-cell dPCR to performing measurements of RNA editing events in single cells. High-throughput dPCR provides a new tool in the arsenal of single-cell analysis methods, with a unique combination of speed, precision, sensitivity, and specificity. We anticipate this approach will enable new studies where high-performance single-cell measurements are essential, including the analysis of transcriptional noise, allelic imbalance, and RNA processing.

  17. Assessing Model Characterization of Single Source ...

    Science.gov (United States)

    Aircraft measurements made downwind from specific coal fired power plants during the 2013 Southeast Nexus field campaign provide a unique opportunity to evaluate single source photochemical model predictions of both O3 and secondary PM2.5 species. The model did well at predicting downwind plume placement. The model shows similar patterns of an increasing fraction of PM2.5 sulfate ion to the sum of SO2 and PM2.5 sulfate ion by distance from the source compared with ambient based estimates. The model was less consistent in capturing downwind ambient based trends in conversion of NOX to NOY from these sources. Source sensitivity approaches capture near-source O3 titration by fresh NO emissions, in particular subgrid plume treatment. However, capturing this near-source chemical feature did not translate into better downwind peak estimates of single source O3 impacts. The model estimated O3 production from these sources but often was lower than ambient based source production. The downwind transect ambient measurements, in particular secondary PM2.5 and O3, have some level of contribution from other sources which makes direct comparison with model source contribution challenging. Model source attribution results suggest contribution to secondary pollutants from multiple sources even where primary pollutants indicate the presence of a single source. The National Exposure Research Laboratory (NERL) Computational Exposure Division (CED) develops and evaluates data, deci

  18. Effect of reactions in small eddies on biomass gasification with eddy dissipation concept - Sub-grid scale reaction model.

    Science.gov (United States)

    Chen, Juhui; Yin, Weijie; Wang, Shuai; Meng, Cheng; Li, Jiuru; Qin, Bai; Yu, Guangbin

    2016-07-01

    Large-eddy simulation (LES) approach is used for gas turbulence, and eddy dissipation concept (EDC)-sub-grid scale (SGS) reaction model is employed for reactions in small eddies. The simulated gas molar fractions are in better agreement with experimental data with EDC-SGS reaction model. The effect of reactions in small eddies on biomass gasification is emphatically analyzed with EDC-SGS reaction model. The distributions of the SGS reaction rates which represent the reactions in small eddies with particles concentration and temperature are analyzed. The distributions of SGS reaction rates have the similar trend with those of total reactions rates and the values account for about 15% of the total reactions rates. The heterogeneous reaction rates with EDC-SGS reaction model are also improved during the biomass gasification process in bubbling fluidized bed. Copyright © 2016 Elsevier Ltd. All rights reserved.

  19. Graphical models for inferring single molecule dynamics

    Directory of Open Access Journals (Sweden)

    Gonzalez Ruben L

    2010-10-01

    Full Text Available Abstract Background The recent explosion of experimental techniques in single molecule biophysics has generated a variety of novel time series data requiring equally novel computational tools for analysis and inference. This article describes in general terms how graphical modeling may be used to learn from biophysical time series data using the variational Bayesian expectation maximization algorithm (VBEM. The discussion is illustrated by the example of single-molecule fluorescence resonance energy transfer (smFRET versus time data, where the smFRET time series is modeled as a hidden Markov model (HMM with Gaussian observables. A detailed description of smFRET is provided as well. Results The VBEM algorithm returns the model’s evidence and an approximating posterior parameter distribution given the data. The former provides a metric for model selection via maximum evidence (ME, and the latter a description of the model’s parameters learned from the data. ME/VBEM provide several advantages over the more commonly used approach of maximum likelihood (ML optimized by the expectation maximization (EM algorithm, the most important being a natural form of model selection and a well-posed (non-divergent optimization problem. Conclusions The results demonstrate the utility of graphical modeling for inference of dynamic processes in single molecule biophysics.

  20. Model photo reaction centers via genetic engineering

    Energy Technology Data Exchange (ETDEWEB)

    Zhiyu Wang; DiMagno, T.J.; Popov, M.; Norris, J.R. [Argonne National Lab., IL (United States)]|[Chicago Univ., IL (United States). Dept. of Chemistry; Chikin Chan; Fleming, G. [Chicago Univ., IL (United States). Dept. of Chemistry; Jau Tang; Hanson, D.; Schiffer, M. [Argonne National Lab., IL (United States)

    1992-12-31

    A series of reaction centers of Rhodococcus capsulatus isolated from a set of mutated organisms modified by site-directed mutagenesis at residues M208 and L181 are described. Changes in the amino acid at these sites affect both the energetics of the systems as well as the chemical kinetics for the initial ET event. Two empirical relations among the different mutants for the reduction potential and the ET rate are presented.

  1. Model photo reaction centers via genetic engineering

    Energy Technology Data Exchange (ETDEWEB)

    Zhiyu Wang; DiMagno, T.J.; Popov, M.; Norris, J.R. (Argonne National Lab., IL (United States) Chicago Univ., IL (United States). Dept. of Chemistry); Chikin Chan; Fleming, G. (Chicago Univ., IL (United States). Dept. of Chemistry); Jau Tang; Hanson, D.; Schiffer, M. (Argonne National Lab., IL (United States))

    1992-01-01

    A series of reaction centers of Rhodococcus capsulatus isolated from a set of mutated organisms modified by site-directed mutagenesis at residues M208 and L181 are described. Changes in the amino acid at these sites affect both the energetics of the systems as well as the chemical kinetics for the initial ET event. Two empirical relations among the different mutants for the reduction potential and the ET rate are presented.

  2. Two-nucleon transfer reactions with form factor models

    International Nuclear Information System (INIS)

    Osman, A.

    1980-04-01

    The theory of two-nucleon transfer reactions is considered. Nuclear reactions are considered with triton or 3 He particles which are used as projectiles in stripping reactions and as detected particles in pick-up reactions. In each channel we have a four-particle problem, three of them are nucleons and the fourth is a heavy particle. These transfer reactions are studied on the basis of the generaled R-matrix method. Different channel functions of the sub-clusters in the triton and 3 He particles are included. Model form factors are obtained and are used in two-nucleon transfer reactions. Differential cross-sections of different two-nucleon transfer reactions are calculated and are found in good agreement with the experimental data. The correct normalization and spectroscopic factors are obtained. (author)

  3. Modeling the Activity of Single Genes

    Science.gov (United States)

    Mjolsness, Eric; Gibson, Michael

    1999-01-01

    The central dogma of molecular biology states that information is stored in DNA, transcribed to messenger RNA (mRNA) and then translated into proteins. This picture is significantly augmentated when we consider the action of certain proteins in regulating transcription. These transcription factors provide a feedback pathway by which genes can regulate one another's expression as mRNA and then as protein. To review: DNA, RNA and proteins have different functions. DNA is the molecular storehouse of genetic information. When cells divide, the DNA is replicated, so that each daughter cell maintains the same genetic information as the mother cell. RNA acts as a go-between from DNA to proteins. Only a single copy of DNA is present, but multiple copies of the same piece of RNA may be present, allowing cells to make huge amounts of protein. In eukaryotes (organisms with a nucleus), DNA is found in the nucleus only. RNA is copied in the nucleus then translocates(moves) outside the nucleus, where it is transcribed into proteins. Along the way, the RNA may be spliced, i.e., may have pieces cut out. RNA then attaches to ribosomes and is translated to proteins. Proteins are the machinery of the cell other than DNA and RNA, all the complex molecules of the cell are proteins. Proteins are specialized machines, each of which fulfills its own task, which may be transporting oxygen, catalyzing reactions, or responding to extracellular signals, just to name a few. One of the more interesting functions a protein may have is binding directly or indirectly to DNA to perform transcriptional regulation, thus forming a closed feedback loop of gene regulation. The structure of DNA and the central dogma were understood in the 50s; in the early 80s it became possible to make arbitrary modifications to DNA and use cellular machinery to transcribe and translate the resulting genes; more recently, genomes (i.e., the complete DNA sequence) of many organisms have been sequenced. This large

  4. Highly Durable Platinum Single-Atom Alloy Catalyst for Electrochemical Reactions

    DEFF Research Database (Denmark)

    Kim, Jiwhan; Roh, Chi-Woo; Sahoo, Suman Kalyan

    2018-01-01

    -doped tin oxide (Pt1/ATO) is synthesized by conventional incipient wetness impregnation, with up to 8 wt% Pt. The single atomic Pt structure is confirmed by high-angle annular dark field scanning tunneling electron microscopy images and extended X-ray absorption fine structure analysis results. Density......Single atomic Pt catalyst can offer efficient utilization of the expensive platinum and provide unique selectivity because it lacks ensemble sites. However, designing such a catalyst with high Pt loading and good durability is very challenging. Here, single atomic Pt catalyst supported on antimony...... functional theory calculations show that replacing Sb sites with Pt atoms in the bulk phase or at the surface of SbSn or ATO is energetically favorable. The Pt1/ATO shows superior activity and durability for formic acid oxidation reaction, compared to a commercial Pt/C catalyst. The single atomic Pt...

  5. Stepwise kinetic equilibrium models of quantitative polymerase chain reaction.

    Science.gov (United States)

    Cobbs, Gary

    2012-08-16

    Numerous models for use in interpreting quantitative PCR (qPCR) data are present in recent literature. The most commonly used models assume the amplification in qPCR is exponential and fit an exponential model with a constant rate of increase to a select part of the curve. Kinetic theory may be used to model the annealing phase and does not assume constant efficiency of amplification. Mechanistic models describing the annealing phase with kinetic theory offer the most potential for accurate interpretation of qPCR data. Even so, they have not been thoroughly investigated and are rarely used for interpretation of qPCR data. New results for kinetic modeling of qPCR are presented. Two models are presented in which the efficiency of amplification is based on equilibrium solutions for the annealing phase of the qPCR process. Model 1 assumes annealing of complementary targets strands and annealing of target and primers are both reversible reactions and reach a dynamic equilibrium. Model 2 assumes all annealing reactions are nonreversible and equilibrium is static. Both models include the effect of primer concentration during the annealing phase. Analytic formulae are given for the equilibrium values of all single and double stranded molecules at the end of the annealing step. The equilibrium values are then used in a stepwise method to describe the whole qPCR process. Rate constants of kinetic models are the same for solutions that are identical except for possibly having different initial target concentrations. Analysis of qPCR curves from such solutions are thus analyzed by simultaneous non-linear curve fitting with the same rate constant values applying to all curves and each curve having a unique value for initial target concentration. The models were fit to two data sets for which the true initial target concentrations are known. Both models give better fit to observed qPCR data than other kinetic models present in the literature. They also give better estimates of

  6. Stepwise kinetic equilibrium models of quantitative polymerase chain reaction

    Directory of Open Access Journals (Sweden)

    Cobbs Gary

    2012-08-01

    Full Text Available Abstract Background Numerous models for use in interpreting quantitative PCR (qPCR data are present in recent literature. The most commonly used models assume the amplification in qPCR is exponential and fit an exponential model with a constant rate of increase to a select part of the curve. Kinetic theory may be used to model the annealing phase and does not assume constant efficiency of amplification. Mechanistic models describing the annealing phase with kinetic theory offer the most potential for accurate interpretation of qPCR data. Even so, they have not been thoroughly investigated and are rarely used for interpretation of qPCR data. New results for kinetic modeling of qPCR are presented. Results Two models are presented in which the efficiency of amplification is based on equilibrium solutions for the annealing phase of the qPCR process. Model 1 assumes annealing of complementary targets strands and annealing of target and primers are both reversible reactions and reach a dynamic equilibrium. Model 2 assumes all annealing reactions are nonreversible and equilibrium is static. Both models include the effect of primer concentration during the annealing phase. Analytic formulae are given for the equilibrium values of all single and double stranded molecules at the end of the annealing step. The equilibrium values are then used in a stepwise method to describe the whole qPCR process. Rate constants of kinetic models are the same for solutions that are identical except for possibly having different initial target concentrations. Analysis of qPCR curves from such solutions are thus analyzed by simultaneous non-linear curve fitting with the same rate constant values applying to all curves and each curve having a unique value for initial target concentration. The models were fit to two data sets for which the true initial target concentrations are known. Both models give better fit to observed qPCR data than other kinetic models present in the

  7. Mass transfer with complex reversible chemical reactions—I. Single reversible chemical reaction

    NARCIS (Netherlands)

    Versteeg, G.F.; Kuipers, J.A.M.; Beckum, F.P.H. van; Swaaij, W.P.M. van

    1989-01-01

    An improved numerical technique was used in order to develop an absorption model with which it is possible to calculate rapidly absorption rates for the phenomenon of mass transfer accompanied by a complex reversible chemical reaction. This model can be applied for the calculation of the mass

  8. Modelling of chemical reactions in metallurgical processes

    OpenAIRE

    Kinaci, M. Efe; Lichtenegger, Thomas; Schneiderbauer, Simon

    2017-01-01

    Iron-ore reduction has attracted much interest in the last three decades since it can be considered as a core process in steel industry. The iron-ore is reduced to iron with the use of blast furnace and fluidized bed technologies. To investigate the harsh conditions inside fluidized bed reactors, computational tools can be utilized. One such tool is the CFD-DEM method, in which the gas phase reactions and governing equations are calculated in the Eulerian (CFD) side, whereas the particle reac...

  9. Measurement of Neutron Reaction Cross Sections in Carbon using a Single Crystal Diamond Detector

    Energy Technology Data Exchange (ETDEWEB)

    Pillon, M.; Angelone, M. [Associazione EURATOM-ENEA sulla Fusione, ENEA C.R. Frascati, via E. Fermi, 45 0044 Frascati, Rome (Italy); Krasa, A.; Plompen, A. J. M.; Schillebeeckx, P. [European Commission, Joint Research Centre, Institute for Reference Materials and Measurements, - 2440 Geel (Belgium); Sergi, M. L. [Dipartimento di Fisica e Astronomia, Universita di Catania e INFN-Laboratori Nazionali del Sud, Catania (Italy)

    2011-12-13

    A single crystal diamond detector was exposed to the quasi mono-energetic neutron fields in the energy range from 7 MeV to 20.5 MeV produced by the Van de Graaff neutron generator of the EC-JRC-IRMM. Pulse Height Spectra (PHS) of the neutron interaction with the diamond (carbon) were recorded in order to derive the experimental response function of this detector to neutrons in view of its use as a compact fast neutron spectrometer. Several peaks produced by outgoing charged particles produced when neutrons interact with carbon were identified using the reaction Q-values. The corresponding nuclear reactions, such as (n,{alpha}), (n,p), (n,d) for different excitation states were identified in the PHS. The analysis of the peaks allows the derivation of some neutron reaction cross sections in carbon. The results are presented in this paper together with the associated uncertainties.

  10. Measurement of Neutron Reaction Cross Sections in Carbon using a Single Crystal Diamond Detector

    Science.gov (United States)

    Pillon, M.; Angelone, M.; Krása, A.; Plompen, A. J. M.; Schillebeeckx, P.; Sergi, M. L.

    2011-12-01

    A single crystal diamond detector was exposed to the quasi mono-energetic neutron fields in the energy range from 7 MeV to 20.5 MeV produced by the Van de Graaff neutron generator of the EC-JRC-IRMM. Pulse Height Spectra (PHS) of the neutron interaction with the diamond (carbon) were recorded in order to derive the experimental response function of this detector to neutrons in view of its use as a compact fast neutron spectrometer. Several peaks produced by outgoing charged particles produced when neutrons interact with carbon were identified using the reaction Q-values. The corresponding nuclear reactions, such as (n,α), (n,p), (n,d) for different excitation states were identified in the PHS. The analysis of the peaks allows the derivation of some neutron reaction cross sections in carbon. The results are presented in this paper together with the associated uncertainties.

  11. A mesoscopic reaction rate model for shock initiation of multi-component PBX explosives.

    Science.gov (United States)

    Liu, Y R; Duan, Z P; Zhang, Z Y; Ou, Z C; Huang, F L

    2016-11-05

    The primary goal of this research is to develop a three-term mesoscopic reaction rate model that consists of a hot-spot ignition, a low-pressure slow burning and a high-pressure fast reaction terms for shock initiation of multi-component Plastic Bonded Explosives (PBX). Thereinto, based on the DZK hot-spot model for a single-component PBX explosive, the hot-spot ignition term as well as its reaction rate is obtained through a "mixing rule" of the explosive components; new expressions for both the low-pressure slow burning term and the high-pressure fast reaction term are also obtained by establishing the relationships between the reaction rate of the multi-component PBX explosive and that of its explosive components, based on the low-pressure slow burning term and the high-pressure fast reaction term of a mesoscopic reaction rate model. Furthermore, for verification, the new reaction rate model is incorporated into the DYNA2D code to simulate numerically the shock initiation process of the PBXC03 and the PBXC10 multi-component PBX explosives, and the numerical results of the pressure histories at different Lagrange locations in explosive are found to be in good agreements with previous experimental data. Copyright © 2016 Elsevier B.V. All rights reserved.

  12. Analytically solvable models of reaction-diffusion systems

    Energy Technology Data Exchange (ETDEWEB)

    Zemskov, E P; Kassner, K [Institut fuer Theoretische Physik, Otto-von-Guericke-Universitaet, Universitaetsplatz 2, 39106 Magdeburg (Germany)

    2004-05-01

    We consider a class of analytically solvable models of reaction-diffusion systems. An analytical treatment is possible because the nonlinear reaction term is approximated by a piecewise linear function. As particular examples we choose front and pulse solutions to illustrate the matching procedure in the one-dimensional case.

  13. Constituent rearrangement model and large transverse momentum reactions

    International Nuclear Information System (INIS)

    Igarashi, Yuji; Imachi, Masahiro; Matsuoka, Takeo; Otsuki, Shoichiro; Sawada, Shoji.

    1978-01-01

    In this chapter, two models based on the constituent rearrangement picture for large p sub( t) phenomena are summarized. One is the quark-junction model, and the other is the correlating quark rearrangement model. Counting rules of the models apply to both two-body reactions and hadron productions. (author)

  14. The Sugar Model: Autocatalytic Activity of the Triose Ammonia Reaction

    Science.gov (United States)

    Weber, Arthur L.

    2007-04-01

    Reaction of triose sugars with ammonia under anaerobic conditions yielded autocatalytic products. The autocatalytic behavior of the products was examined by measuring the effect of the crude triose ammonia reaction product on the kinetics of a second identical triose ammonia reaction. The reaction product showed autocatalytic activity by increasing both the rate of disappearance of triose and the rate of formation of pyruvaldehyde, the product of triose dehydration. This synthetic process is considered a reasonable model of origin-of-life chemistry because it uses plausible prebiotic substrates, and resembles modern biosynthesis by employing the energized carbon groups of sugars to drive the synthesis of autocatalytic molecules.

  15. Reading and a diffusion model analysis of reaction time.

    Science.gov (United States)

    Naples, Adam; Katz, Leonard; Grigorenko, Elena L

    2012-01-01

    Processing speed is associated with reading performance. However, the literature is not clear either on the definition of processing speed or on why and how it contributes to reading performance. In this study we demonstrated that processing speed, as measured by reaction time, is not a unitary construct. Using the diffusion model of two-choice reaction time, we assessed processing speed in a series of same-different reaction time tasks for letter and number strings. We demonstrated that the association between reaction time and reading performance is driven by processing speed for reading-related information, but not motor or sensory encoding speed.

  16. Deeper Insight into the Diels-Alder Reaction through the Activation Strain Model

    NARCIS (Netherlands)

    Fernandez, I.; Bickelhaupt, F.M.

    2016-01-01

    The Diels–Alder (DA) cycloaddition reaction has the ability to significantly increase molecular complexity regioselectively and stereospecifically in a single synthetic step. In this review it is discussed how the activation strain model of chemical reactivity reveals the physical factors that

  17. Electrochemical Dynamics of a Single Platinum Nanoparticle Collision Event for the Hydrogen Evolution Reaction.

    Science.gov (United States)

    Xiang, Zhi-Peng; Deng, Hai-Qiang; Peljo, Pekka; Fu, Zhi-Yong; Wang, Su-Li; Mandler, Daniel; Sun, Gong-Quan; Liang, Zhen-Xing

    2018-03-19

    Chronoamperometry was used to study the dynamics of Pt nanoparticle (NP) collision with an inert ultramicroelectrode via electrocatalytic amplification (ECA) in the hydrogen evolution reaction. ECA and dynamic light scattering (DLS) results reveal that the NP colloid remains stable only at low proton concentrations (1.0 mm) under a helium (He) atmosphere, ensuring that the collision events occur at genuinely single NP level. Amperometry of single NP collisions under a He atmosphere shows that each discrete current profile of the collision event evolves from spike to staircase at more negative potentials, while a staircase response is observed at all of the applied potentials under hydrogen-containing atmospheres. The particle size distribution estimated from the diffusion-controlled current in He agrees well with electron microscopy and DLS observations. These results shed light on the interfacial dynamics of the single nanoparticle collision electrochemistry. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  18. Modeling Electric Double-Layers Including Chemical Reaction Effects

    DEFF Research Database (Denmark)

    Paz-Garcia, Juan Manuel; Johannesson, Björn; Ottosen, Lisbeth M.

    2014-01-01

    A physicochemical and numerical model for the transient formation of an electric double-layer between an electrolyte and a chemically-active flat surface is presented, based on a finite elements integration of the nonlinear Nernst-Planck-Poisson model including chemical reactions. The model works...

  19. A brief overview of models of nucleon-induced reactions

    International Nuclear Information System (INIS)

    Carlson, B.V.

    2003-01-01

    The basic features of low to intermediate energy nucleon-induced reactions are discussed within the contexts of the optical model, the statistical model, preequilibrium and intranuclear cascade models. The calculation of cross sections and other scattering quantities are described. (author)

  20. Retrosynthetic Reaction Prediction Using Neural Sequence-to-Sequence Models.

    Science.gov (United States)

    Liu, Bowen; Ramsundar, Bharath; Kawthekar, Prasad; Shi, Jade; Gomes, Joseph; Luu Nguyen, Quang; Ho, Stephen; Sloane, Jack; Wender, Paul; Pande, Vijay

    2017-10-25

    We describe a fully data driven model that learns to perform a retrosynthetic reaction prediction task, which is treated as a sequence-to-sequence mapping problem. The end-to-end trained model has an encoder-decoder architecture that consists of two recurrent neural networks, which has previously shown great success in solving other sequence-to-sequence prediction tasks such as machine translation. The model is trained on 50,000 experimental reaction examples from the United States patent literature, which span 10 broad reaction types that are commonly used by medicinal chemists. We find that our model performs comparably with a rule-based expert system baseline model, and also overcomes certain limitations associated with rule-based expert systems and with any machine learning approach that contains a rule-based expert system component. Our model provides an important first step toward solving the challenging problem of computational retrosynthetic analysis.

  1. The Effects of Mixing, Reaction Rates, and Stoichiometry on Yield for Mixing Sensitive Reactions—Part I: Model Development

    Directory of Open Access Journals (Sweden)

    Syed Imran A. Shah

    2012-01-01

    Full Text Available There are two classes of mixing sensitive reactions: competitive-consecutive and competitive-parallel. The yield of desired product from these coupled reactions depends on how fast the reactants are brought together. Recent experimental results have suggested that the mixing effect may depend strongly on the stoichiometry of the reactions. To investigate this, a 1D, dimensionless, reaction-diffusion model at the micromixing scale was developed. Assuming constant mass concentration and mass diffusivities, systems of PDE's were derived on a mass fraction basis for both types of reactions. Two dimensionless reaction rate ratios and a single general Damköhler number emerged from the analysis. The resulting dimensionless equations were used to investigate the effects of mixing, reaction rate ratio, and reaction stoichiometry. As expected, decreasing either the striation thickness or the dimensionless rate ratio maximizes yield, the reaction stoichiometry has a considerable effect on yield, and all three variables interact strongly.

  2. Cellular automaton model of coupled mass transport and chemical reactions

    International Nuclear Information System (INIS)

    Karapiperis, T.

    1994-01-01

    Mass transport, coupled with chemical reactions, is modelled as a cellular automaton in which solute molecules perform a random walk on a lattice and react according to a local probabilistic rule. Assuming molecular chaos and a smooth density function, we obtain the standard reaction-transport equations in the continuum limit. The model is applied to the reactions a + b ↔c and a + b →c, where we observe interesting macroscopic effects resulting from microscopic fluctuations and spatial correlations between molecules. We also simulate autocatalytic reaction schemes displaying spontaneous formation of spatial concentration patterns. Finally, we propose and discuss the limitations of a simple model for mineral-solute interaction. (author) 5 figs., 20 refs

  3. Stop-Frame Filming and Discovery of Reactions at the Single-Molecule Level by Transmission Electron Microscopy

    Science.gov (United States)

    2017-01-01

    We report an approach, named chemTEM, to follow chemical transformations at the single-molecule level with the electron beam of a transmission electron microscope (TEM) applied as both a tunable source of energy and a sub-angstrom imaging probe. Deposited on graphene, disk-shaped perchlorocoronene molecules are precluded from intermolecular interactions. This allows monomolecular transformations to be studied at the single-molecule level in real time and reveals chlorine elimination and reactive aryne formation as a key initial stage of multistep reactions initiated by the 80 keV e-beam. Under the same conditions, perchlorocoronene confined within a nanotube cavity, where the molecules are situated in very close proximity to each other, enables imaging of intermolecular reactions, starting with the Diels–Alder cycloaddition of a generated aryne, followed by rearrangement of the angular adduct to a planar polyaromatic structure and the formation of a perchlorinated zigzag nanoribbon of graphene as the final product. ChemTEM enables the entire process of polycondensation, including the formation of metastable intermediates, to be captured in a one-shot “movie”. A molecule with a similar size and shape but with a different chemical composition, octathio[8]circulene, under the same conditions undergoes another type of polycondensation via thiyl biradical generation and subsequent reaction leading to polythiophene nanoribbons with irregular edges incorporating bridging sulfur atoms. Graphene or carbon nanotubes supporting the individual molecules during chemTEM studies ensure that the elastic interactions of the molecules with the e-beam are the dominant forces that initiate and drive the reactions we image. Our ab initio DFT calculations explicitly incorporating the e-beam in the theoretical model correlate with the chemTEM observations and give a mechanism for direct control not only of the type of the reaction but also of the reaction rate. Selection of the

  4. Stop-Frame Filming and Discovery of Reactions at the Single-Molecule Level by Transmission Electron Microscopy.

    Science.gov (United States)

    Chamberlain, Thomas W; Biskupek, Johannes; Skowron, Stephen T; Markevich, Alexander V; Kurasch, Simon; Reimer, Oliver; Walker, Kate E; Rance, Graham A; Feng, Xinliang; Müllen, Klaus; Turchanin, Andrey; Lebedeva, Maria A; Majouga, Alexander G; Nenajdenko, Valentin G; Kaiser, Ute; Besley, Elena; Khlobystov, Andrei N

    2017-03-28

    We report an approach, named chemTEM, to follow chemical transformations at the single-molecule level with the electron beam of a transmission electron microscope (TEM) applied as both a tunable source of energy and a sub-angstrom imaging probe. Deposited on graphene, disk-shaped perchlorocoronene molecules are precluded from intermolecular interactions. This allows monomolecular transformations to be studied at the single-molecule level in real time and reveals chlorine elimination and reactive aryne formation as a key initial stage of multistep reactions initiated by the 80 keV e-beam. Under the same conditions, perchlorocoronene confined within a nanotube cavity, where the molecules are situated in very close proximity to each other, enables imaging of intermolecular reactions, starting with the Diels-Alder cycloaddition of a generated aryne, followed by rearrangement of the angular adduct to a planar polyaromatic structure and the formation of a perchlorinated zigzag nanoribbon of graphene as the final product. ChemTEM enables the entire process of polycondensation, including the formation of metastable intermediates, to be captured in a one-shot "movie". A molecule with a similar size and shape but with a different chemical composition, octathio[8]circulene, under the same conditions undergoes another type of polycondensation via thiyl biradical generation and subsequent reaction leading to polythiophene nanoribbons with irregular edges incorporating bridging sulfur atoms. Graphene or carbon nanotubes supporting the individual molecules during chemTEM studies ensure that the elastic interactions of the molecules with the e-beam are the dominant forces that initiate and drive the reactions we image. Our ab initio DFT calculations explicitly incorporating the e-beam in the theoretical model correlate with the chemTEM observations and give a mechanism for direct control not only of the type of the reaction but also of the reaction rate. Selection of the

  5. Studying Chemical Reactions, One Bond at a Time, with Single Molecule AFM Techniques

    Science.gov (United States)

    Fernandez, Julio M.

    2008-03-01

    The mechanisms by which mechanical forces regulate the kinetics of a chemical reaction are unknown. In my lecture I will demonstrate how we use single molecule force-clamp spectroscopy and protein engineering to study the effect of force on the kinetics of thiol/disulfide exchange. Reduction of disulfide bond via the thiol/disulfide exchange chemical reaction is crucial in regulating protein function and is of common occurrence in mechanically stressed proteins. While reduction is thought to proceed through a substitution nucleophilic bimolecular (SN2) reaction, the role of a mechanical force in modulating this chemical reaction is unknown. We apply a constant stretching force to single engineered disulfide bonds and measure their rate of reduction by dithiothreitol (DTT). We find that while the reduction rate is linearly dependent on the concentration of DTT, it is exponentially dependent on the applied force, increasing 10-fold over a 300 pN range. This result predicts that the disulfide bond lengthens by 0.34 å at the transition state of the thiol/disulfide exchange reaction. In addition to DTT, we also study the reduction of the engineered disulfide bond by the E. coli enzyme thioredoxin (Trx). Thioredoxins are enzymes that catalyze disulfide bond reduction in all organisms. As before, we apply a mechanical force in the range of 25-450 pN to the engineered disulfide bond substrate and monitor the reduction of these bonds by individual enzymes. In sharp contrast with the data obtained with DTT, we now observe two alternative forms of the catalytic reaction, the first requiring a reorientation of the substrate disulfide bond, causing a shortening of the substrate polypeptide by 0.76±0.07 å, and the second elongating the substrate disulfide bond by 0.21±0.01 å. These results support the view that the Trx active site regulates the geometry of the participating sulfur atoms, with sub-ångström precision, in order to achieve efficient catalysis. Single molecule

  6. Force-induced chemical reactions on the metal centre in a single metalloprotein molecule.

    Science.gov (United States)

    Zheng, Peng; Arantes, Guilherme M; Field, Martin J; Li, Hongbin

    2015-06-25

    Metalloproteins play indispensable roles in biology owing to the versatile chemical reactivity of metal centres. However, studying their reactivity in many metalloproteins is challenging, as protein three-dimensional structure encloses labile metal centres, thus limiting their access to reactants and impeding direct measurements. Here we demonstrate the use of single-molecule atomic force microscopy to induce partial unfolding to expose metal centres in metalloproteins to aqueous solution, thus allowing for studying their chemical reactivity in aqueous solution for the first time. As a proof-of-principle, we demonstrate two chemical reactions for the FeS4 centre in rubredoxin: electrophilic protonation and nucleophilic ligand substitution. Our results show that protonation and ligand substitution result in mechanical destabilization of the FeS4 centre. Quantum chemical calculations corroborated experimental results and revealed detailed reaction mechanisms. We anticipate that this novel approach will provide insights into chemical reactivity of metal centres in metalloproteins under biologically more relevant conditions.

  7. Measurement of adenosine triphosphate (ATP) content in single red blood cells using the firefly bioluminescent reaction

    Energy Technology Data Exchange (ETDEWEB)

    Kostuk, R.K.; Muhs, A.G.; Kirkpatrick, F.H.; Gabel, C.W.

    1977-01-01

    A unique optical instrument is described which uses the firefly bioluminscent reaction to measure adenosine triphosphate (ATP) levels in single red blood cells. The method allows chemical content level to be associated with individual cell features. The optical instrument consists of a phase contrast microscope to view cells, a pulsed argon-ion laser to rupture the cell membrane, and a photon counting system to measure the bioluminescent yield. The technique has been calibrated against a standard ATP measurement using bulk analysis methods. The ATP loss mechanism for blood cells in a controlled depletion experiment was also investigated.

  8. Uncertainty quantification for quantum chemical models of complex reaction networks.

    Science.gov (United States)

    Proppe, Jonny; Husch, Tamara; Simm, Gregor N; Reiher, Markus

    2016-12-22

    For the quantitative understanding of complex chemical reaction mechanisms, it is, in general, necessary to accurately determine the corresponding free energy surface and to solve the resulting continuous-time reaction rate equations for a continuous state space. For a general (complex) reaction network, it is computationally hard to fulfill these two requirements. However, it is possible to approximately address these challenges in a physically consistent way. On the one hand, it may be sufficient to consider approximate free energies if a reliable uncertainty measure can be provided. On the other hand, a highly resolved time evolution may not be necessary to still determine quantitative fluxes in a reaction network if one is interested in specific time scales. In this paper, we present discrete-time kinetic simulations in discrete state space taking free energy uncertainties into account. The method builds upon thermo-chemical data obtained from electronic structure calculations in a condensed-phase model. Our kinetic approach supports the analysis of general reaction networks spanning multiple time scales, which is here demonstrated for the example of the formose reaction. An important application of our approach is the detection of regions in a reaction network which require further investigation, given the uncertainties introduced by both approximate electronic structure methods and kinetic models. Such cases can then be studied in greater detail with more sophisticated first-principles calculations and kinetic simulations.

  9. [Predictive analysis on Shenmai injection-induced adverse reactions with Logistic model and ROC curve].

    Science.gov (United States)

    Ding, Feng; Shi, Qing-ping; Jiang, Xiao-dong; Liu, Yan; Sang, Ran; Zhu, Jin-xiu; Wei, Sheng-tong; Xin, Zhi-ming; Song, Ru

    2015-04-01

    To study relevant risk factors of Shenmai injection induced adverse reactions by using Logistic model and ROC curve, and made the prediction for the occurrence of relevant adverse reactions/events. Case data of patients treated with Shenmai injection were collected by using the prospective, multi-center, large-sample, nested-case control method, in order to analyze the risk factors of Shenmai injection-induced adverse reactions/events, establish the logistic model and draw the receiver operating characteristic (ROC) curve for risk factors. During the study, 7632 patients (including 3 477 males and 4 155 females) were included, and eight of them suffered adverse reactions/events. Based on a multi-factor Logistic model analysis, the age (> or = 50 years) (OR = 5.061, 95% CI: 2.197-7.924; P = 0.001), the total number of medication days (OR = -1.020, 95% CI: -l.652 - 0.388; P = 0.002) and the single dose (OR = 0.245, 95% CI: 0.127-0.364; P = 0.000) were significant independent risk factors for Shenmai injection-induced adverse reactions/events. According to the results, ROC curves were drawn with age (> or = 50 years), the total number of days of inedication and single dose; The area under ROC curves the joint predictor (0.9753, 95% CI: 0.9443-1.000, P adverse reactions/events included the age (> or = 50 years), the total number of days of medication and single dose. In clinical practice, the age (> or = 50 years), the total number of days of medication and the medication dose can be substituted in the joint predictor calculation formula (P = 1 / [1 + e(-(-21.58 + 5.061 x Xage - 1.020 x Xd + 0.245 x X(mL)] to predict the potential adverse reactions of patients and adjust the dosage regimen.

  10. Thermally reversible single-crystal to single-crystal transformation of mononuclear to dinuclear Zn(II) complexes by [2+2] cycloaddition reaction.

    Science.gov (United States)

    Medishetty, Raghavender; Yap, Terence Teck Sheng; Koh, Lip Lin; Vittal, Jagadese J

    2013-10-25

    Two Zn(II) complexes of trans-4-styrylpyridine ligands undergo [2+2] cycloaddition reaction forming Zn(II) complex dimers in a single-crystal to single-crystal (SCSC) manner which were thermally reversible. The dimers are presumed to be the stable intermediates in the formation of 1D coordination polymers upon prolonged exposure to UV light.

  11. Ligand-tailored single-site silica supported titanium catalysts: Synthesis, characterization and towards cyanosilylation reaction

    International Nuclear Information System (INIS)

    Xu, Wei; Li, Yani; Yu, Bo; Yang, Jindou; Zhang, Ying; Chen, Xi; Zhang, Guofang; Gao, Ziwei

    2015-01-01

    A successive anchoring of Ti(NMe 2 ) 4 , cyclopentadiene and a O-donor ligand, 1-hydroxyethylbenzene (PEA), 1,1′-bi-2-naphthol (Binol) or 2,3-dihydroxybutanedioic acid diethyl ester (Tartrate), on silica was conducted by SOMC strategy in moderate conditions. The silica, monitored by in-situ Fourier transform infrared spectroscopy (in-situ FT-IR), was pretreated at different temperatures (200, 500 and 800 °C). The ligand tailored silica-supported titanium complexes were characterized by in-situ FT-IR, 13 C CP MAS-NMR, X-ray photoelectron spectroscopy (XPS), X-ray absorption near edge structure (XANES) and elemental analysis in detail, verifying that the surface titanium species are single sited. The catalytic activity of the ligand tailored single-site silica supported titanium complexes was evaluated by a cyanosilylation of benzaldehyde. The results showed that the catalytic activity is dependent strongly on the dehydroxylation temperatures of silica and the configuration of the ligands. - Graphical abstract: The ligand-tailored silica supported “single site” titanium complexes were synthesized by SOMC strategy and fully characterized. Their catalytic activity were evaluated by benzaldehyde silylcyanation. - Highlights: • Single-site silica supported Ti active species was prepared by SOMC technique. • O-donor ligand tailored Ti surface species was synthesized. • The surface species was characterized by XPS, 13 C CP-MAS NMR, XANES etc. • Catalytic activity of the Ti active species in silylcyanation reaction was evaluated

  12. Exploiting the tetrazine-norbornene reaction for single polymer chain collapse

    Science.gov (United States)

    Hansell, Claire F.; Lu, Annhelen; Patterson, Joseph P.; O'Reilly, Rachel K.

    2014-03-01

    Single chain polymer nanoparticles (SCNPs) have been formed using polystyrenes decorated with pendent norbornenes and a bifunctional tetrazine crosslinker. Characterisation by size exclusion chromatography and 1H NMR gives evidence for the formation of SCNPs by the tetrazine-norbornene reaction, whilst light scattering, neutron scattering, transmission electron microscopy and atomic force microscopy show that discrete well-defined nanoparticles are formed and their size in solution calculated.Single chain polymer nanoparticles (SCNPs) have been formed using polystyrenes decorated with pendent norbornenes and a bifunctional tetrazine crosslinker. Characterisation by size exclusion chromatography and 1H NMR gives evidence for the formation of SCNPs by the tetrazine-norbornene reaction, whilst light scattering, neutron scattering, transmission electron microscopy and atomic force microscopy show that discrete well-defined nanoparticles are formed and their size in solution calculated. Electronic supplementary information (ESI) available: Further synthetic detail, 1H and 13C NMR spectra, control experiments, TEM images, SANS and DLS data. See DOI: 10.1039/c3nr06706h

  13. Microfluidic Fabrication of Porous Polymer Microspheres: Dual Reactions in Single Droplets

    KAUST Repository

    Gong, Xiuqing

    2009-06-16

    We report the microfluidic fabrication of macroporous polymer microspheres via the simultaneous reactions within single droplets, induced by LTV irradiation. The aqueous phase of the reaction is the decomposition of H 2O2 to yield oxygen, whereas the organic phase is the polymerization of NO A 61, ethylene glycol dimethacrylate (EGDMA), and tri (propylene glycol) diacrylate (TPGDA) precursors. We first used a liquid polymer precursor to encapsulate a multiple number of magnetic Fe3O 4 colloidal suspension (MCS) droplets in a core-shell structure, for the purpose of studying the number of such encapsulated droplets that can be reliably controlled through the variation of flow rates. It was found that the formation of one shell with one, two, three, or more encapsulated droplets is possible. Subsequently, the H2O2 solution was encapsulated in the same way, after which we investigated its decomposition under UV irradiation, which simultaneously induces the polymerization of the encapsulating shell. Because the H2O2 decomposition leads to the release of oxygen, porous microspheres were obtained from a combined H2O2 decomposition/polymer precursor polymerization reaction. The multiplicity of the initially encapsulated H2O 2 droplets ensures the homogeneous distribution of the pores. The pores inside the micrometer-sized spheres range from several micrometers to tens of micrometers, and the maximum internal void volume fraction can attain 70%, similar to that of high polymerized high internal phase emulsion (polyHIPE). © 2009 American Chemical Society.

  14. Cellular automaton model of mass transport with chemical reactions

    International Nuclear Information System (INIS)

    Karapiperis, T.; Blankleider, B.

    1993-10-01

    The transport and chemical reactions of solutes are modelled as a cellular automaton in which molecules of different species perform a random walk on a regular lattice and react according to a local probabilistic rule. The model describes advection and diffusion in a simple way, and as no restriction is placed on the number of particles at a lattice site, it is also able to describe a wide variety of chemical reactions. Assuming molecular chaos and a smooth density function, we obtain the standard reaction-transport equations in the continuum limit. Simulations on one-and two-dimensional lattices show that the discrete model can be used to approximate the solutions of the continuum equations. We discuss discrepancies which arise from correlations between molecules and how these discrepancies disappear as the continuum limit is approached. Of particular interest are simulations displaying long-time behaviour which depends on long-wavelength statistical fluctuations not accounted for by the standard equations. The model is applied to the reactions a + b ↔ c and a + b → c with homogeneous and inhomogeneous initial conditions as well as to systems subject to autocatalytic reactions and displaying spontaneous formation of spatial concentration patterns. (author) 9 figs., 34 refs

  15. Implementation of a vibrationally linked chemical reaction model for DSMC

    Science.gov (United States)

    Carlson, A. B.; Bird, Graeme A.

    1994-01-01

    A new procedure closely linking dissociation and exchange reactions in air to the vibrational levels of the diatomic molecules has been implemented in both one- and two-dimensional versions of Direct Simulation Monte Carlo (DSMC) programs. The previous modeling of chemical reactions with DSMC was based on the continuum reaction rates for the various possible reactions. The new method is more closely related to the actual physics of dissociation and is more appropriate to the particle nature of DSMC. Two cases are presented: the relaxation to equilibrium of undissociated air initially at 10,000 K, and the axisymmetric calculation of shuttle forebody heating during reentry at 92.35 km and 7500 m/s. Although reaction rates are not used in determining the dissociations or exchange reactions, the new method produces rates which agree astonishingly well with the published rates derived from experiment. The results for gas properties and surface properties also agree well with the results produced by earlier DSMC models, equilibrium air calculations, and experiment.

  16. Chemical Reaction and Flow Modeling in Fullerene and Nanotube Production

    Science.gov (United States)

    Scott, Carl D.; Farhat, Samir; Greendyke, Robert B.

    2004-01-01

    addresses modeling of the arc process for fullerene and carbon nanotube production using O-D, 1-D and 2-D fluid flow models. The third part addresses simulations of the pulsed laser ablation process using time-dependent techniques in 2-D, and a steady state 2-D simulation of a continuous laser ablation process. The fourth part addresses steady state modeling in O-D and 2-D of the HiPco process. In each of the simulations, there is a variety of simplifications that are made that enable one to concentrate on one aspect or another of the process. There are simplifications that can be made to the chemical reaction models , e.g. reduction in number of species by lumping some of them together in a representative species. Other simulations are carried out by eliminating the chemistry altogether in order to concentrate on the fluid dynamics. When solving problems with a large number of species in more than one spatial dimension, it is almost imperative that the problem be decoupled by solving for the fluid dynamics to find the fluid motion and temperature history of "particles" of fluid moving through a reactor. Then one can solve the chemical rate equations with complex chemistry following the temperature and pressure history. One difficulty is that often mixing with an ambient gas is involved. Therefore, one needs to take dilution and mixing into account. This changes the ratio of carbon species to background gas. Commercially available codes may have no provision for including dilution as part of the input. One must the write special solvers for including dilution in decoupled problems. The article addresses both ful1erene production and single-walled carbon nanotube (SWNT) production. There are at least two schemes or concepts of SWNT growth. This article will only address growth in the gas phase by carbon and catalyst cluster growth and SW T formation by the addition of carbon. There are other models that conceive of SWNT growth as a phase separation process from clusters me

  17. Mechanistic interpretation of glass reaction: Input to kinetic model development

    International Nuclear Information System (INIS)

    Bates, J.K.; Ebert, W.L.; Bradley, J.P.; Bourcier, W.L.

    1991-05-01

    Actinide-doped SRL 165 type glass was reacted in J-13 groundwater at 90 degree C for times up to 278 days. The reaction was characterized by both solution and solid analyses. The glass was seen to react nonstoichiometrically with preferred leaching of alkali metals and boron. High resolution electron microscopy revealed the formation of a complex layer structure which became separated from the underlying glass as the reaction progressed. The formation of the layer and its effect on continued glass reaction are discussed with respect to the current model for glass reaction used in the EQ3/6 computer simulation. It is concluded that the layer formed after 278 days is not protective and may eventually become fractured and generate particulates that may be transported by liquid water. 5 refs., 5 figs. , 3 tabs

  18. A chain reaction approach to modelling gene pathways.

    Science.gov (United States)

    Cheng, Gary C; Chen, Dung-Tsa; Chen, James J; Soong, Seng-Jaw; Lamartiniere, Coral; Barnes, Stephen

    2012-08-01

    BACKGROUND: Of great interest in cancer prevention is how nutrient components affect gene pathways associated with the physiological events of puberty. Nutrient-gene interactions may cause changes in breast or prostate cells and, therefore, may result in cancer risk later in life. Analysis of gene pathways can lead to insights about nutrient-gene interactions and the development of more effective prevention approaches to reduce cancer risk. To date, researchers have relied heavily upon experimental assays (such as microarray analysis, etc.) to identify genes and their associated pathways that are affected by nutrient and diets. However, the vast number of genes and combinations of gene pathways, coupled with the expense of the experimental analyses, has delayed the progress of gene-pathway research. The development of an analytical approach based on available test data could greatly benefit the evaluation of gene pathways, and thus advance the study of nutrient-gene interactions in cancer prevention. In the present study, we have proposed a chain reaction model to simulate gene pathways, in which the gene expression changes through the pathway are represented by the species undergoing a set of chemical reactions. We have also developed a numerical tool to solve for the species changes due to the chain reactions over time. Through this approach we can examine the impact of nutrient-containing diets on the gene pathway; moreover, transformation of genes over time with a nutrient treatment can be observed numerically, which is very difficult to achieve experimentally. We apply this approach to microarray analysis data from an experiment which involved the effects of three polyphenols (nutrient treatments), epigallo-catechin-3-O-gallate (EGCG), genistein, and resveratrol, in a study of nutrient-gene interaction in the estrogen synthesis pathway during puberty. RESULTS: In this preliminary study, the estrogen synthesis pathway was simulated by a chain reaction model. By

  19. Challenges in modelling the reaction chemistry of interstellar dust.

    Science.gov (United States)

    Bromley, S T; Goumans, T P M; Herbst, E; Jones, A P; Slater, B

    2014-09-21

    Studies aiming to understand the physicochemical properties of interstellar dust and the chemical reactions that occur on and in it have traditionally been the preserve of astronomical observation and experimental attempts to mimic astronomically relevant conditions in the laboratory. Increasingly, computational modelling in its various guises is establishing a complementary third pillar of support to this endeavour by providing detailed insights into the complexities of interstellar dust chemistry. Inherently, the basis of computational modelling is to be found in the details (e.g. atomic structure/composition, reaction barriers) that are difficult to probe accurately from observation and experiment. This bottom-up atom-based theoretical approach, often itself based on deeper quantum mechanical principles, although extremely powerful, also has limitations when systems become too large or complex. In this Perspective, after first providing a general background to the current state of observational-based knowledge, we introduce a number of computational modelling methods with reference to recent state-of-the-art studies, in order to highlight the capabilities of such approaches in this field. Specifically, we first outline the use of computational chemistry methods for dust nucleation, structure, and individual reactions on bare and icy dust surfaces. Later, we review kinetic modelling of networks of reactions relevant to dust chemistry and how to take into account quantum tunnelling effects in the low temperature reactions in the interstellar medium. Finally, we point to the future challenges that need to be overcome for computational modelling to provide even more detailed and encompassing perspectives on the nature and reaction chemistry of interstellar dust.

  20. Structure and Reactions of 11Be: Many-Body Basis for Single-Neutron Halo

    Science.gov (United States)

    Barranco, F.; Potel, G.; Broglia, R. A.; Vigezzi, E.

    2017-08-01

    The exotic nucleus 11Be has been extensively studied and much experimental information is available on the structure of this system. We treat, within the framework of renormalized nuclear field theory in both configuration and 3D space, the mixing of bound and continuum single-particle states through the coupling to collective vibrations of the 10Be core. We also take care of the Pauli principle acting not only between the single valence particle explicitly considered and those participating in the collective states, but also between fermions involved in two-phonon virtual states dressing the single-particle motion. In this way, it is possible to simultaneously and quantitatively account for the energies of the 1 /2+ , 1 /2- low-lying states, the centroid and line shape of the 5 /2+ resonance and the one-nucleon stripping and pickup absolute differential cross sections involving 11Be as either target or residual nucleus. Also for the dipole transition connecting the 1 /2+ and 1 /2- parity inverted levels as well as the isotopic shift of the charge radius. Theory provides a unified and exhaustive nuclear structure and reaction characterization of the many-body effects which are at the basis of this paradigmatic one-neutron halo system.

  1. A model for reaction rates in turbulent reacting flows

    Science.gov (United States)

    Chinitz, W.; Evans, J. S.

    1984-01-01

    To account for the turbulent temperature and species-concentration fluctuations, a model is presented on the effects of chemical reaction rates in computer analyses of turbulent reacting flows. The model results in two parameters which multiply the terms in the reaction-rate equations. For these two parameters, graphs are presented as functions of the mean values and intensity of the turbulent fluctuations of the temperature and species concentrations. These graphs will facilitate incorporation of the model into existing computer programs which describe turbulent reacting flows. When the model was used in a two-dimensional parabolic-flow computer code to predict the behavior of an experimental, supersonic hydrogen jet burning in air, some improvement in agreement with the experimental data was obtained in the far field in the region near the jet centerline. Recommendations are included for further improvement of the model and for additional comparisons with experimental data.

  2. Propensity approach to nonequilibrium thermodynamics of a chemical reaction network: controlling single E-coli β-galactosidase enzyme catalysis through the elementary reaction steps.

    Science.gov (United States)

    Das, Biswajit; Banerjee, Kinshuk; Gangopadhyay, Gautam

    2013-12-28

    In this work, we develop an approach to nonequilibrium thermodynamics of an open chemical reaction network in terms of the elementary reaction propensities. The method is akin to the microscopic formulation of the dissipation function in terms of the Kullback-Leibler distance of phase space trajectories in Hamiltonian system. The formalism is applied to a single oligomeric enzyme kinetics at chemiostatic condition that leads the reaction system to a nonequilibrium steady state, characterized by a positive total entropy production rate. Analytical expressions are derived, relating the individual reaction contributions towards the total entropy production rate with experimentally measurable reaction velocity. Taking a real case of Escherichia coli β-galactosidase enzyme obeying Michaelis-Menten kinetics, we thoroughly analyze the temporal as well as the steady state behavior of various thermodynamic quantities for each elementary reaction. This gives a useful insight in the relative magnitudes of various energy terms and the dissipated heat to sustain a steady state of the reaction system operating far-from-equilibrium. It is also observed that, the reaction is entropy-driven at low substrate concentration and becomes energy-driven as the substrate concentration rises.

  3. Ligand-tailored single-site silica supported titanium catalysts: Synthesis, characterization and towards cyanosilylation reaction

    Energy Technology Data Exchange (ETDEWEB)

    Xu, Wei; Li, Yani; Yu, Bo; Yang, Jindou; Zhang, Ying; Chen, Xi; Zhang, Guofang, E-mail: gfzhang@snnu.edu.cn; Gao, Ziwei, E-mail: zwgao@snnu.edu.cn

    2015-01-15

    A successive anchoring of Ti(NMe{sub 2}){sub 4}, cyclopentadiene and a O-donor ligand, 1-hydroxyethylbenzene (PEA), 1,1′-bi-2-naphthol (Binol) or 2,3-dihydroxybutanedioic acid diethyl ester (Tartrate), on silica was conducted by SOMC strategy in moderate conditions. The silica, monitored by in-situ Fourier transform infrared spectroscopy (in-situ FT-IR), was pretreated at different temperatures (200, 500 and 800 °C). The ligand tailored silica-supported titanium complexes were characterized by in-situ FT-IR, {sup 13}C CP MAS-NMR, X-ray photoelectron spectroscopy (XPS), X-ray absorption near edge structure (XANES) and elemental analysis in detail, verifying that the surface titanium species are single sited. The catalytic activity of the ligand tailored single-site silica supported titanium complexes was evaluated by a cyanosilylation of benzaldehyde. The results showed that the catalytic activity is dependent strongly on the dehydroxylation temperatures of silica and the configuration of the ligands. - Graphical abstract: The ligand-tailored silica supported “single site” titanium complexes were synthesized by SOMC strategy and fully characterized. Their catalytic activity were evaluated by benzaldehyde silylcyanation. - Highlights: • Single-site silica supported Ti active species was prepared by SOMC technique. • O-donor ligand tailored Ti surface species was synthesized. • The surface species was characterized by XPS, {sup 13}C CP-MAS NMR, XANES etc. • Catalytic activity of the Ti active species in silylcyanation reaction was evaluated.

  4. A Multiple Reaction Modelling Framework for Microbial Electrochemical Technologies

    Directory of Open Access Journals (Sweden)

    Tolutola Oyetunde

    2017-01-01

    Full Text Available A mathematical model for the theoretical evaluation of microbial electrochemical technologies (METs is presented that incorporates a detailed physico-chemical framework, includes multiple reactions (both at the electrodes and in the bulk phase and involves a variety of microbial functional groups. The model is applied to two theoretical case studies: (i A microbial electrolysis cell (MEC for continuous anodic volatile fatty acids (VFA oxidation and cathodic VFA reduction to alcohols, for which the theoretical system response to changes in applied voltage and VFA feed ratio (anode-to-cathode as well as membrane type are investigated. This case involves multiple parallel electrode reactions in both anode and cathode compartments; (ii A microbial fuel cell (MFC for cathodic perchlorate reduction, in which the theoretical impact of feed flow rates and concentrations on the overall system performance are investigated. This case involves multiple electrode reactions in series in the cathode compartment. The model structure captures interactions between important system variables based on first principles and provides a platform for the dynamic description of METs involving electrode reactions both in parallel and in series and in both MFC and MEC configurations. Such a theoretical modelling approach, largely based on first principles, appears promising in the development and testing of MET control and optimization strategies.

  5. Traveling Wave Solutions in a Reaction-Diffusion Epidemic Model

    OpenAIRE

    Wang, Sheng; Liu, Wenbin; Guo, Zhengguang; Wang, Weiming

    2013-01-01

    We investigate the traveling wave solutions in a reaction-diffusion epidemic model. The existence of the wave solutions is derived through monotone iteration of a pair of classical upper and lower solutions. The traveling wave solutions are shown to be unique and strictly monotonic. Furthermore, we determine the critical minimal wave speed.

  6. Python framework for kinetic modeling of electronically excited reaction pathways

    Science.gov (United States)

    Verboncoeur, John; Parsey, Guy; Guclu, Yaman; Christlieb, Andrew

    2012-10-01

    The use of plasma energy to enhance and control the chemical reactions during combustion, a technology referred to as ``plasma assisted combustion'' (PAC), can result in a variety of beneficial effects: e.g. stable lean operation, pollution reduction, and wider range of p-T operating conditions. While experimental evidence abounds, theoretical understanding of PAC is at best incomplete, and numerical tools still lack in reliable predictive capabilities. In the context of a joint experimental-numerical effort at Michigan State University, we present here an open-source modular Python framework dedicated to the dynamic optimization of non-equilibrium PAC systems. Multiple sources of experimental reaction data, e.g. reaction rates, cross-sections and oscillator strengths, are used in order to quantify the effect of data uncertainty and limiting assumptions. A collisional-radiative model (CRM) is implemented to organize reactions by importance and as a potential means of measuring a non-Maxwellian electron energy distribution function (EEDF), when coupled to optical emission spectroscopy data. Finally, we explore scaling laws in PAC parameter space using a kinetic global model (KGM) accelerated with CRM optimized reaction sequences and sparse stiff integrators.

  7. Understanding the Oxygen Reduction Reaction on a Y/Pt(111) Single Crystal

    DEFF Research Database (Denmark)

    Ulrikkeholm, Elisabeth Therese; Johansson, Tobias Peter; Malacrida, Paolo

    2014-01-01

    Polymer electrolyte membrane fuel cells (PEMFC) hold promise as a zero-emission source of power, particularly suitable for automotive vehicles. However, the high loading of Pt required to catalyse the oxygen reduction reaction (ORR) at the PEMFC cathode, prevents the commercialisation of this tec......Polymer electrolyte membrane fuel cells (PEMFC) hold promise as a zero-emission source of power, particularly suitable for automotive vehicles. However, the high loading of Pt required to catalyse the oxygen reduction reaction (ORR) at the PEMFC cathode, prevents the commercialisation...... of this technology. Improving the activity of Pt by alloying it with other metals could decrease the loading of Pt. An earlier theoretical study conducted at our laboratory identified PtxY as an active and stable catalyst for oxygen reduction. Experiments conducted on sputter-cleaned polycrystalline Pt3Y confirmed...... was significantly different from our initial expectations. In order to understand this phenomenon, we investigated a Y/Pt(111) single crystal, formed by depositing large amounts of Y om Pt(111) under ultra-high vacuum (UHV) conditions and annealing to high temperatures. We subsequently characterised the surface...

  8. A detector system for studying nuclear reactions relevant to Single Event Effects

    Energy Technology Data Exchange (ETDEWEB)

    Murin, Yu. [V.G. Khlopin Radium Institute, 2nd Murinski 28, 194021 St. Petersburg (Russian Federation)]. E-mail: murin@jinr.ru; Babain, Yu. [V.G. Khlopin Radium Institute, 2nd Murinski 28, 194021 St. Petersburg (Russian Federation); Chubarov, M. [V.G. Khlopin Radium Institute, 2nd Murinski 28, 194021 St. Petersburg (Russian Federation); Tuboltsev, Yu. [V.G. Khlopin Radium Institute, 2nd Murinski 28, 194021 St. Petersburg (Russian Federation); Pljuschev, V. [V.G. Khlopin Radium Institute, 2nd Murinski 28, 194021 St. Petersburg (Russian Federation); Zubkov, M. [V.G. Khlopin Radium Institute, 2nd Murinski 28, 194021 St. Petersburg (Russian Federation); Nomokonov, P. [High Energy Laboratory, Joint Institute for Nuclear Research, 141980 Moscow Region (Russian Federation); Voronin, A. [Moscow State University, 119992 Moscow (Russian Federation); Merkin, M. [Moscow State University, 119992 Moscow (Russian Federation); Kondratiev, V. [St. Petersburg State University, 198504 St. Petersburg (Russian Federation); Olsson, N.; Blomgren, J. [Department of Neutron Research, Uppsala University, Box 525, SE 751 20 Uppsala (Sweden); Westerberg, L. [Department of Physics, Uppsala University, Box 530, SE 751 21 Uppsala (Sweden); Ekstroem, C.; Kolozhvari, A. [The Svedberg Laboratory, Uppsala University, Box 533, SE 751 21 Uppsala (Sweden); Jaederstroem, H. [Department of Nuclear and Particle Physics, Uppsala University, Box 531, SE 751 21 Uppsala (Sweden); Jakobsson, B.; Golubev, P. [Department of Physics, Lund University, Box 118, SE 221 00 Lund (Sweden); Bargholz, Chr.; Geren, L.; Tegner, P.-E.; Zartova, I. [Department of Physics, Stockholm University, AlbaNova, SE 10691 Stockholm (Sweden); Budzanowski, A.; Czech, B.; Skwirczynska, I. [H. Niewodniczanski Institute of Nuclear Physics, PL 31 342 Cracow (Poland); Tang, H.H.K. [IBM, T.J. Watson Research Center, Yorktown Heights, NY 10598 (United States)

    2007-08-01

    We describe a device to study reactions relevant for the Single Event Effect (SEE) in microelectronics by means of 200A and 300AMeV, inverse kinematics, Si+H and Si+D reactions. The work is focused on the possibility to measure Z=2-14 projectile fragments as efficiently as possible. During commissioning and first experiments the fourth quadrant of the CELSIUS storage ring acted as a spectrometer to register fragments in two planes of Si strip detectors in the angular region 0{sup a}t -0.6{sup a}t. A combination of ring-structured and sector-structured Si strip detector planes operated at angles 0.6{sup a}t-1.1{sup a}t. For specific event tagging a Si+ phoswich scintillator wall operated in the range 3.9{sup a}t-11.7{sup a}t and Si {delta}E-E telescopes of CHICSi type operated at large angles.

  9. Reaction pathway towards formation of cobalt single chain magnets and nanoparticles

    Energy Technology Data Exchange (ETDEWEB)

    Balaji, G.; Desilva, Rohini M.; Palshin, V. [Center for Advanced Microstructures and Devices, Louisiana State University, 6980 Jefferson Highway, Baton Rouge, LA 70806 (United States); Desilva, N. [Department of Chemistry, Louisiana State University, Baton Rouge, LA 70803 (United States); Palmer, G. [Department of Biochemistry and Cell Biology, Rice University, MS 140, 6100 Main street, Houston, TX 77251 (United States); Kumar, Challa S.S.R., E-mail: ckumar1@lsu.ed [Center for Advanced Microstructures and Devices, Louisiana State University, 6980 Jefferson Highway, Baton Rouge, LA 70806 (United States)

    2010-03-15

    With the advent of molecular magnets the quest for suitable high density magnetic storage materials has fuelled further research in this area. Here in this report, we present a detailed mechanistic investigation of thermal decomposition of cyclopentadienyl cobalt [CoCp(CO){sub 2}] precursor where Cp is the cyclopentadienyl moiety. The reaction revealed the formation of cobalt nanoparticles (Co-NPs) through an isolable reaction intermediate characterized as a Single Chain Magnet (SCM), [Co(Cp){sub 2}]{sub 2}CoCl{sub 4} (1). The SQUID magnetic measurements showed the presence of very strong antiferromagnetic interactions between Co{sup 2+} ions. The zero-field cooled (ZFC) and field cooled (FC) magnetization curves branch out below 5 K and there is evidence for frequency dependent complex susceptibility along with a maximum observed around 2.5 K. The optical studies indicated that the Co{sup 2+} d-d transition is influenced by the polarity of the solvents. The cobalt nanoparticles (Co-NPs) were obtained, either directly from 1 or from its precursor. They are spherical in shape with a mean size 15 nm, have fcc crystal structure and were found to be ferromagnetic at room temperature.

  10. Single particle transfer reactions: what can they tell us about vibrational states

    International Nuclear Information System (INIS)

    Hering, W.R.

    1975-01-01

    The topic discussed concerns single particle transfer reactions (SPTR) which are, in general, used to study SP states. However, good SP states are rare objects in nature and people who try to look for them have often to settle with something less than ideal. Indeed the picture of a pure SP state is physically not even reasonable. It means that a nucleon is moving around a core nucleus which stays in its ground state: a process which one could call equivalent to elastic scattering of a nucleon which is not free but rather in a bound state. However it is shown that inelastic scattering is a very strong competitor to elastic scattering if the nucleus possesses states of high collectivity. Thus one would expect inelastic scattering to happen also while the nucleon is bound. This is a very intuitive picture of what is called the fragmentation of SP states. A final state psi sub(B) is populated by the transfer reaction A + a → B + b where psi sub(B) = α 1 phi 1 phi sub(A)(0) + α 2 phi 2 phi sub(A)(lambda). Hence the population of psi sub(B) automatically involves the collective state phi sub(A)(lambda). A discussion of how one can get information about phi sub(A)(lambda) out of the experimental data is given. (Auth.)

  11. Single particle tracking-based reaction progress kinetic analysis reveals a series of molecular mechanisms of cetuximab-induced EGFR processes in a single living cell.

    Science.gov (United States)

    Kim, Do-Hyeon; Kim, Dong-Kyun; Zhou, Kai; Park, Soyeon; Kwon, Yonghoon; Jeong, Min Gyu; Lee, Nam Ki; Ryu, Sung Ho

    2017-07-01

    Cellular processes occur through the orchestration of multi-step molecular reactions. Reaction progress kinetic analysis (RPKA) can provide the mechanistic details to elucidate the multi-step molecular reactions. However, current tools have limited ability to simultaneously monitor dynamic variations in multiple complex states at the single molecule level to apply RPKA in living cells. In this research, a single particle tracking-based reaction progress kinetic analysis (sptRPKA) was developed to simultaneously determine the kinetics of multiple states of protein complexes in the membrane of a single living cell. The subpopulation ratios of different states were quantitatively (and statistically) reliably extracted from the diffusion coefficient distribution rapidly acquired by single particle tracking at constant and high density over a long period of time using super-resolution microscopy. Using sptRPKA, a series of molecular mechanisms of epidermal growth factor receptor (EGFR) cellular processing induced by cetuximab were investigated. By comprehensively measuring the rate constants and cooperativity of the molecular reactions involving four EGFR complex states, a previously unknown intermediate state was identified that represents the rate limiting step responsible for the selectivity of cetuximab-induced EGFR endocytosis to cancer cells.

  12. Experimental animal model for late postradiation reaction of the colon

    International Nuclear Information System (INIS)

    Trott, K.R.

    1987-01-01

    Experimental animal model worked out in Muenchen is discussed in which late postradiation reaction in Wistar rats following local irradiation of the colon manifests itself by appearance of colonic stenoses causing death of the animal. Clinical symptoms of this reaction together with results of histopathologic examination of the excised parts of the colon localized in the irradiated area are discussed. The relationships effect-dose obtained in this system for X radiation applying different regimen of dose fractionation and different total times of irradiation are presented. 8 refs., 5 figs., 1 tab. (author)

  13. N2O + CO reaction over single Ga or Ge atom embedded graphene: A DFT study

    Science.gov (United States)

    Esrafili, Mehdi D.; Vessally, Esmail

    2018-01-01

    The possibility of using a single Ga or Ge atom embedded graphene as an efficient catalyst for the reduction of N2O molecule by CO is examined. We perform density functional theory calculations to calculate adsorption energies as well as analysis of the structural and electronic properties of different species involved in the N2O + CO reaction. The large activation energy for the diffusion of the single Ga or Ge atom on the C vacancy site of graphene shows the high stability of both Ga- and Ge-embedded graphene sheets in the N2O reduction. The activation energy needed for the decomposition of N2O is calculated to be 18.4 and 14.1 kcal/mol over Ga- and Ge-embedded graphene, respectively. The results indicate that the Ge-embedded graphene may serve as an effective catalyst for the N2O reduction. Moreover, the activation energy for the disproportionation of N2O molecules that generates N2 and O2 is relatively high; so, the generation of these side products may be hindered by decreasing the temperature.

  14. Modelling biochemical reaction systems by stochastic differential equations with reflection.

    Science.gov (United States)

    Niu, Yuanling; Burrage, Kevin; Chen, Luonan

    2016-05-07

    In this paper, we gave a new framework for modelling and simulating biochemical reaction systems by stochastic differential equations with reflection not in a heuristic way but in a mathematical way. The model is computationally efficient compared with the discrete-state Markov chain approach, and it ensures that both analytic and numerical solutions remain in a biologically plausible region. Specifically, our model mathematically ensures that species numbers lie in the domain D, which is a physical constraint for biochemical reactions, in contrast to the previous models. The domain D is actually obtained according to the structure of the corresponding chemical Langevin equations, i.e., the boundary is inherent in the biochemical reaction system. A variant of projection method was employed to solve the reflected stochastic differential equation model, and it includes three simple steps, i.e., Euler-Maruyama method was applied to the equations first, and then check whether or not the point lies within the domain D, and if not perform an orthogonal projection. It is found that the projection onto the closure D¯ is the solution to a convex quadratic programming problem. Thus, existing methods for the convex quadratic programming problem can be employed for the orthogonal projection map. Numerical tests on several important problems in biological systems confirmed the efficiency and accuracy of this approach. Copyright © 2016 Elsevier Ltd. All rights reserved.

  15. Modeling adsorption and reactions of organic molecules at metal surfaces.

    Science.gov (United States)

    Liu, Wei; Tkatchenko, Alexandre; Scheffler, Matthias

    2014-11-18

    CONSPECTUS: The understanding of adsorption and reactions of (large) organic molecules at metal surfaces plays an increasingly important role in modern surface science and technology. Such hybrid inorganic/organic systems (HIOS) are relevant for many applications in catalysis, light-emitting diodes, single-molecule junctions, molecular sensors and switches, and photovoltaics. Obviously, the predictive modeling and understanding of the structure and stability of such hybrid systems is an essential prerequisite for tuning their electronic properties and functions. At present, density-functional theory (DFT) is the most promising approach to study the structure, stability, and electronic properties of complex systems, because it can be applied to both molecules and solids comprising thousands of atoms. However, state-of-the-art approximations to DFT do not provide a consistent and reliable description for HIOS, which is largely due to two issues: (i) the self-interaction of the electrons with themselves arising from the Hartree term of the total energy that is not fully compensated in approximate exchange-correlation functionals, and (ii) the lack of long-range part of the ubiquitous van der Waals (vdW) interactions. The self-interaction errors sometimes lead to incorrect description of charge transfer and electronic level alignment in HIOS, although for molecules adsorbed on metals these effects will often cancel out in total energy differences. Regarding vdW interactions, several promising vdW-inclusive DFT-based methods have been recently demonstrated to yield remarkable accuracy for intermolecular interactions in the gas phase. However, the majority of these approaches neglect the nonlocal collective electron response in the vdW energy tail, an effect that is particularly strong in condensed phases and at interfaces between different materials. Here we show that the recently developed DFT+vdW(surf) method that accurately accounts for the collective electronic

  16. Improvement on reaction model for sodium-water reaction jet code and application analysis

    International Nuclear Information System (INIS)

    Itooka, Satoshi; Saito, Yoshinori; Okabe, Ayao; Fujimata, Kazuhiro; Murata, Shuuichi

    2000-03-01

    In selecting the reasonable DBL on steam generator (SG), it is necessary to improve analytical method for estimating the sodium temperature on failure propagation due to overheating. Improvement on sodium-water reaction (SWR) jet code (LEAP-JET ver.1.30) and application analysis to the water injection tests for confirmation of code propriety were performed. On the improvement of the code, a gas-liquid interface area density model was introduced to develop a chemical reaction model with a little dependence on calculation mesh size. The test calculation using the improved code (LEAP-JET ver.1.40) were carried out with conditions of the SWAT-3·Run-19 test and an actual scale SG. It is confirmed that the SWR jet behavior on the results and the influence to analysis result of a model are reasonable. For the application analysis to the water injection tests, water injection behavior and SWR jet behavior analyses on the new SWAT-1 (SWAT-1R) and SWAT-3 (SWAT-3R) tests were performed using the LEAP-BLOW code and the LEAP-JET code. In the application analysis of the LEAP-BLOW code, parameter survey study was performed. As the results, the condition of the injection nozzle diameter needed to simulate the water leak rate was confirmed. In the application analysis of the LEAP-JET code, temperature behavior of the SWR jet was investigated. (author)

  17. Applications of a single-molecule detection in early disease diagnosis and enzymatic reaction study

    Energy Technology Data Exchange (ETDEWEB)

    Li, Jiangwei [Iowa State Univ., Ames, IA (United States)

    2008-01-01

    Various single-molecule techniques were utilized for ultra-sensitive early diagnosis of viral DNA and antigen and basic mechanism study of enzymatic reactions. DNA of human papilloma virus (HPV) served as the screening target in a flow system. Alexa Fluor 532 (AF532) labeled single-stranded DNA probes were hybridized to the target HPV-16 DNA in solution. The individual hybridized molecules were imaged with an intensified charge-coupled device (ICCD) in two ways. In the single-color mode, target molecules were detected via fluorescence from hybridized probes only. This system could detect HPV-16 DNA in the presence of human genomic DNA down to 0.7 copy/cell and had a linear dynamic range of over 6 orders of magnitude. In the dual-color mode, fluorescence resonance energy transfer (FRET) was employed to achieve zero false-positive count. We also showed that DNA extracts from Pap test specimens did not interfere with the system. A surface-based method was used to improve the throughput of the flow system. HPV-16 DNA was hybridized to probes on a glass surface and detected with a total internal reflection fluorescence (TIRF) microscope. In the single-probe mode, the whole genome and target DNA were fluorescently labeled before hybridization, and the detection limit is similar to the flow system. In the dual-probe mode, a second probe was introduced. The linear dynamic range covers 1.44-7000 copies/cell, which is typical of early infection to near-cancer stages. The dual-probe method was tested with a crudely prepared sample. Even with reduced hybridization efficiency caused by the interference of cellular materials, we were still able to differentiate infected cells from healthy cells. Detection and quantification of viral antigen with a novel single-molecule immunosorbent assay (SMISA) was achieved. Antigen from human immunodeficiency virus type 1(HIV-1) was chosen to be the target in this study. The target was sandwiched between a monoclonal capture antibody and a

  18. Single determinantal reaction theory as a Schroedinger analog: the time-dependent S-matrix Hartree-Fock method

    International Nuclear Information System (INIS)

    Griffin, J.J.; Lichtner, P.C.; Dworzecka, M.; Kan, K.K.

    1979-01-01

    It is suggested that the TDHF method be viewed, not as an approximation to but as a model of the exact Schroedinger system; that is, as a gedanken many-body experiment whose analysis with digital computers provides data worthy in itself of theoretical study. From such a viewpoint attention is focused on the structural analogies of the TDHF system with the exact theory rather than upon its quantitative equivalence, and the TDHF many-body system is studied as a challenge of its own which, although much simpler than the realistic problem, may still offer complexity enough to educate theorists in the present state of knowledge. In this spirit, the TDHF description of continuum reactions can be restructured from an initial-value problem into a form analogous to the S-matrix version of the Schroedinger theory. The resulting TD-S-HF theory involves only self-consistent single determinantal solutions of the TDHF equations and invokes time averaging to obtain a consistent interpretation of the TDHF analogs of quantities which are constant in the exact theory, such as the S-matrix and the asymptotic reaction channel characteristics. Periodic solutions then play the role of stationary eigenstates in the construction of suitable asymptotic reaction channels. If these periodic channel states occur only at discrete energies, then the resulting channels are mutually orthogonal (on the time average) and the theory exhibits a structure fully analogous to the exact theory. In certain special cases where the periodic solutions are known to occur as an energy continuum, the requirement that the periodicity of the channel solutions be gauge invariant provides a natural requantization condition which (suggestively) turns out to be identical with the Bohr-Sommerfeld quantization rule. 11 references

  19. A stochastic modeling of isotope exchange reactions in glutamine synthetase

    Science.gov (United States)

    Kazmiruk, N. V.; Boronovskiy, S. E.; Nartsissov, Ya R.

    2017-11-01

    The model presented in this work allows simulation of isotopic exchange reactions at chemical equilibrium catalyzed by a glutamine synthetase. To simulate the functioning of the enzyme the algorithm based on the stochastic approach was applied. The dependence of exchange rates for 14C and 32P on metabolite concentration was estimated. The simulation results confirmed the hypothesis of the ascertained validity for preferred order random binding mechanism. Corresponding values of K0.5 were also obtained.

  20. Diabatic models with transferrable parameters for generalized chemical reactions

    Science.gov (United States)

    Reimers, Jeffrey R.; McKemmish, Laura K.; McKenzie, Ross H.; Hush, Noel S.

    2017-05-01

    Diabatic models applied to adiabatic electron-transfer theory yield many equations involving just a few parameters that connect ground-state geometries and vibration frequencies to excited-state transition energies and vibration frequencies to the rate constants for electron-transfer reactions, utilizing properties of the conical-intersection seam linking the ground and excited states through the Pseudo Jahn-Teller effect. We review how such simplicity in basic understanding can also be obtained for general chemical reactions. The key feature that must be recognized is that electron-transfer (or hole transfer) processes typically involve one electron (hole) moving between two orbitals, whereas general reactions typically involve two electrons or even four electrons for processes in aromatic molecules. Each additional moving electron leads to new high-energy but interrelated conical-intersection seams that distort the shape of the critical lowest-energy seam. Recognizing this feature shows how conical-intersection descriptors can be transferred between systems, and how general chemical reactions can be compared using the same set of simple parameters. Mathematical relationships are presented depicting how different conical-intersection seams relate to each other, showing that complex problems can be reduced into an effective interaction between the ground-state and a critical excited state to provide the first semi-quantitative implementation of Shaik’s “twin state” concept. Applications are made (i) demonstrating why the chemistry of the first-row elements is qualitatively so different to that of the second and later rows, (ii) deducing the bond-length alternation in hypothetical cyclohexatriene from the observed UV spectroscopy of benzene, (iii) demonstrating that commonly used procedures for modelling surface hopping based on inclusion of only the first-derivative correction to the Born-Oppenheimer approximation are valid in no region of the chemical

  1. Contribution to the modelling of gas-solid reactions and reactors; Contribution a la modelisation des reactions et des reacteurs gaz-solide

    Energy Technology Data Exchange (ETDEWEB)

    Patisson, F

    2005-09-15

    Gas-solid reactions control a great number of major industrial processes involving matter transformation. This dissertation aims at showing that mathematical modelling is a useful tool for both understanding phenomena and optimising processes. First, the physical processes associated with a gas-solid reaction are presented in detail for a single particle, together with the corresponding available kinetic grain models. A second part is devoted to the modelling of multiparticle reactors. Different approaches, notably for coupling grain models and reactor models, are illustrated through various case studies: coal pyrolysis in a rotary kiln, production of uranium tetrafluoride in a moving bed furnace, on-grate incineration of municipal solid wastes, thermogravimetric apparatus, nuclear fuel making, steel-making electric arc furnace. (author)

  2. Accurate quantification of microRNA via single strand displacement reaction on DNA origami motif.

    Directory of Open Access Journals (Sweden)

    Jie Zhu

    Full Text Available DNA origami is an emerging technology that assembles hundreds of staple strands and one single-strand DNA into certain nanopattern. It has been widely used in various fields including detection of biological molecules such as DNA, RNA and proteins. MicroRNAs (miRNAs play important roles in post-transcriptional gene repression as well as many other biological processes such as cell growth and differentiation. Alterations of miRNAs' expression contribute to many human diseases. However, it is still a challenge to quantitatively detect miRNAs by origami technology. In this study, we developed a novel approach based on streptavidin and quantum dots binding complex (STV-QDs labeled single strand displacement reaction on DNA origami to quantitatively detect the concentration of miRNAs. We illustrated a linear relationship between the concentration of an exemplary miRNA as miRNA-133 and the STV-QDs hybridization efficiency; the results demonstrated that it is an accurate nano-scale miRNA quantifier motif. In addition, both symmetrical rectangular motif and asymmetrical China-map motif were tested. With significant linearity in both motifs, our experiments suggested that DNA Origami motif with arbitrary shape can be utilized in this method. Since this DNA origami-based method we developed owns the unique advantages of simple, time-and-material-saving, potentially multi-targets testing in one motif and relatively accurate for certain impurity samples as counted directly by atomic force microscopy rather than fluorescence signal detection, it may be widely used in quantification of miRNAs.

  3. Accurate Quantification of microRNA via Single Strand Displacement Reaction on DNA Origami Motif

    Science.gov (United States)

    Lou, Jingyu; Li, Weidong; Li, Sheng; Zhu, Hongxin; Yang, Lun; Zhang, Aiping; He, Lin; Li, Can

    2013-01-01

    DNA origami is an emerging technology that assembles hundreds of staple strands and one single-strand DNA into certain nanopattern. It has been widely used in various fields including detection of biological molecules such as DNA, RNA and proteins. MicroRNAs (miRNAs) play important roles in post-transcriptional gene repression as well as many other biological processes such as cell growth and differentiation. Alterations of miRNAs' expression contribute to many human diseases. However, it is still a challenge to quantitatively detect miRNAs by origami technology. In this study, we developed a novel approach based on streptavidin and quantum dots binding complex (STV-QDs) labeled single strand displacement reaction on DNA origami to quantitatively detect the concentration of miRNAs. We illustrated a linear relationship between the concentration of an exemplary miRNA as miRNA-133 and the STV-QDs hybridization efficiency; the results demonstrated that it is an accurate nano-scale miRNA quantifier motif. In addition, both symmetrical rectangular motif and asymmetrical China-map motif were tested. With significant linearity in both motifs, our experiments suggested that DNA Origami motif with arbitrary shape can be utilized in this method. Since this DNA origami-based method we developed owns the unique advantages of simple, time-and-material-saving, potentially multi-targets testing in one motif and relatively accurate for certain impurity samples as counted directly by atomic force microscopy rather than fluorescence signal detection, it may be widely used in quantification of miRNAs. PMID:23990889

  4. Developed Hybrid Model for Propylene Polymerisation at Optimum Reaction Conditions

    Directory of Open Access Journals (Sweden)

    Mohammad Jakir Hossain Khan

    2016-02-01

    Full Text Available A statistical model combined with CFD (computational fluid dynamic method was used to explain the detailed phenomena of the process parameters, and a series of experiments were carried out for propylene polymerisation by varying the feed gas composition, reaction initiation temperature, and system pressure, in a fluidised bed catalytic reactor. The propylene polymerisation rate per pass was considered the response to the analysis. Response surface methodology (RSM, with a full factorial central composite experimental design, was applied to develop the model. In this study, analysis of variance (ANOVA indicated an acceptable value for the coefficient of determination and a suitable estimation of a second-order regression model. For better justification, results were also described through a three-dimensional (3D response surface and a related two-dimensional (2D contour plot. These 3D and 2D response analyses provided significant and easy to understand findings on the effect of all the considered process variables on expected findings. To diagnose the model adequacy, the mathematical relationship between the process variables and the extent of polymer conversion was established through the combination of CFD with statistical tools. All the tests showed that the model is an excellent fit with the experimental validation. The maximum extent of polymer conversion per pass was 5.98% at the set time period and with consistent catalyst and co-catalyst feed rates. The optimum conditions for maximum polymerisation was found at reaction temperature (RT 75 °C, system pressure (SP 25 bar, and 75% monomer concentration (MC. The hydrogen percentage was kept fixed at all times. The coefficient of correlation for reaction temperature, system pressure, and monomer concentration ratio, was found to be 0.932. Thus, the experimental results and model predicted values were a reliable fit at optimum process conditions. Detailed and adaptable CFD results were capable

  5. Forced thermal cycling of catalytic reactions: experiments and modelling

    DEFF Research Database (Denmark)

    Jensen, Søren; Olsen, Jakob Lind; Thorsteinsson, Sune

    2007-01-01

    Recent studies of catalytic reactions subjected to fast forced temperature oscillations have revealed a rate enhancement increasing with temperature oscillation frequency. We present detailed studies of the rate enhancement up to frequencies of 2.5 Hz. A maximum in the rate enhancement is observed...... at about 1 Hz. A model for the rate enhancement that includes the surface kinetics and the dynamic partial pressure variations in the reactor is introduced. The model predicts a levelling off of the rate enhancement with frequency at about 1 Hz. The experimentally observed decrease above 1 Hz is explained...

  6. Ground reaction forces and knee kinetics during single and repeated badminton lunges.

    Science.gov (United States)

    Lam, Wing Kai; Ding, Rui; Qu, Yi

    2017-03-01

    Repeated movement (RM) lunge that frequently executed in badminton might be used for footwear evaluation. This study examined the influence of single movement (SM) and RM lunges on the ground reaction forces (GRFs) and knee kinetics during the braking phase of a badminton lunge step. Thirteen male university badminton players performed left-forward lunges in both SM and RM sessions. Force platform and motion capturing system were used to measure GRFs and knee kinetics variables. Paired t-test was performed to determine any significant differences between SM and RM lunges regarding mean and coefficient of variation (CV) in each variable. The kinetics results indicated that compared to SM lunges, the RM lunges had shorter contact time and generated smaller maximum loading rate of impact force, peak knee anterior-posterior force, and peak knee sagittal moment but generated larger peak horizontal resultant forces (Ps forces (Ps < 0.05). These results suggested that the RM testing protocols had a distinct loading response and adaptation pattern during lunge and that the RM protocol showed higher within-trial reliability, which may be beneficial for the knee joint loading evaluation under different interventions.

  7. Single hole spectroscopic strength in 98Ru through the 99Ru(d,t) reaction

    International Nuclear Information System (INIS)

    Rodrigues, M.R.D.; Borello-Lewin, T.; Horodynski-Matsushigue, L.B.; Duarte, J.L.M.; Rodrigues, C.L.; Barbosa, M.D.L.; Silva, G.B. da; Ukita, G.M.

    2002-01-01

    The 99 Ru(d,t) 98 Ru reaction was measured for the first time at 16 MeV incident energy with the Sao Paulo Pelletron-Enge-spectrograph facility employing the nuclear emulsion technique. In all, up to 3.5 MeV, 23 levels were detected, eight of them new; angular distributions are presented for all of them. Least squares fits of distorted wave Born approximation one-neutron pickup predictions to the rather well structured experimental angular distributions enabled the determination of l transfers and of the corresponding spectroscopic factors for 19 of these states, some being tentative attributions. Only transfers of l=0, 2, and 4 were observed. Several states were populated through single l transfers. A pure l=2 transfer is associated with the 2 1 + level and with several other states which are considered collective, as well as with the (4 + ) state at 2.277 MeV, which presents the highest spectroscopic strength. Considering five valence neutrons above the N=50 core, only 41% of the spectroscopic strength expected for 99 Ru was detected

  8. Bayesian inference of chemical kinetic models from proposed reactions

    KAUST Repository

    Galagali, Nikhil

    2015-02-01

    © 2014 Elsevier Ltd. Bayesian inference provides a natural framework for combining experimental data with prior knowledge to develop chemical kinetic models and quantify the associated uncertainties, not only in parameter values but also in model structure. Most existing applications of Bayesian model selection methods to chemical kinetics have been limited to comparisons among a small set of models, however. The significant computational cost of evaluating posterior model probabilities renders traditional Bayesian methods infeasible when the model space becomes large. We present a new framework for tractable Bayesian model inference and uncertainty quantification using a large number of systematically generated model hypotheses. The approach involves imposing point-mass mixture priors over rate constants and exploring the resulting posterior distribution using an adaptive Markov chain Monte Carlo method. The posterior samples are used to identify plausible models, to quantify rate constant uncertainties, and to extract key diagnostic information about model structure-such as the reactions and operating pathways most strongly supported by the data. We provide numerical demonstrations of the proposed framework by inferring kinetic models for catalytic steam and dry reforming of methane using available experimental data.

  9. Reaction

    African Journals Online (AJOL)

    abp

    19 oct. 2017 ... Axillary block is an easy and recommended technique in children. Its use in children with acute hepatitis A is not risk free especially when associated with sedation using remifentanil and propofol. Similarly, the presence of a single hydatid cyst allows general anesthesia with mono- pulmonary ventilation.

  10. A discrete model to study reaction-diffusion-mechanics systems.

    Science.gov (United States)

    Weise, Louis D; Nash, Martyn P; Panfilov, Alexander V

    2011-01-01

    This article introduces a discrete reaction-diffusion-mechanics (dRDM) model to study the effects of deformation on reaction-diffusion (RD) processes. The dRDM framework employs a FitzHugh-Nagumo type RD model coupled to a mass-lattice model, that undergoes finite deformations. The dRDM model describes a material whose elastic properties are described by a generalized Hooke's law for finite deformations (Seth material). Numerically, the dRDM approach combines a finite difference approach for the RD equations with a Verlet integration scheme for the equations of the mass-lattice system. Using this framework results were reproduced on self-organized pacemaking activity that have been previously found with a continuous RD mechanics model. Mechanisms that determine the period of pacemakers and its dependency on the medium size are identified. Finally it is shown how the drift direction of pacemakers in RDM systems is related to the spatial distribution of deformation and curvature effects.

  11. A discrete model to study reaction-diffusion-mechanics systems.

    Directory of Open Access Journals (Sweden)

    Louis D Weise

    Full Text Available This article introduces a discrete reaction-diffusion-mechanics (dRDM model to study the effects of deformation on reaction-diffusion (RD processes. The dRDM framework employs a FitzHugh-Nagumo type RD model coupled to a mass-lattice model, that undergoes finite deformations. The dRDM model describes a material whose elastic properties are described by a generalized Hooke's law for finite deformations (Seth material. Numerically, the dRDM approach combines a finite difference approach for the RD equations with a Verlet integration scheme for the equations of the mass-lattice system. Using this framework results were reproduced on self-organized pacemaking activity that have been previously found with a continuous RD mechanics model. Mechanisms that determine the period of pacemakers and its dependency on the medium size are identified. Finally it is shown how the drift direction of pacemakers in RDM systems is related to the spatial distribution of deformation and curvature effects.

  12. Single nanowire resistive nano-heater for highly localized thermo-chemical reactions: localized hierarchical heterojunction nanowire growth.

    Science.gov (United States)

    Yeo, Junyeob; Kim, Gunho; Hong, Sukjoon; Lee, Jinhwan; Kwon, Jinhyeong; Lee, Habeom; Park, Heeseung; Manoroktul, Wanit; Lee, Ming-Tsang; Lee, Bong Jae; Grigoropoulos, Costas P; Ko, Seung Hwan

    2014-12-29

    A single nanowire resistive nano-heater (RNH) is fabricated, and it is demonstrated that the RNH can induce highly localized temperature fields, which can trigger highly localized thermo-chemical reactions to grow hierarchical nanowires directly at the desired specific spot such as ZnO nanowire branch growth on a single Ag nanowire. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  13. On quark model relations for hypercharge-exchange reactions

    International Nuclear Information System (INIS)

    Kluyver, J.C.; Blokzijl, R.; Massaro, G.G.G.; Wolters, G.F.; Grossmann, P.; Lamb, P.R.; Wells, J.

    1978-01-01

    Peripheral two-body reactions of the type K - p → M 0 + Λ, Σ 0 or Σ 0 (1385) are considered. Predictions based on the additive quark model and SU(6) baryon wave functions are tested against data on cross sections and polarisations for given momentum transfer. Data obtained in a high statistics experiment at 4.2 GeV/c K - momentum, as well as data from a large variety of other experiments are used. Highly significant violations of these predictions are observed in the data. These violations are shown to occur in a systematic fashion, according to which SU(6) must be relaxed, but the amplitude structure implied by additivity would remain valid. As an application an amplitude analysis for natural parity exchange reactions with M 0 = π, phi and rho respectively is performed, which determines a relative phase, which cannot be obtained in model-independent analysis. Also reactions with M 0 = delta or B are considered, and some implications for coupling constants are discussed. (Auth.)

  14. Theoretical studies on thermal degradation reaction mechanism of model compound of bisphenol A polycarbonate.

    Science.gov (United States)

    Huang, Jinbao; He, Chao; Li, Xinsheng; Pan, Guiying; Tong, Hong

    2018-01-01

    Density functional theory methods (DFT) M062X have been used to investigate the thermal degradation processes of model compound of bisphenol A polycarbonate (MPC) and to identify the optimal reaction paths in the thermal decomposition of bisphenol A polycarbonate (PC). The bond dissociation energies of main bonds in MPC were calculated, and it is found that the weakest bond in MPC is the single bond between the methylic carbon and carbon atom and the second weakest bond in MPC is the single bond between oxygen atom and the carbonyl carbon. On the basis of computational results of kinetic parameters, a mechanism is proposed where the hydrolysis (or alcoholysis) reaction is the main degradation pathways for the formation of the evolved products, and the homolytic cleavage and rearrangement reactions are the competitive reaction pathways in the thermal degradation of PC. The proposed mechanism is consistent with experimental observations of CO 2 , bisphenol A and 1,1-bis(4-hydroxyphenyl)-ethane as the main degradation products, together with a small amount of CO, alkyl phenol and diphenyl carbonate. Copyright © 2017 Elsevier Ltd. All rights reserved.

  15. Students' Visualisation of Chemical Reactions--Insights into the Particle Model and the Atomic Model

    Science.gov (United States)

    Cheng, Maurice M. W.

    2018-01-01

    This paper reports on an interview study of 18 Grade 10-12 students' model-based reasoning of a chemical reaction: the reaction of magnesium and oxygen at the submicro level. It has been proposed that chemical reactions can be conceptualised using two models: (i) the "particle model," in which a reaction is regarded as the simple…

  16. Radiolytic oxidation of propane: computer modeling of the reaction scheme

    International Nuclear Information System (INIS)

    Gupta, A.K.; Hanrahan, R.J.

    1991-01-01

    The oxidation of gaseous propane under gamma radiolysis was studied at 100 torr pressure and 25 o C, at oxygen pressures from 1 to 15 torr. Major oxygen-containing products and their G-values with 10% added oxygen are as follows: acetone, 0.98; i-propyl alcohol, 0.86; propionaldehyde, 0.43; n-propyl alcohol, 0.11; acrolein, 0.14; and allyl alcohol, 0.038. The formation of major oxygen-containing products was explained on the basis that the alkyl radicals combine with molecular oxygen to give peroxyl radicals; the peroxyl radicals react with one another to give alkoxyl radicals, which in turn react with one another to form carbonyl compounds and alcohols. The reaction scheme for the formation of major products was examined using computer modeling based on a mechanism involving 28 reactions. Yields could be brought into agreement with the data within experimental error in nearly all cases. (author)

  17. Reaction-diffusion modeling of hydrogen in beryllium

    Energy Technology Data Exchange (ETDEWEB)

    Wensing, Mirko; Matveev, Dmitry; Linsmeier, Christian [Forschungszentrum Juelich GmbH, Institut fuer Energie- und Klimaforschung - Plasmaphysik (Germany)

    2016-07-01

    Beryllium will be used as first-wall material for the future fusion reactor ITER as well as in the breeding blanket of DEMO. In both cases it is important to understand the mechanisms of hydrogen retention in beryllium. In earlier experiments with beryllium low-energy binding states of hydrogen were observed by thermal desorption spectroscopy (TDS) which are not yet well understood. Two candidates for these states are considered: beryllium-hydride phases within the bulk and surface effects. The retention of deuterium in beryllium is studied by a reaction rate approach using a coupled reaction diffusion system (CRDS)-model relying on ab initio data from density functional theory calculations (DFT). In this contribution we try to assess the influence of surface recombination.

  18. Reactions of Lignin Model Compounds in Ionic Liquids

    Energy Technology Data Exchange (ETDEWEB)

    Holladay, John E.; Binder, Joseph B.; Gray, Michel J.; White, James F.; Zhang, Z. Conrad

    2009-09-15

    Lignin, a readily available form of biomass, awaits novel chemistry for converting it to valuable aromatic chemicals. Recent work has demonstrated that ionic liquids are excellent solvents for processing woody biomass and lignin. Seeking to exploit ionic liquids as media for depolymerization of lignin, we investigated reactions of lignin model compounds in these solvents. Using Brønsted acid catalysts in 1-ethyl-3-methylimidazolium triflate at moderate temperatures, we obtained up to 11.6% yield of the dealkylation product guaiacol from the model compound eugenol and cleaved phenethyl phenyl ether, a model for lignin ethers. Despite these successes, acid catalysis failed in dealkylation of the unsaturated model compound 4-ethylguaiacol and did not produce monomeric products from organosolv lignin, demonstrating that further work is required to understand the complex chemistry of lignin depolymerization.

  19. New paradigm for simplified combustion modeling of energetic solids: Branched chain gas reaction

    Energy Technology Data Exchange (ETDEWEB)

    Brewster, M.Q.; Ward, M.J. [Univ. of Illinois, Urbana, IL (United States); Son, S.F. [Los Alamos National Lab., NM (United States)

    1997-09-01

    Two combustion models with simple but rational chemistry are compared: the classical high gas activation energy (E{sub g}/RT {much_gt} 1) Denison-Baum-Williams (DBW) model, and a new low gas activation energy (E{sub g}/RT {much_lt} 1) model recently proposed by Ward, Son, and Brewster (WSB). Both models make the same simplifying assumptions of constant properties, Lewis number unity, single-step, second order gas phase reaction, and single-step, zero order, high activation energy condensed phase decomposition. The only difference is in the gas reaction activation energy E{sub g} which is asymptotically large for DBW and vanishingly small for WSB. For realistic parameters the DBW model predicts a nearly constant temperature sensitivity {sigma}{sub p} and a pressure exponent n approaching 1. The WSB model predicts generally observed values of n = 0.7 to 0.9 and {sigma}{sub p}(T{sub o},P) with the generally observed variations with temperature (increasing) and pressure (decreasing). The WSB temperature profile also matches measured profiles better. Comparisons with experimental data are made using HMX as an illustrative example (for which WSB predictions for {sigma}{sub p}(T{sub o},P) are currently more accurate than even complex chemistry models). WSB has also shown good agreement with NC/NG double base propellant and HNF, suggesting that at the simplest level of combustion modeling, a vanishingly small gas activation energy is more realistic than an asymptotically large one. The authors conclude from this that the important (regression rate determining) gas reaction zone near the surface has more the character of chain branching than thermal decomposition.

  20. Computational comparison of quantum-mechanical models for multistep direct reactions

    International Nuclear Information System (INIS)

    Koning, A.J.; Akkermans, J.M.

    1993-01-01

    We have carried out a computational comparison of all existing quantum-mechanical models for multistep direct (MSD) reactions. The various MSD models, including the so-called Feshbach-Kerman-Koonin, Tamura-Udagawa-Lenske and Nishioka-Yoshida-Weidenmueller models, have been implemented in a single computer system. All model calculations thus use the same set of parameters and the same numerical techniques; only one adjustable parameter is employed. The computational results have been compared with experimental energy spectra and angular distributions for several nuclear reactions, namely, 90 Zr(p,p') at 80 MeV, 209 Bi(p,p') at 62 MeV, and 93 Nb(n,n') at 25.7 MeV. In addition, the results have been compared with the Kalbach systematics and with semiclassical exciton model calculations. All quantum MSD models provide a good fit to the experimental data. In addition, they reproduce the systematics very well and are clearly better than semiclassical model calculations. We furthermore show that the calculated predictions do not differ very strongly between the various quantum MSD models, leading to the conclusion that the simplest MSD model (the Feshbach-Kerman-Koonin model) is adequate for the analysis of experimental data

  1. The incidence of perioperative hypersensitivity reactions: a single-center, prospective, cohort study.

    Science.gov (United States)

    Berroa, Felicia; Lafuente, Alberto; Javaloyes, Gracia; Cabrera-Freitag, Paula; de la Borbolla, Juan M; Moncada, Rafael; Goikoetxea, Maria J; Sanz, Maria L; Ferrer, Marta; Gastaminza, Gabriel

    2015-07-01

    The incidence of perioperative hypersensitivity reactions, which can be life-threatening, ranges from 1 in 20,000 to 1 in 1361. These reactions are usually classified as IgE or non-IgE mediated. The aim of this study was to determine the incidence of allergic reactions during general anesthesia in our hospital, to establish the incidence of the allergic reactions for each drug used, to assess the frequency of IgE-mediated reactions in even mild reactions, and to compare the degree of agreement between anesthesiologist suspicion and allergy diagnosis. We included patients diagnosed with a clinical hypersensitivity reaction during a procedure under general anesthesia over a 30-month period (February 2008 to August 2010). Plasma histamine and serum tryptase concentrations were determined in these patients. We performed skin tests to diagnose the causative agent. Data from the hospital electronic prescribing system were collected to determine the ratio of reactions for each drug. During the study period, 16,946 anesthetic procedures were performed (53% involved males; mean age, 51.6 years). Forty-four perianesthetic reactions were recorded, and the ratio of reactions was 1 in 385 operations (95% confidence interval, 1/529-1/287). Twenty-five reactions (25/44; 57%) occurred during the induction of anesthesia. Twenty-one reactions (21/44; 48%) were mild, involving only skin, and 23 of 44 (52%) were anaphylactic reactions. Four of 10 patients who had only a rash experienced IgE-mediated reactions. Five surgeries (11%) were suspended because of the severity of the reactions. Fifteen reactions (15/30; 50%) were IgE mediated, and, in 2 of 30 (7%), a non-IgE agent was found (cold urticaria and nonsteroidal anti-inflammatory drug intolerance). The ratio of reactions for each drug was as follows: protamine, 1 in 468; cisatracurium, 1 in 1388; amoxicillin-clavulanate, 1 in 1968; atracurium, 1 in 2039; and dipyrone, 1 in 3159. Perioperative reactions are more common than

  2. A reaction-diffusion model of cytosolic hydrogen peroxide.

    Science.gov (United States)

    Lim, Joseph B; Langford, Troy F; Huang, Beijing K; Deen, William M; Sikes, Hadley D

    2016-01-01

    As a signaling molecule in mammalian cells, hydrogen peroxide (H2O2) determines the thiol/disulfide oxidation state of several key proteins in the cytosol. Localization is a key concept in redox signaling; the concentrations of signaling molecules within the cell are expected to vary in time and in space in manner that is essential for function. However, as a simplification, all theoretical studies of intracellular hydrogen peroxide and many experimental studies to date have treated the cytosol as a well-mixed compartment. In this work, we incorporate our previously reported reduced kinetic model of the network of reactions that metabolize hydrogen peroxide in the cytosol into a model that explicitly treats diffusion along with reaction. We modeled a bolus addition experiment, solved the model analytically, and used the resulting equations to quantify the spatiotemporal variations in intracellular H2O2 that result from this kind of perturbation to the extracellular H2O2 concentration. We predict that micromolar bolus additions of H2O2 to suspensions of HeLa cells (0.8 × 10(9)cells/l) result in increases in the intracellular concentration that are localized near the membrane. These findings challenge the assumption that intracellular concentrations of H2O2 are increased uniformly throughout the cell during bolus addition experiments and provide a theoretical basis for differing phenotypic responses of cells to intracellular versus extracellular perturbations to H2O2 levels. Copyright © 2015 Elsevier Inc. All rights reserved.

  3. WINKLER'S SINGLE-PARAMETER SUBGRADE MODEL FROM ...

    African Journals Online (AJOL)

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    SUBGRADE MODELING. Asrat Worku. Department of ... The models give consistently larger stiffness for the Winkler springs as compared to previously proposed similar continuum-based models that ignore the lateral stresses. ...... (ν = 0.25 and E = 40MPa); (b) a medium stiff clay (ν = 0.45 and E = 50MPa). In contrast to this, ...

  4. Reaction-time-resolved measurements of laser-induced fluorescence in a shock tube with a single laser pulse

    Science.gov (United States)

    Zabeti, S.; Fikri, M.; Schulz, C.

    2017-11-01

    Shock tubes allow for the study of ultra-fast gas-phase reactions on the microsecond time scale. Because the repetition rate of the experiments is low, it is crucial to gain as much information as possible from each individual measurement. While reaction-time-resolved species concentration and temperature measurements with fast absorption methods are established, conventional laser-induced fluorescence (LIF) measurements with pulsed lasers provide data only at a single reaction time. Therefore, fluorescence methods have rarely been used in shock-tube diagnostics. In this paper, a novel experimental concept is presented that allows reaction-time-resolved LIF measurements with one single laser pulse using a test section that is equipped with several optical ports. After the passage of the shock wave, the reactive mixture is excited along the center of the tube with a 266-nm laser beam directed through a window in the end wall of the shock tube. The emitted LIF signal is collected through elongated sidewall windows and focused onto the entrance slit of an imaging spectrometer coupled to an intensified CCD camera. The one-dimensional spatial resolution of the measurement translates into a reaction-time-resolved measurement while the species information can be gained from the spectral axis of the detected two-dimensional image. Anisole pyrolysis was selected as the benchmark reaction to demonstrate the new apparatus.

  5. Three-dimensional on-chip continuous-flow polymerase chain reaction employing a single heater.

    Science.gov (United States)

    Wu, Wenming; Lee, Nae Yoon

    2011-06-01

    Multi-step temperature control in a polymerase chain reaction (PCR) is a limiting factor in device miniaturization and portability. In this study, we propose the fabrication of a three-dimensional (3D) microdevice employing a single heater to minimize temperature control required for an on-chip continuous-flow PCR as well as the overall footprint by stacking the device in multi-layers. Two poly(dimethylsiloxane) (PDMS) layers with differing thicknesses are vertically stacked with their microchannel-engraved sides facing down. Through-holes are made in the thicker PDMS layer, which is sandwiched between a glass substrate at the bottom and the thinner PDMS layer at the top. In this way, a fluidic conduit is realized in a 3D configuration. The assembled 3D microdevice is then placed onto a heater glass-side down. The interface of the two PDMS layers displays a relatively lower temperature than that of the PDMS and glass layers due to the low thermal conductivity of the PDMS and its physical distance from the heater. The denaturation temperature can be controlled by adjusting the temperature of the heater, while the annealing/extension temperature can be controlled automatically by molding the thicker bottom PDMS layer into the appropriate thickness calculated using a numerical derivation proposed in this study. In this way, a cumbersome temperature measurement step is eliminated. DNA amplification was successfully carried out using the proposed 3D fluidic microdevice, and the intensity of the resulting amplicon was comparable to that obtained using a thermal cycler. This novel concept of adopting a single heating source greatly simplifies the temperature control issue present in an on-chip continuous-flow PCR. It also allows the use of a commercialized hot plate as a potential heat source, paving the way for device miniaturization and portability in a highly cost-effective manner. In this study, a simple and facile technique to make arrays of through-holes for the

  6. Deuterium cluster model for low energy nuclear reactions (LENR)

    Science.gov (United States)

    Miley, George; Hora, Heinrich

    2007-11-01

    For studying the possible reactions of high density deuterons on the background of a degenerate electron gas, a summary of experimental observations resulted in the possibility of reactions in pm distance and more than ksec duration similar to the K-shell electron capture [1]. The essential reason was the screening of the deuterons by a factor of 14 based on the observations. Using the bosonic properties for a cluster formation of the deuterons and a model of compound nuclear reactions [2], the measured distribution of the resulting nuclei may be explained as known from the Maruhn-Greiner theory for fission. The local maximum of the distribution at the main minimum indicates the excited states of the compound nuclei during their intermediary state. This measured local maximum may be an independent proof for the deuteron clusters at LENR. [1] H. Hora, G.H. Miley et al. Physics Letters A175, 138 (1993) [2] H. Hora and G.H. Miley, APS March Meeting 2007, Program p. 116

  7. Systematic development of reduced reaction mechanisms for dynamic modeling

    Science.gov (United States)

    Frenklach, M.; Kailasanath, K.; Oran, E. S.

    1986-01-01

    A method for systematically developing a reduced chemical reaction mechanism for dynamic modeling of chemically reactive flows is presented. The method is based on the postulate that if a reduced reaction mechanism faithfully describes the time evolution of both thermal and chain reaction processes characteristic of a more complete mechanism, then the reduced mechanism will describe the chemical processes in a chemically reacting flow with approximately the same degree of accuracy. Here this postulate is tested by producing a series of mechanisms of reduced accuracy, which are derived from a full detailed mechanism for methane-oxygen combustion. These mechanisms were then tested in a series of reactive flow calculations in which a large-amplitude sinusoidal perturbation is applied to a system that is initially quiescent and whose temperature is high enough to start ignition processes. Comparison of the results for systems with and without convective flow show that this approach produces reduced mechanisms that are useful for calculations of explosions and detonations. Extensions and applicability to flames are discussed.

  8. Evaluation of canine adverse food reactions by patch testing with single proteins, single carbohydrates and commercial foods.

    Science.gov (United States)

    Johansen, Cornelia; Mariani, Claire; Mueller, Ralf S

    2017-10-01

    Adverse food reaction (AFR) is an important differential diagnosis for the pruritic dog. It is usually diagnosed by feeding an elimination diet with a novel protein and carbohydrate source for eight weeks followed by subsequent food provocation. A previous study demonstrated that patch testing dogs with foods had a high sensitivity and negative predictability for selection of elimination diet ingredients. The aim of this study was to investigate patch testing with proteins, carbohydrates and dry commercial dog food in dogs to determine whether there was value in patch testing to aid the diagnosis of canine adverse food reaction. Twenty five privately owned dogs, with confirmed AFR, underwent provocation trials with selected food antigens and patch testing. For proteins, carbohydrates and dry dog food the sensitivity of patch testing was 100%, 70% and 22.2%, respectively; the negative predictive values of patch testing were 100%, 79% and 72%. The positive predictive values of patch testing for proteins and carbohydrates were 75% and 74%, respectively. This study confirmed that patch testing may be useful for the selection of a suitable protein source for an elimination diet in dogs with suspected AFR, but not as a diagnostic tool for canine AFR. Results for proteins are more reliable than for carbohydrates and the majority of positive patch test reactions were observed with raw protein. Patch testing with commercial dog food does not seem to be useful. © 2017 ESVD and ACVD.

  9. A mathematical model for the chemical reactions induced by radiation

    International Nuclear Information System (INIS)

    Negron M, A.; Ramos B, S.; Frias, D.; Sanchez M, G.

    2007-01-01

    Full text: Ferrous sulfate salt in acid solutions is one of the systems most extensively studied and most widely used. This dosimeter has received considerable attention because of its high sensitivity to X-rays and gamma radiation. With care this dosimetry is capable of a 0.1% precision for Co gamma rays. It is an easily available commercial product and can easily be prepared. However, our experimental results have shown that kinetics of the reaction mechanism initiated by radiolysis is strongly affected by changes in the temperature of irradiation. To evaluate energy deposited by gamma radiation on samples irradiated below room temperature is a truly difficult task. In fact, irradiating iron salts with gamma rays at different decreasing temperatures keeping constant the rest of irradiation conditions, we have observed a diminution of the rate of conversions of Fe 2+ into Fe 3+ . Several factors can contribute in order that the same absorbed dose will produce different amount of production of Fe 3+ . In the present paper, we present some experimental results of the response of ferrous sulfate in frozen solutions as a function of the irradiation temperature. The considered values were from 77 K, 198 K, 273 K, and 300 K. However this aim of e article concerns with the implementation of a theoretical model framework. This is a computational numerical simulation of the kinetics of reaction induced by radiation via radiolysis and the comparison with our experimental results which allowed the study of the effect of low temperature in such contexts. We also describe the mathematical model for the reaction kinetics as well as haw is obtained the temperature dependent yield by radiolysis tem. On the other hand it is detailed the computational approach. Finally a comparison between both experimental and theoretical results was compared in order to verify the reproducibility of our results from our theoretical model. (Author)

  10. Single-cluster dynamics for the random-cluster model

    NARCIS (Netherlands)

    Deng, Y.; Qian, X.; Blöte, H.W.J.

    2009-01-01

    We formulate a single-cluster Monte Carlo algorithm for the simulation of the random-cluster model. This algorithm is a generalization of the Wolff single-cluster method for the q-state Potts model to noninteger values q>1. Its results for static quantities are in a satisfactory agreement with those

  11. BlenX-based compositional modeling of complex reaction mechanisms

    Directory of Open Access Journals (Sweden)

    Judit Zámborszky

    2010-02-01

    Full Text Available Molecular interactions are wired in a fascinating way resulting in complex behavior of biological systems. Theoretical modeling provides a useful framework for understanding the dynamics and the function of such networks. The complexity of the biological networks calls for conceptual tools that manage the combinatorial explosion of the set of possible interactions. A suitable conceptual tool to attack complexity is compositionality, already successfully used in the process algebra field to model computer systems. We rely on the BlenX programming language, originated by the beta-binders process calculus, to specify and simulate high-level descriptions of biological circuits. The Gillespie's stochastic framework of BlenX requires the decomposition of phenomenological functions into basic elementary reactions. Systematic unpacking of complex reaction mechanisms into BlenX templates is shown in this study. The estimation/derivation of missing parameters and the challenges emerging from compositional model building in stochastic process algebras are discussed. A biological example on circadian clock is presented as a case study of BlenX compositionality.

  12. An anisotropic three-fluid model for heavy ion reactions

    International Nuclear Information System (INIS)

    Lovas, I.; Zimanyi, J.; Csernai, L.P.; Greiner, W.

    1981-01-01

    The nucleons taking part in heavy ion reactions are considered as a three-fluid system. The first and second components correspond to the target and the projectile, while the thermalised nucleons produced in the course of the collision belong to the third component. Making use of the Boltzmann-equation, hydrodynamical equations are derived which yield also the anisotropy of the momentum distribution. The equation of state for anisotropic nuclear matter is derived from a field theoretical model in the mean field approximation. (Auth.)

  13. Parametric pattern selection in a reaction-diffusion model.

    Directory of Open Access Journals (Sweden)

    Michael Stich

    Full Text Available We compare spot patterns generated by Turing mechanisms with those generated by replication cascades, in a model one-dimensional reaction-diffusion system. We determine the stability region of spot solutions in parameter space as a function of a natural control parameter (feed-rate where degenerate patterns with different numbers of spots coexist for a fixed feed-rate. While it is possible to generate identical patterns via both mechanisms, we show that replication cascades lead to a wider choice of pattern profiles that can be selected through a tuning of the feed-rate, exploiting hysteresis and directionality effects of the different pattern pathways.

  14. Inclusive reaction π- + p → p + anything at Fermilab energies and comparison to Triple Regge Models

    International Nuclear Information System (INIS)

    Blanar, G.J.

    1975-01-01

    An experiment which measured the inclusive reaction π - + p → p + anything at incident beam momentum of 40, 100, 200 and 240 GeV is described. Measurements were made in the t region -.1 to -.4 GeV 2 . The apparatus, calibration methods, data reduction and analysis techniques are discussed in detail. Comparisons between the observed single particle invariant cross sections and Triple Regge Models are made. The experiment used the missing mass technique with a liquid hydrogen target and a single arm spectrometer. The spectrometer consisted of four spark chambers, and one proportional chamber to determine the trajectory, and an array of five large scintillator counters to determine the kinetic energy of the recoil proton. A single proportional chamber was located downstream of the target to provide calibration data from the elastic reaction, π - + p → π - + p. Approximately five million triggers were taken with almost a million events appearing in the final cross sections. A comparison to a simple four term Triple Regge Model (PPP, PPR, RRP, RRR) gave a poor fit. However, including the pion contributions explicitly (ππR and ππP) gave good agreement. Adding the interference terms (PRP and PRR) did not significantly improve the fit

  15. Do voluntary step reactions in dual task conditions have an added value over single task for fall prediction? A prospective study.

    Science.gov (United States)

    Melzer, Itshak; Kurz, Ilan; Shahar, Danit; Oddsson, Lars I E

    2010-01-01

    Stepping reactions play a critical role in responding to balance perturbations, whether they are a consequence of external perturbation or self-induced in nature. The aim of the present study was to determine prospectively the capacity of voluntary stepping performance in singleand dual-task conditions, to predict future falls among older community-dwelling persons. We also aimed to assess whether dual task conditions have an added value over single tasks for fall prediction. A total of 100 healthy old volunteers (mean age 78.4±5.7 yrs), from two self-care protected retirement homes for older adults, performed the Voluntary Step Execution Test in single- and dual-task conditions as a reaction time task while standing on a single force platform. Step initiation, preparatory and swing phases, and foot-contact time were extracted from data on center of pressure and ground reaction force. One-year fall incidences were monitored. Ninety-eight subjects completed the one-year follow-up, 49 non-fallers, 32 one-time fallers, and 17 recurrent fallers (two or more falls). Recurrent fallers had significantly slower voluntary step execution times in both single- and dual-task conditions, especially due to a slower preparation phase. Two stepwise (backward) logistic regression models showed that longer step execution times have strong predictive value for falls in both single- and dual-task conditions (odds ratio (OR) 8.7 and 5.4, respectively, ppredict future falls, with no added value to dual- over single-task condition.

  16. Single-layer model for surface roughness.

    Science.gov (United States)

    Carniglia, C K; Jensen, D G

    2002-06-01

    Random roughness of an optical surface reduces its specular reflectance and transmittance by the scattering of light. The reduction in reflectance can be modeled by a homogeneous layer on the surface if the refractive index of the layer is intermediate to the indices of the media on either side of the surface. Such a layer predicts an increase in the transmittance of the surface and therefore does not provide a valid model for the effects of scatter on the transmittance. Adding a small amount of absorption to the layer provides a model that predicts a reduction in both reflectance and transmittance. The absorbing layer model agrees with the predictions of a scalar scattering theory for a layer with a thickness that is twice the rms roughness of the surface. The extinction coefficient k for the layer is proportional to the thickness of the layer.

  17. In silico strain optimization by adding reactions to metabolic models.

    Science.gov (United States)

    Correia, Sara; Rocha, Miguel

    2012-07-24

    Nowadays, the concerns about the environment and the needs to increase the productivity at low costs, demand for the search of new ways to produce compounds with industrial interest. Based on the increasing knowledge of biological processes, through genome sequencing projects, and high-throughput experimental techniques as well as the available computational tools, the use of microorganisms has been considered as an approach to produce desirable compounds. However, this usually requires to manipulate these organisms by genetic engineering and/ or changing the enviromental conditions to make the production of these compounds possible. In many cases, it is necessary to enrich the genetic material of those microbes with hereologous pathways from other species and consequently adding the potential to produce novel compounds. This paper introduces a new plug-in for the OptFlux Metabolic Engineering platform, aimed at finding suitable sets of reactions to add to the genomes of selected microbes (wild type strain), as well as finding complementary sets of deletions, so that the mutant becomes able to overproduce compounds with industrial interest, while preserving their viability. The necessity of adding reactions to the metabolic model arises from existing gaps in the original model or motivated by the productions of new compounds by the organism. The optimization methods used are metaheuristics such as Evolutionary Algorithms and Simulated Annealing. The usefulness of this plug-in is demonstrated by a case study, regarding the production of vanillin by the bacterium E. coli.

  18. Pion-nucleus reactions in a microscopic transport model

    International Nuclear Information System (INIS)

    Engel, A.; Cassing, W.; Mosel, U.; Schaefer, M.; Wolf, G.

    1994-01-01

    We analyse pion-nucleus reactions in a microscopic transport model of the BUU type, which propagates nucleons, pions, deltas and N(1440) resonances explicitly in space and time. In particular we examine pion absorption and inelastic-scattering cross sections for pion kinetic energies T π =85-315 MeV and various target masses. In general, the mass dependence of the experimental data is well described for energies up to the Δ-resonance (∼160 MeV), while the absorption cross sections are somewhat overestimated for the higher energies. In addition we study the possible dynamical effects of delta and pion potentials in the medium on various observables as well as alternative models for the in-medium Δ-width. ((orig.))

  19. Enrichment of semiconducting single-walled carbon nanotubes by carbothermic reaction for use in all-nanotube field effect transistors.

    Science.gov (United States)

    Li, Shisheng; Liu, Chang; Hou, Peng-Xiang; Sun, Dong-Ming; Cheng, Hui-Ming

    2012-11-27

    Selective removal of metallic single-walled carbon nanotubes (SWCNTs) and consequent enrichment of semiconducting SWCNTs were achieved through an efficient carbothermic reaction with a NiO thin film at a relatively low temperature of 350 °C. All-SWCNT field effect transistors (FETs) were fabricated with the aid of a patterned NiO mask, in which the as-grown SWCNTs behaving as source/drain electrodes and the remaining semiconducting SWCNTs that survive in the carbothermic reaction as a channel material. The all-SWCNT FETs demonstrate improved current ON/OFF ratios of ∼10(3).

  20. Modeling the formation and reactions of benzene metabolites.

    Science.gov (United States)

    Golding, Bernard T; Barnes, Martine L; Bleasdale, Christine; Henderson, Alistair P; Jiang, Dong; Li, Xin; Mutlu, Esra; Petty, Hannah J; Sadeghi, Majid M

    2010-03-19

    One or more of the muconaldehyde isomers is a putative product of benzene metabolism. As muconaldehydes are highly reactive dienals and potentially mutagenic they might be relevant to the carcinogenicity of benzene. Muconaldehydes may be derived through the action of a cytochrome P450 mono-oxygenase on benzene oxide-oxepin, which are established metabolites of benzene. Oxidation of benzene oxide-oxepin either by the one-electron oxidant cerium(IV) ammonium nitrate (CAN) or by iron(III) tris(1,10-phenanthroline) hexafluorophosphate in acetone at -78 degrees C or acetonitrile at -40 degrees C gave (E,Z)-muconaldehyde, which was a single diastereoisomer according to analysis by (1)H NMR spectroscopy. Reaction of toluene-1,2-oxide/2-methyloxepin with CAN gave (2E,4Z)-6-oxo-hepta-2,4-dienal. Similarly, the action of CAN on 1,6-dimethylbenzene oxide-2,7-dimethyloxepin gave (3Z,5E)-octa-3,5-diene-2,7-dione. In vivo, benzene oxide-oxepin could suffer one-electron oxidation by cytochrome P450 mono-oxygenase giving (E,Z)-muconaldehyde. The observations presented may be relevant to the toxicology of benzene oxide-oxepin and other arene oxide-oxepins as we have previously shown that (E,Z)-muconaldehyde, analogously to (Z,Z)-muconaldehyde, affords pyrrole adducts with the exocyclic amino groups of the DNA bases adenine and guanine. Independent of their possible toxicological significance, the experiments described provide preparatively useful routes to (E,Z)-muconaldehyde and its congeners. Methods are also described for the trapping and analysis of reactive benzene metabolites, e.g. using the Diels-Alder reaction with the dienophile 4-phenyl-1,2,4-triazoline-3,5-dione to trap arene oxides and with the diene 1,3-diphenylisobenzofuran to trap enals. Copyright (c) 2010 Elsevier Ireland Ltd. All rights reserved.

  1. Radiolytic oxidation of propane: Computer modeling of the reaction scheme

    Science.gov (United States)

    Gupta, Avinash K.; Hanrahan, Robert J.

    The oxidation of gaseous propane under gamma radiolysis was studied at 100 torr pressure and 25°C, at oxygen pressures from 1 to 15 torr. Major oxygen-containing products and their G-values with 10% added oxygen are as follows: acetone, 0.98; i-propyl alcohol, 0.86; propionaldehyde, 0.43; n-propyl alcohol, 0.11; acrolein, 0.14; and allyl alcohol, 0.038. Minor products include i-butyl alcohol, t-amyl alcohol, n-butyl alcohol, n-amyl alcohol, and i-amyl alcohol. Small yields of i-hexyl alcohol and n-hexyl alcohol were also observed. There was no apparent difference in the G-values at pressures of 50, 100 and 150 torr. When the oxygen concentration was decreased below 5%, the yields of acetone, i-propyl alcohol, and n-propyl alcohol increased, the propionaldehyde yield decreased, and the yields of other products remained constant. The formation of major oxygen-containing products was explained on the basis that the alkyl radicals combine with molecular oxygen to give peroxyl radicals; the peroxyl radicals react with one another to give alkoxyl radicals, which in turn react with one another to form carbonyl compounds and alcohols. The reaction scheme for the formation of major products was examined using computer modeling based on a mechanism involving 28 reactions. Yields could be brought into agreement with the data within experimental error in nearly all cases.

  2. A multi-pathway model for photosynthetic reaction center

    Science.gov (United States)

    Qin, M.; Shen, H. Z.; Yi, X. X.

    2016-03-01

    Charge separation occurs in a pair of tightly coupled chlorophylls at the heart of photosynthetic reaction centers of both plants and bacteria. Recently it has been shown that quantum coherence can, in principle, enhance the efficiency of a solar cell, working like a quantum heat engine. Here, we propose a biological quantum heat engine (BQHE) motivated by Photosystem II reaction center (PSII RC) to describe the charge separation. Our model mainly considers two charge-separation pathways which is more than that typically considered in the published literature. We explore how these cross-couplings increase the current and power of the charge separation and discuss the effects of multiple pathways in terms of current and power. The robustness of the BQHE against the charge recombination in natural PSII RC and dephasing induced by environments is also explored, and extension from two pathways to multiple pathways is made. These results suggest that noise-induced quantum coherence helps to suppress the influence of acceptor-to-donor charge recombination, and besides, nature-mimicking architectures with engineered multiple pathways for charge separations might be better for artificial solar energy devices considering the influence of environments.

  3. A multi-pathway model for photosynthetic reaction center

    International Nuclear Information System (INIS)

    Qin, M.; Shen, H. Z.; Yi, X. X.

    2016-01-01

    Charge separation occurs in a pair of tightly coupled chlorophylls at the heart of photosynthetic reaction centers of both plants and bacteria. Recently it has been shown that quantum coherence can, in principle, enhance the efficiency of a solar cell, working like a quantum heat engine. Here, we propose a biological quantum heat engine (BQHE) motivated by Photosystem II reaction center (PSII RC) to describe the charge separation. Our model mainly considers two charge-separation pathways which is more than that typically considered in the published literature. We explore how these cross-couplings increase the current and power of the charge separation and discuss the effects of multiple pathways in terms of current and power. The robustness of the BQHE against the charge recombination in natural PSII RC and dephasing induced by environments is also explored, and extension from two pathways to multiple pathways is made. These results suggest that noise-induced quantum coherence helps to suppress the influence of acceptor-to-donor charge recombination, and besides, nature-mimicking architectures with engineered multiple pathways for charge separations might be better for artificial solar energy devices considering the influence of environments.

  4. A reaction-diffusion model of cholinergic retinal waves.

    Directory of Open Access Journals (Sweden)

    Benjamin Lansdell

    2014-12-01

    Full Text Available Prior to receiving visual stimuli, spontaneous, correlated activity in the retina, called retinal waves, drives activity-dependent developmental programs. Early-stage waves mediated by acetylcholine (ACh manifest as slow, spreading bursts of action potentials. They are believed to be initiated by the spontaneous firing of Starburst Amacrine Cells (SACs, whose dense, recurrent connectivity then propagates this activity laterally. Their inter-wave interval and shifting wave boundaries are the result of the slow after-hyperpolarization of the SACs creating an evolving mosaic of recruitable and refractory cells, which can and cannot participate in waves, respectively. Recent evidence suggests that cholinergic waves may be modulated by the extracellular concentration of ACh. Here, we construct a simplified, biophysically consistent, reaction-diffusion model of cholinergic retinal waves capable of recapitulating wave dynamics observed in mice retina recordings. The dense, recurrent connectivity of SACs is modeled through local, excitatory coupling occurring via the volume release and diffusion of ACh. In addition to simulation, we are thus able to use non-linear wave theory to connect wave features to underlying physiological parameters, making the model useful in determining appropriate pharmacological manipulations to experimentally produce waves of a prescribed spatiotemporal character. The model is used to determine how ACh mediated connectivity may modulate wave activity, and how parameters such as the spontaneous activation rate and sAHP refractory period contribute to critical wave size variability.

  5. An Equilibrium-Based Model of Gas Reaction and Detonation

    International Nuclear Information System (INIS)

    Trowbridge, L.D.

    2000-01-01

    During gaseous diffusion plant operations, conditions leading to the formation of flammable gas mixtures may occasionally arise. Currently, these could consist of the evaporative coolant CFC-114 and fluorinating agents such as F2 and ClF3. Replacement of CFC-114 with a non-ozone-depleting substitute is planned. Consequently, in the future, the substitute coolant must also be considered as a potential fuel in flammable gas mixtures. Two questions of practical interest arise: (1) can a particular mixture sustain and propagate a flame if ignited, and (2) what is the maximum pressure that can be generated by the burning (and possibly exploding) gas mixture, should it ignite? Experimental data on these systems, particularly for the newer coolant candidates, are limited. To assist in answering these questions, a mathematical model was developed to serve as a tool for predicting the potential detonation pressures and for estimating the composition limits of flammability for these systems based on empirical correlations between gas mixture thermodynamics and flammability for known systems. The present model uses the thermodynamic equilibrium to determine the reaction endpoint of a reactive gas mixture and uses detonation theory to estimate an upper bound to the pressure that could be generated upon ignition. The model described and documented in this report is an extended version of related models developed in 1992 and 1999

  6. Reaction modeling of drainage quality in the Duluth Complex, northern Minnesota, USA

    Science.gov (United States)

    Seal, Robert; Lapakko, Kim; Piatak, Nadine; Woodruff, Laurel G.

    2015-01-01

    Reaction modeling can be a valuable tool in predicting the long-term behavior of waste material if representative rate constants can be derived from long-term leaching tests or other approaches. Reaction modeling using the REACT program of the Geochemist’s Workbench was conducted to evaluate long-term drainage quality affected by disseminated Cu-Ni-(Co-)-PGM sulfide mineralization in the basal zone of the Duluth Complex where significant resources have been identified. Disseminated sulfide minerals, mostly pyrrhotite and Cu-Fe sulfides, are hosted by clinopyroxene-bearing troctolites. Carbonate minerals are scarce to non-existent. Long-term simulations of up to 20 years of weathering of tailings used two different sets of rate constants: one based on published laboratory single-mineral dissolution experiments, and one based on leaching experiments using bulk material from the Duluth Complex conducted by the Minnesota Department of Natural Resources (MNDNR). The simulations included only plagioclase, olivine, clinopyroxene, pyrrhotite, and water as starting phases. Dissolved oxygen concentrations were assumed to be in equilibrium with atmospheric oxygen. The simulations based on the published single-mineral rate constants predicted that pyrrhotite would be effectively exhausted in less than two years and pH would rise accordingly. In contrast, only 20 percent of the pyrrhotite was depleted after two years using the MNDNR rate constants. Predicted pyrrhotite depletion by the simulation based on the MNDNR rate constant matched well with published results of laboratory tests on tailings. Modeling long-term weathering of mine wastes also can provide important insights into secondary reactions that may influence the permeability of tailings and thereby affect weathering behavior. Both models predicted the precipitation of a variety of secondary phases including goethite, gibbsite, and clay (nontronite).

  7. Enhancement of cutaneous delayed hypersensitivity reactions by a single exposure to UV-A or PUVA

    International Nuclear Information System (INIS)

    Moberg, S.; Mobacken, H.

    1982-01-01

    The influence of irradiation with UV-A and PUVA (8-methoxy-psoralen and UV-A) on delayed hypersensitivity reactions to microbial antigens was studied in healthy human individuals. Skin reactions to Candida albicans antigen and PPD were enhanced by UV-A als well as by PUVA compared with nonirradiated tests. A statistically significant difference was reached with UV-A for both antigens. For PUVA, erythemogenic doses to Candida tests produced a significant increase of response. (orig.)

  8. General single phase wellbore flow model

    Energy Technology Data Exchange (ETDEWEB)

    Ouyang, Liang-Biao; Arbabi, S.; Aziz, K.

    1997-02-05

    A general wellbore flow model, which incorporates not only frictional, accelerational and gravitational pressure drops, but also the pressure drop caused by inflow, is presented in this report. The new wellbore model is readily applicable to any wellbore perforation patterns and well completions, and can be easily incorporated in reservoir simulators or analytical reservoir inflow models. Three dimensionless numbers, the accelerational to frictional pressure gradient ratio R{sub af}, the gravitational to frictional pressure gradient ratio R{sub gf}, and the inflow-directional to accelerational pressure gradient ratio R{sub da}, have been introduced to quantitatively describe the relative importance of different pressure gradient components. For fluid flow in a production well, it is expected that there may exist up to three different regions of the wellbore: the laminar flow region, the partially-developed turbulent flow region, and the fully-developed turbulent flow region. The laminar flow region is located near the well toe, the partially-turbulent flow region lies in the middle of the wellbore, while the fully-developed turbulent flow region is at the downstream end or the heel of the wellbore. Length of each region depends on fluid properties, wellbore geometry and flow rate. As the distance from the well toe increases, flow rate in the wellbore increases and the ratios R{sub af} and R{sub da} decrease. Consequently accelerational and inflow-directional pressure drops have the greatest impact in the toe region of the wellbore. Near the well heel the local wellbore flow rate becomes large and close to the total well production rate, here R{sub af} and R{sub da} are small, therefore, both the accelerational and inflow-directional pressure drops can be neglected.

  9. Modelling a singly resonant, intracavity ring optical parametric oscillator

    DEFF Research Database (Denmark)

    Buchhave, Preben; Tidemand-Lichtenberg, Peter; Wei, Hou

    2003-01-01

    We study theoretically and experimentally the dynamics of a single-frequency, unidirectional ring laser with an intracavity nonlinear singly resonant OPO-crystal in a coupled resonator. We find for a range of operating conditions good agreement between model results and measurements of the laser...

  10. Homology modelling and bivalent single-chain Fv construction of ...

    Indian Academy of Sciences (India)

    Homology modelling and bivalent single-chain Fv construction of anti-HepG2 single-chain immunoglobulin Fv fragments from a phage display library ... Department of Infectious Diseases, Tongji Hospital, Tongji Medical College, Huazhong University of Science and Technology, Wuhan 430030, China; Department of ...

  11. DL-ADR: a novel deep learning model for classifying genomic variants into adverse drug reactions.

    Science.gov (United States)

    Liang, Zhaohui; Huang, Jimmy Xiangji; Zeng, Xing; Zhang, Gang

    2016-08-10

    Genomic variations are associated with the metabolism and the occurrence of adverse reactions of many therapeutic agents. The polymorphisms on over 2000 locations of cytochrome P450 enzymes (CYP) due to many factors such as ethnicity, mutations, and inheritance attribute to the diversity of response and side effects of various drugs. The associations of the single nucleotide polymorphisms (SNPs), the internal pharmacokinetic patterns and the vulnerability of specific adverse reactions become one of the research interests of pharmacogenomics. The conventional genomewide association studies (GWAS) mainly focuses on the relation of single or multiple SNPs to a specific risk factors which are a one-to-many relation. However, there are no robust methods to establish a many-to-many network which can combine the direct and indirect associations between multiple SNPs and a serial of events (e.g. adverse reactions, metabolic patterns, prognostic factors etc.). In this paper, we present a novel deep learning model based on generative stochastic networks and hidden Markov chain to classify the observed samples with SNPs on five loci of two genes (CYP2D6 and CYP1A2) respectively to the vulnerable population of 14 types of adverse reactions. A supervised deep learning model is proposed in this study. The revised generative stochastic networks (GSN) model with transited by the hidden Markov chain is used. The data of the training set are collected from clinical observation. The training set is composed of 83 observations of blood samples with the genotypes respectively on CYP2D6*2, *10, *14 and CYP1A2*1C, *1 F. The samples are genotyped by the polymerase chain reaction (PCR) method. A hidden Markov chain is used as the transition operator to simulate the probabilistic distribution. The model can perform learning at lower cost compared to the conventional maximal likelihood method because the transition distribution is conditional on the previous state of the hidden Markov

  12. Single particle degrees of freedom in the interacting boson model

    NARCIS (Netherlands)

    Scholten, O.

    1985-01-01

    An overview is given of different aspects of the Interacting Boson Fermion Model, the extension of the interacting Boson Model to odd mass nuclei. The microscopic model for the coupling of single-particle degrees of freedom to the system of bosons is outlined and the interaction between the bosons

  13. Atmospheric reaction systems as null-models to identify structural traces of evolution in metabolism.

    Directory of Open Access Journals (Sweden)

    Petter Holme

    Full Text Available The metabolism is the motor behind the biological complexity of an organism. One problem of characterizing its large-scale structure is that it is hard to know what to compare it to. All chemical reaction systems are shaped by the same physics that gives molecules their stability and affinity to react. These fundamental factors cannot be captured by standard null-models based on randomization. The unique property of organismal metabolism is that it is controlled, to some extent, by an enzymatic machinery that is subject to evolution. In this paper, we explore the possibility that reaction systems of planetary atmospheres can serve as a null-model against which we can define metabolic structure and trace the influence of evolution. We find that the two types of data can be distinguished by their respective degree distributions. This is especially clear when looking at the degree distribution of the reaction network (of reaction connected to each other if they involve the same molecular species. For the Earth's atmospheric network and the human metabolic network, we look into more detail for an underlying explanation of this deviation. However, we cannot pinpoint a single cause of the difference, rather there are several concurrent factors. By examining quantities relating to the modular-functional organization of the metabolism, we confirm that metabolic networks have a more complex modular organization than the atmospheric networks, but not much more. We interpret the more variegated modular arrangement of metabolism as a trace of evolved functionality. On the other hand, it is quite remarkable how similar the structures of these two types of networks are, which emphasizes that the constraints from the chemical properties of the molecules has a larger influence in shaping the reaction system than does natural selection.

  14. Mixture of Regression Models with Single-Index

    OpenAIRE

    Xiang, Sijia; Yao, Weixin

    2016-01-01

    In this article, we propose a class of semiparametric mixture regression models with single-index. We argue that many recently proposed semiparametric/nonparametric mixture regression models can be considered special cases of the proposed model. However, unlike existing semiparametric mixture regression models, the new pro- posed model can easily incorporate multivariate predictors into the nonparametric components. Backfitting estimates and the corresponding algorithms have been proposed for...

  15. Reaction-diffusion model of hair-bundle morphogenesis.

    Science.gov (United States)

    Jacobo, Adrian; Hudspeth, A J

    2014-10-28

    The hair bundle, an apical specialization of the hair cell composed of several rows of regularly organized stereocilia and a kinocilium, is essential for mechanotransduction in the ear. Its precise organization allows the hair bundle to convert mechanical stimuli to electrical signals; mutations that alter the bundle's morphology often cause deafness. However, little is known about the proteins involved in the process of morphogenesis and how the structure of the bundle arises through interactions between these molecules. We present a mathematical model based on simple reaction-diffusion mechanisms that can reproduce the shape and organization of the hair bundle. This model suggests that the boundary of the cell and the kinocilium act as signaling centers that establish the bundle's shape. The interaction of two proteins forms a hexagonal Turing pattern--a periodic modulation of the concentrations of the morphogens, sustained by local activation and long-range inhibition of the reactants--that sets a blueprint for the location of the stereocilia. Finally we use this model to predict how different alterations to the system might impact the shape and organization of the hair bundle.

  16. Theoretical intercomparison of multi-step direct reaction models and computational intercomparison of multi-step direct reaction models

    International Nuclear Information System (INIS)

    Koning, A.J.

    1992-08-01

    In recent years several statistical theories have been developed concerning multistep direct (MSD) nuclear reactions. In addition, dominant in applications is a whole class of semiclassical models that may be subsumed under the heading of 'generalized exciton models'. These are basically MSD-type extensions on top of compound-like concepts. In this report the relationship between their underlying statistical MSD-postulates is highlighted. A command framework is outlined that enables to generate the various MSD theories through assigning statistical properties to different parts of the nuclear Hamiltonian. Then it is shown that distinct forms of nuclear randomness are embodied in the mentioned theories. All these theories appear to be very similar at a qualitative level. In order to explain the high energy-tails and forward-peaked angular distribution typical for particles emitted in MSD reactions, it is imagined that the incident continuum particle stepwise looses its energy and direction in a sequence of collisions, thereby creating new particle-hole pairs in the target system. At each step emission may take place. The statistical aspect comes in because many continuum states are involved in the process. These are supposed to display chaotic behavior, the associated randomness assumption giving rise to important simplifications in the expression for MSD emission cross sections. This picture suggests that mentioned MSD models can be interpreted as a variant of essentially one and the same theory. However, this appears not to be the case. To show this usual MSD distinction within the composite reacting nucleus between the fast continuum particle and the residual interactions, the nucleons of the residual core are to be distinguished from those of the leading particle with the residual system. This distinction will turn out to be crucial to present analysis. 27 refs.; 5 figs.; 1 tab

  17. Global Asymptotic Stability for Discrete Single Species Population Models

    Directory of Open Access Journals (Sweden)

    A. Bilgin

    2017-01-01

    Full Text Available We present some basic discrete models in populations dynamics of single species with several age classes. Starting with the basic Beverton-Holt model that describes the change of single species we discuss its basic properties such as a convergence of all solutions to the equilibrium, oscillation of solutions about the equilibrium solutions, Allee’s effect, and Jillson’s effect. We consider the effect of the constant and periodic immigration and emigration on the global properties of Beverton-Holt model. We also consider the effect of the periodic environment on the global properties of Beverton-Holt model.

  18. [Incidence rate of adverse reaction/event by Qingkailing injection: a Meta-analysis of single rate].

    Science.gov (United States)

    Ai, Chun-ling; Xie, Yan-ming; Li, Ming-quan; Wang, Lian-xin; Liao, Xing

    2015-12-01

    To systematically review the incidence rate of adverse drug reaction/event by Qingkailing injection. Such databases as the PubMed, EMbase, the Cochrane library, CNKI, VIP WanFang data and CBM were searched by computer from foundation to July 30, 2015. Two reviewers independently screened literature according to the inclusion and exclusion criteria, extracted data and cross check data. Then, Meta-analysis was performed by using the R 3.2.0 software, subgroup sensitivity analysis was performed based on age, mode of medicine, observation time and research quality. Sixty-three studies involving 9,793 patients with Qingkailing injection were included, 367 cases of adverse reactions/events were reported in total. The incidence rate of adverse reaction in skin and mucosa group was 2% [95% CI (0.02; 0.03)]; the digestive system adverse reaction was 6% [95% CI(0.05; 0.07); the injection site adverse reaction was 4% [95% CI (0.02; 0.07)]. In the digestive system as the main types of adverse reactions/events, incidence of children and adults were 4.6% [0.021 1; 0.097 7] and 6.9% [0.053 5; 0.089 8], respectively. Adverse reactions to skin and mucous membrane damage as the main performance/event type, the observation time > 7 days and ≤ 7 days incidence of 3% [0.012 9; 0.068 3] and 1.9% [0.007 8; 0.046 1], respectively. Subgroup analysis showed that different types of adverse reactions, combination in the incidence of adverse reactions/events were higher than that of single drug, the difference was statistically significant (P reactions occur, and clinical rational drug use, such as combination, age and other fators, and the influence factors vary in different populations. Therefore, clinical doctors for children and the elderly use special care was required for a clear and open spirit injection, the implementation of individualized medication.

  19. Variance Function Partially Linear Single-Index Models1.

    Science.gov (United States)

    Lian, Heng; Liang, Hua; Carroll, Raymond J

    2015-01-01

    We consider heteroscedastic regression models where the mean function is a partially linear single index model and the variance function depends upon a generalized partially linear single index model. We do not insist that the variance function depend only upon the mean function, as happens in the classical generalized partially linear single index model. We develop efficient and practical estimation methods for the variance function and for the mean function. Asymptotic theory for the parametric and nonparametric parts of the model is developed. Simulations illustrate the results. An empirical example involving ozone levels is used to further illustrate the results, and is shown to be a case where the variance function does not depend upon the mean function.

  20. Winkler's single-parameter subgrade model from the perspective of ...

    African Journals Online (AJOL)

    ... tensor are taken into consideration, whereas the shear stresses are intentionally dropped with the purpose of providing a useful perspective, with which Winkler's model and its associated coefficient of subgrade reaction can be viewed. The formulation takes into account the variation of the elasticity modulus with depth.

  1. Model reactions and natural occurrence of furans from hypersaline environments

    Directory of Open Access Journals (Sweden)

    T. Krause

    2014-05-01

    Full Text Available Volatile organic compounds like furan and its derivatives are important for atmospheric properties and reactions. In this work the known abiotic formation of furan from catechol under Fenton-like conditions with Fe3+ sulfate was revised by the use of a bispidine Fe2+ complex as a model compound for iron with well-known characteristics. While total yields were comparable to those with the Fe3+ salt, the bispidine Fe2+ complex is a better catalyst as the turnover numbers of the active iron species were higher. Additionally, the role of iron and pH is discussed in relation to furan formation from model compounds and in natural sediment and water samples collected from the Dead Sea and several salt lakes in Western Australia. Various alkylated furans and even traces of halogenated furans (3-chlorofuran and 3-bromofuran were found in some Australian samples. 3-chlorofuran was found in three sediments and four water samples, whereas 3-bromofuran was detected in three water samples. Further, the emission of furans is compared to the abundance of several possible precursors such as isoprene and aromatic hydrocarbons as well as to the related thiophenes. It is deduced that the emissions of volatile organic compounds such as furans contribute to the formation of ultra-fine particles in the vicinity of salt lakes and are important for the local climate.

  2. Monodisperse Picoliter Droplets for Low-Bias and Contamination-Free Reactions in Single-Cell Whole Genome Amplification.

    Directory of Open Access Journals (Sweden)

    Yohei Nishikawa

    Full Text Available Whole genome amplification (WGA is essential for obtaining genome sequences from single bacterial cells because the quantity of template DNA contained in a single cell is very low. Multiple displacement amplification (MDA, using Phi29 DNA polymerase and random primers, is the most widely used method for single-cell WGA. However, single-cell MDA usually results in uneven genome coverage because of amplification bias, background amplification of contaminating DNA, and formation of chimeras by linking of non-contiguous chromosomal regions. Here, we present a novel MDA method, termed droplet MDA, that minimizes amplification bias and amplification of contaminants by using picoliter-sized droplets for compartmentalized WGA reactions. Extracted DNA fragments from a lysed cell in MDA mixture are divided into 105 droplets (67 pL within minutes via flow through simple microfluidic channels. Compartmentalized genome fragments can be individually amplified in these droplets without the risk of encounter with reagent-borne or environmental contaminants. Following quality assessment of WGA products from single Escherichia coli cells, we showed that droplet MDA minimized unexpected amplification and improved the percentage of genome recovery from 59% to 89%. Our results demonstrate that microfluidic-generated droplets show potential as an efficient tool for effective amplification of low-input DNA for single-cell genomics and greatly reduce the cost and labor investment required for determination of nearly complete genome sequences of uncultured bacteria from environmental samples.

  3. Numerical model of spray combustion in a single cylinder diesel engine

    Science.gov (United States)

    Acampora, Luigi; Sequino, Luigi; Nigro, Giancarlo; Continillo, Gaetano; Vaglieco, Bianca Maria

    2017-11-01

    A numerical model is developed for predicting the pressure cycle from Intake Valve Closing (IVC) to the Exhaust Valve Opening (EVO) events. The model is based on a modified one-dimensional (1D) Musculus and Kattke spray model, coupled with a zero-dimensional (0D) non-adiabatic transient Fed-Batch reactor model. The 1D spray model provides an estimate of the fuel evaporation rate during the injection phenomenon, as a function of time. The 0D Fed-Batch reactor model describes combustion. The main goal of adopting a 0D (perfectly stirred) model is to use highly detailed reaction mechanisms for Diesel fuel combustion in air, while keeping the computational cost as low as possible. The proposed model is validated by comparing its predictions with experimental data of pressure obtained from an optical single cylinder Diesel engine.

  4. Reaction plane angle dependence of dihadron azimuthal correlations from a multiphase transport model calculation

    International Nuclear Information System (INIS)

    Li, W.; Zhang, S.; Ma, Y. G.; Cai, X. Z.; Chen, J. H.; Ma, G. L.; Zhong, C.; Huang, H. Z.

    2009-01-01

    Dihadron azimuthal angle correlations relative to the reaction plane have been investigated in Au+Au collisions at √(s NN )=200 GeV using a multiphase transport model (AMPT). Such reaction plane azimuthal-angle-dependent correlations can shed light on the path-length effect of energy loss of high-transverse-momentum particles propagating through a hot dense medium. The correlations vary with the trigger particle azimuthal angle with respect to the reaction plane direction, φ s =φ T -Ψ EP , which is consistent with the experimental observation by the STAR Collaboration. The dihadron azimuthal angle correlation functions on the away side of the trigger particle present a distinct evolution from a single-peak to a broad, possibly double-peak structure when the trigger particle direction goes from in-plane to out-of-plane with the reaction plane. The away-side angular correlation functions are asymmetric with respect to the back-to-back direction in some regions of φ s , which could provide insight into the testing v 1 method for reconstructing the reaction plane. In addition, both the root-mean-square width (W rms ) of the away-side correlation distribution and the splitting parameter (D) between the away-side double peaks increase slightly with φ s , and the average transverse momentum of away-side-associated hadrons shows a strong φ s dependence. Our results indicate that a strong parton cascade and resultant energy loss could play an important role in the appearance of a double-peak structure in the dihadron azimuthal angular correlation function on the away side of the trigger particle.

  5. A comprehensive model to determine the effects of temperature and species fluctuations on reaction rates in turbulent reaction flows

    Science.gov (United States)

    Magnotti, F.; Diskin, G.; Matulaitis, J.; Chinitz, W.

    1984-01-01

    The use of silane (SiH4) as an effective ignitor and flame stabilizing pilot fuel is well documented. A reliable chemical kinetic mechanism for prediction of its behavior at the conditions encountered in the combustor of a SCRAMJET engine was calculated. The effects of hydrogen addition on hydrocarbon ignition and flame stabilization as a means for reduction of lengthy ignition delays and reaction times were studied. The ranges of applicability of chemical kinetic models of hydrogen-air combustors were also investigated. The CHARNAL computer code was applied to the turbulent reaction rate modeling.

  6. Modeling non-adiabatic photoexcited reaction dynamics in condensed phases

    International Nuclear Information System (INIS)

    Coker, D.F.

    2003-01-01

    Reactions of photoexcited molecules, ions, and radicals in condensed phase environments involve non-adiabatic dynamics over coupled electronic surfaces. We focus on how local environmental symmetries can effect non-adiabatic coupling between excited electronic states and thus influence, in a possibly controllable way, the outcome of photo-excited reactions. Semi-classical and mixed quantum-classical non-adiabatic molecular dynamics methods, together with semi-empirical excited state potentials are used to probe the dynamical mixing of electronic states in different environments from molecular clusters, to simple liquids and solids, and photo-excited reactions in complex reaction environments such as zeolites

  7. Reaction of the (111) faces of single-crystal indium phosphide with alkylating agents: evidence for selective reaction of the p-rich face

    Energy Technology Data Exchange (ETDEWEB)

    Spool, A.M.; Daube, K.A.; Mallouk, T.E.; Belmont, J.A.; Wrighton, M.S.

    1986-05-28

    We wish to report that the P-rich, (111)B, face of single-crystal InP, but not the In-rich, (111)A, face of the same crystal, reacts with molecular reagents to yield surface-bound material derived from the apparent alkylation of a surface P atom. Exploitation of surface functional groups has been demonstrated to be very important in the attachment of molecular reagents and polymers to electrode surfaces. Electrodes derivatized with molecules have potential uses in analysis, fuel cells, electrosynthetic cells, and photoelectrochemical cells. We now wish to present evidence showing that an important photoelectrode material, InP, can be functionalized with molecules by reaction of the P-rich, (111)B, face with alkylating reagents.

  8. Planning Single-Event Nutrition Education: A New Model

    Science.gov (United States)

    Brown, Lora Beth

    2011-01-01

    A theoretical model for planning single-event nutrition education contrasts a Practical, Foods, and Positive (PFP) emphasis to an Abstract, Nutrient, and Negative (ANN) focus on nutrition topics. Use of this model makes messages more appealing to consumers and may increase the likelihood that people will apply the nutrition information in their…

  9. Molecular electronics of a single photosystem I reaction center: Studies with scanning tunneling microscopy and spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Lee, I.; Lee, J.W.; Warmack, R.J.; Allison, D.P.; Greenbaum, E. [Oak Ridge National Lab., TN (United States)

    1995-03-14

    Thylakoids and photosystem I (PSI) reaction centers were imaged by scanning tunneling microscopy. The thylakoids were isolated from spinach chloroplasts, and PSI reaction centers were extracted from thylakoid membranes. Because thylakoids are relatively thick nonconductors, they were sputter-coated with Pd/Au before imaging. PSI photosynthetic centers and chemically platinized PSI were investigated without sputter-coating. They were mounted on flat gold substrates that had been treated with mercaptoacetic acid to help bind the proteins. With tunneling spectroscopy, the PSI centers displayed a semiconductor-like response with a band gap of 1.8 eV. Lightly platinized (platinized for 1 hr) centers displayed diode-like conduction that resulted in dramatic contrast changes between images taken with opposite bias voltages. The electronic properties of this system were stable under long-term storage. 42 refs., 7 figs.

  10. A single residue controls electron transfer gating in photosynthetic reaction centers

    Czech Academy of Sciences Publication Activity Database

    Shlyk, O.; Samish, I.; Matěnová, M.; Dulebo, A.; Poláková, H.; Kaftan, David; Scherz, A.

    2017-01-01

    Roč. 7, MAR 16 (2017), s. 1-13, č. článku 44580. ISSN 2045-2322 R&D Projects: GA ČR GA15-00703S; GA MŠk(CZ) LO1416 Institutional support: RVO:61388971 Keywords : BACTERIAL REACTION CENTERS * INDUCED STRUCTURAL-CHANGES * ATOMIC-FORCE MICROSCOPE Subject RIV: EE - Microbiology, Virology OBOR OECD: Microbiology Impact factor: 4.259, year: 2016

  11. Single crystal plasticity by modeling dislocation density rate behavior

    Energy Technology Data Exchange (ETDEWEB)

    Hansen, Benjamin L [Los Alamos National Laboratory; Bronkhorst, Curt [Los Alamos National Laboratory; Beyerlein, Irene [Los Alamos National Laboratory; Cerreta, E. K. [Los Alamos National Laboratory; Dennis-Koller, Darcie [Los Alamos National Laboratory

    2010-12-23

    The goal of this work is to formulate a constitutive model for the deformation of metals over a wide range of strain rates. Damage and failure of materials frequently occurs at a variety of deformation rates within the same sample. The present state of the art in single crystal constitutive models relies on thermally-activated models which are believed to become less reliable for problems exceeding strain rates of 10{sup 4} s{sup -1}. This talk presents work in which we extend the applicability of the single crystal model to the strain rate region where dislocation drag is believed to dominate. The elastic model includes effects from volumetric change and pressure sensitive moduli. The plastic model transitions from the low-rate thermally-activated regime to the high-rate drag dominated regime. The direct use of dislocation density as a state parameter gives a measurable physical mechanism to strain hardening. Dislocation densities are separated according to type and given a systematic set of interactions rates adaptable by type. The form of the constitutive model is motivated by previously published dislocation dynamics work which articulated important behaviors unique to high-rate response in fcc systems. The proposed material model incorporates thermal coupling. The hardening model tracks the varying dislocation population with respect to each slip plane and computes the slip resistance based on those values. Comparisons can be made between the responses of single crystals and polycrystals at a variety of strain rates. The material model is fit to copper.

  12. Unravelling the Maillard reaction network by multiresponse kinetic modelling

    NARCIS (Netherlands)

    Martins, S.I.F.S.

    2003-01-01

    The Maillard reaction is an important reaction in food industry. It is responsible for the formation of colour and aroma, as well as toxic compounds as the recent discovered acrylamide. The knowledge of kinetic parameters, such as rate constants and activation energy, is necessary to predict its

  13. Nonlinear variational models for reaction and diffusion systems

    International Nuclear Information System (INIS)

    Tanyi, G.E.

    1983-08-01

    There exists a natural metric w.r.t. which the density dependent diffusion operator is harmonic in the sense of Eells and Sampson. A physical corollary of this statement is the property that any two regular points on the orbit of a reaction or diffusion operator can be connected by a path along which the reaction rate is constant. (author)

  14. Stability Analysis of a Reaction-Diffusion System Modeling Atherogenesis

    KAUST Repository

    Ibragimov, Akif

    2010-01-01

    This paper presents a linear, asymptotic stability analysis for a reaction-diffusionconvection system modeling atherogenesis, the initiation of atherosclerosis, as an inflammatory instability. Motivated by the disease paradigm articulated by Ross, atherogenesis is viewed as an inflammatory spiral with a positive feedback loop involving key cellular and chemical species interacting and reacting within the intimal layer of muscular arteries. The inflammatory spiral is initiated as an instability from a healthy state which is defined to be an equilibrium state devoid of certain key inflammatory markers. Disease initiation is studied through a linear, asymptotic stability analysis of a healthy equilibrium state. Various theorems are proved, giving conditions on system parameters guaranteeing stability of the health state, and a general framework is developed for constructing perturbations from a healthy state that exhibit blow-up, which are interpreted as corresponding to disease initiation. The analysis reveals key features that arterial geometry, antioxidant levels, and the source of inflammatory components (through coupled third-kind boundary conditions or through body sources) play in disease initiation. © 2010 Society for Industrial and Applied Mathematics.

  15. Atmospheric pressure reaction cell for operando sum frequency generation spectroscopy of ultrahigh vacuum grown model catalysts

    Science.gov (United States)

    Roiaz, Matteo; Pramhaas, Verena; Li, Xia; Rameshan, Christoph; Rupprechter, Günther

    2018-04-01

    A new custom-designed ultrahigh vacuum (UHV) chamber coupled to a UHV and atmospheric-pressure-compatible spectroscopic and catalytic reaction cell is described, which allows us to perform IR-vis sum frequency generation (SFG) vibrational spectroscopy during catalytic (kinetic) measurements. SFG spectroscopy is an exceptional tool to study vibrational properties of surface adsorbates under operando conditions, close to those of technical catalysis. This versatile setup allows performing surface science, SFG spectroscopy, catalysis, and electrochemical investigations on model systems, including single crystals, thin films, and deposited metal nanoparticles, under well-controlled conditions of gas composition, pressure, temperature, and potential. The UHV chamber enables us to prepare the model catalysts and to analyze their surface structure and composition by low energy electron diffraction and Auger electron spectroscopy, respectively. Thereafter, a sample transfer mechanism moves samples under UHV to the spectroscopic cell, avoiding air exposure. In the catalytic cell, SFG spectroscopy and catalytic tests (reactant/product analysis by mass spectrometry or gas chromatography) are performed simultaneously. A dedicated sample manipulation stage allows the model catalysts to be examined from LN2 temperature to 1273 K, with gaseous reactants in a pressure range from UHV to atmospheric. For post-reaction analysis, the SFG cell is rapidly evacuated and samples are transferred back to the UHV chamber. The capabilities of this new setup are demonstrated by benchmark results of CO adsorption on Pt and Pd(111) single crystal surfaces and of CO adsorption and oxidation on a ZrO2 supported Pt nanoparticle model catalyst grown by atomic layer deposition.

  16. A Non-Isothermal Chemical Lattice Boltzmann Model Incorporating Thermal Reaction Kinetics and Enthalpy Changes

    Directory of Open Access Journals (Sweden)

    Stuart Bartlett

    2017-08-01

    Full Text Available The lattice Boltzmann method is an efficient computational fluid dynamics technique that can accurately model a broad range of complex systems. As well as single-phase fluids, it can simulate thermohydrodynamic systems and passive scalar advection. In recent years, it also gained attention as a means of simulating chemical phenomena, as interest in self-organization processes increased. This paper will present a widely-used and versatile lattice Boltzmann model that can simultaneously incorporate fluid dynamics, heat transfer, buoyancy-driven convection, passive scalar advection, chemical reactions and enthalpy changes. All of these effects interact in a physically accurate framework that is simple to code and readily parallelizable. As well as a complete description of the model equations, several example systems will be presented in order to demonstrate the accuracy and versatility of the method. New simulations, which analyzed the effect of a reversible reaction on the transport properties of a convecting fluid, will also be described in detail. This extra chemical degree of freedom was utilized by the system to augment its net heat flux. The numerical method outlined in this paper can be readily deployed for a vast range of complex flow problems, spanning a variety of scientific disciplines.

  17. Understanding the Oxygen Reduction Reaction on a Y/Pt(111) Single Crystal

    DEFF Research Database (Denmark)

    Ulrikkeholm, Elisabeth Therese; Johansson, Tobias Peter; Malacrida, Paolo

    2014-01-01

    was significantly different from our initial expectations. In order to understand this phenomenon, we investigated a Y/Pt(111) single crystal, formed by depositing large amounts of Y om Pt(111) under ultra-high vacuum (UHV) conditions and annealing to high temperatures. We subsequently characterised the surface...

  18. Single Cobalt Atoms with Precise N-Coordination as Superior Oxygen Reduction Reaction Catalysts.

    Science.gov (United States)

    Yin, Peiqun; Yao, Tao; Wu, Yuen; Zheng, Lirong; Lin, Yue; Liu, Wei; Ju, Huanxin; Zhu, Junfa; Hong, Xun; Deng, Zhaoxiang; Zhou, Gang; Wei, Shiqiang; Li, Yadong

    2016-08-26

    A new strategy for achieving stable Co single atoms (SAs) on nitrogen-doped porous carbon with high metal loading over 4 wt % is reported. The strategy is based on a pyrolysis process of predesigned bimetallic Zn/Co metal-organic frameworks, during which Co can be reduced by carbonization of the organic linker and Zn is selectively evaporated away at high temperatures above 800 °C. The spherical aberration correction electron microscopy and extended X-ray absorption fine structure measurements both confirm the atomic dispersion of Co atoms stabilized by as-generated N-doped porous carbon. Surprisingly, the obtained Co-Nx single sites exhibit superior ORR performance with a half-wave potential (0.881 V) that is more positive than commercial Pt/C (0.811 V) and most reported non-precious metal catalysts. Durability tests revealed that the Co single atoms exhibit outstanding chemical stability during electrocatalysis and thermal stability that resists sintering at 900 °C. Our findings open up a new routine for general and practical synthesis of a variety of materials bearing single atoms, which could facilitate new discoveries at the atomic scale in condensed materials. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  19. Rutherford backscattering, nuclear reaction and channeling studies of nitrogen implanted single-crystal stainless steel

    International Nuclear Information System (INIS)

    Ferguson, M.M.; Ewan, G.T.; Mitchell, I.V.; Plattner, H.H.

    1983-01-01

    The three different methods were used to investigate a single crystal of stainless steel implanted to different doses by 40 keV 15 N 2 + ions. Conclusions are drawn on the position of nitrogen; comparison is made with implantation of deuterium and neon. (G.Q.)

  20. Studies of Nuclei Close to 132Sn Using Single-Neutron Transfer Reactions

    International Nuclear Information System (INIS)

    Jones, K.L.; Pain, S.D.; Kozub, R.L.; Adekola, Aderemi S.; Bardayan, Daniel W.; Blackmon, Jeff C.; Catford, Wilton N.; Chae, K.Y.; Chipps, K.; Cizewski, J.A.; Erikson, Luke; Gaddis, A.L.; Greife, U.; Grzywacz, R.K.; Harlin, Christopher W.; Hatarik, Robert; Howard, Joshua A.; James, J.; Kapler, R.; Krolas, W.; Liang, J. Felix; Ma, Zhanwen; Matei, Catalin; Moazen, Brian; Nesaraja, Caroline D.; O'Malley, Patrick; Patterson, N.P.; Paulauskas, Stanley; Shapira, Dan; Shriner, J.F. Jr.; Sikora, M.; Sissom, D.J.; Smith, Michael Scott; Swan, T.P.; Thomas, J.S.; Wilson, Gemma L.

    2009-01-01

    Neutron transfer reactions were performed in inverse kinematics using radioactive ion beams of 132Sn, 130Sn, and 134Te and deuterated polyethylene targets. Preliminary results are presented. The Q-value spectra for 133Sn, 131Sn and 135Te reveal a number of previously unobserved peaks. The angular distributions are compatible with the expected lf7/2 nature of the ground state of 133Sn, and 2p3/2 for the 3.4 MeV state in 131Sn.

  1. Single supplier single retailer inventory model controlled by the reorder and shipping points with sharing information

    Science.gov (United States)

    Ho, Wen-Tsung; Hsiao, Yu-Cheng

    2012-04-01

    This study investigated the integrated stochastic inventory problem for a two-stage supply chain consisting of a single retailer and a single supplier. By using batch shipment policy, the expected total cost can be significantly reduced. An equally sized batch shipment model, controlled by both the reorder and shipping points, with sharing information by enterprise resource planning and radio frequency identification is constructed. The problem is solved optimally by the proposed algorithm that determines the economic lot size, the optimal batch sizes and number of batches. A numerical example is included to illustrate the algorithmic procedures and to prove that the model controlled both by the reorder and shipping points is superior to the classic model controlled only by the reorder point.

  2. Dynamic and reversible self-assembly of photoelectrochemical complexes based on lipid bilayer disks, photosynthetic reaction centers, and single-walled carbon nanotubes.

    Science.gov (United States)

    Boghossian, Ardemis A; Choi, Jong Hyun; Ham, Moon-Ho; Strano, Michael S

    2011-03-01

    An aqueous solution containing photosynthetic reaction centers (RCs), membrane scaffold proteins (MSPs), phospholipids, and single-walled carbon nanotubes (SWCNTs) solubilized with the surfactant sodium cholate (SC) reversibly self-assembles into a highly ordered structure upon dialysis of the latter. The resulting structure is photoelectrochemically active and consists of 4-nm-thick lipid bilayer disks (nanodisks, NDs) arranged parallel to the surface of the SWCNT with the RC housed within the bilayer such that its hole injecting site faces the nanotube surface. The structure can be assembled and disassembled autonomously with the addition or removal of surfactant. We model the kinetic and thermodynamic forces that drive the dynamics of this reversible self-assembly process. The assembly is monitored using spectrofluorimetry during dialysis and subsequent surfactant addition and used to fit a kinetic model to determine the forward and reverse rate constants of ND and ND-SWCNT formation. The calculated ND and ND-SWCNT forward rate constants are 79 mM(-1) s(-1) and 5.4 × 10(2) mM(-1) s(-1), respectively, and the reverse rate constants are negligible over the dialysis time scale. We find that the reaction is not diffusion-controlled since the ND-SWCNT reaction, which consists of entities with smaller diffusion coefficients, has a larger reaction rate constant. Using these rate parameters, we were able to develop a kinetic phase diagram for the formation of ND-SWCNT complexes, which indicates an optimal dialysis rate of approximately 8 × 10(-4) s(-1). We also fit the model to cyclic ND-SWCNT assembly and disassembly experiments and hence mimic the thermodynamic forces used in regeneration processes detailed previously. Such forces may form the basis of both synthetic and natural photoelectrochemical complexes capable of dynamic component replacement and repair.

  3. Reactions and single-particle structure of nuclei near the drip lines

    International Nuclear Information System (INIS)

    Hansen, P.G.; Sherrill, B.M.

    2001-01-01

    The techniques that have allowed the study of reactions of nuclei situated at or near the neutron or proton drip line are described. Nuclei situated just inside the drip line have low nucleon separation energies and, at most, a few bound states. If the angular momentum in addition is small, large halo states are formed where the wave function of the valency nucleon extends far beyond the nuclear radius. We begin with examples of the properties of nuclear halos and of their study in radioactive-beam experiments. We then turn to the continuum states existing above the particle threshold and also discuss the possibility of exciting them from the halo states in processes that may be thought of as 'collateral damage'. Finally, we show that the experience from studies of halo states has pointed to knockout reactions as a new way to perform spectroscopic studies of more deeply bound non-halo states. Examples are given of measurements of l values and spectroscopic factors

  4. Ares I Reaction Control System Propellant Feedline Decontamination Modeling

    Science.gov (United States)

    Pasch, James J.

    2010-01-01

    The objective of the work presented here is to quantify the effects of purge gas temperature, pressure, and mass flow rate on Hydrazine (Hz) decontamination rates of the Ares I Roll Control System and Reaction Control System. A survey of experts in this field revealed the absence of any decontamination rate prediction models. Three basic decontamination methods were identified for analysis and modeling. These include low pressure eduction, high flow rate purge, and pulse purge. For each method, an approach to predict the Hz mass transfer rate, as a function of system pressure, temperature, and purge gas mass flow rate, is developed based on the applicable physics. The models show that low pressure eduction is two orders of magnitude more effective than the high velocity purge, which in turn is two orders of magnitude more effective than the pure diffusion component of pulse purging of deadheads. Eduction subjects the system to low pressure conditions that promote the extraction of Hz vapors. At 120 F, Hz is saturated at approximately 1 psia. At lower pressures and 120 F, Hz will boil, which is an extremely efficient means to remove liquid Hz. The Hz boiling rate is predicted by equating the rate at which energy is added to the saturated liquid Hz through heaters at the tube outer wall with the energy removed from the liquid through evaporation. Boil-off fluxes were predicted by iterating through the range of local pressures with limits set by the minimum allowed pressure of 0.2 psia and maximum allowed wall temperature of 120 F established by the heaters, which gives a saturation pressure of approximately 1.0 psia. Figure 1 shows the resulting boil-off fluxes as a function of local eduction pressure. As depicted in figure 1, the flux is a strong inverse function of eduction pressure, and that minimizing the eduction pressure maximizes the boil-off flux. Also, higher outer wall temperatures lead to higher boil-off fluxes and allow for boil-off over a greater range

  5. Spectra for the A = 6 reactions calculated from a three-body resonance model

    Directory of Open Access Journals (Sweden)

    Paris Mark W.

    2016-01-01

    Full Text Available We develop a resonance model of the transition matrix for three-body breakup reactions of the A = 6 system and present calculations for the nucleon observed spectra, which are important for inertial confinement fusion and Big Bang nucleosynthesis (BBN. The model is motivated by the Faddeev approach where the form of the T matrix is written as a sum of the distinct Jacobi coordinate systems corresponding to particle configurations (α, n-n and (n; n-α to describe the final state. The structure in the spectra comes from the resonances of the two-body subsystems of the three-body final state, namely the singlet (T = 1 nucleon-nucleon (NN anti-bound resonance, and the Nα resonances designated the ground state (Jπ = 3−2${{{3^ - }} \\over 2}$ and first excited state (Jπ = 1−2${{{1^ - }} \\over 2}$ of the A = 5 systems 5He and 5Li. These resonances are described in terms of single-level, single-channel R-matrix parameters that are taken from analyses of NN and Nα scattering data. While the resonance parameters are approximately charge symmetric, external charge-dependent effects are included in the penetrabilities, shifts, and hard-sphere phases, and in the level energies to account for internal Coulomb differences. The shapes of the resonance contributions to the spectrum are fixed by other, two-body data and the only adjustable parameters in the model are the combinatorial amplitudes for the compound system. These are adjusted to reproduce the observed nucleon spectra from measurements at the Omega and NIF facilities. We perform a simultaneous, least-squares fit of the tt neutron spectra and the 3He3He proton spectra. Using these amplitudes we make a prediction of the α spectra for both reactions at low energies. Significant differences in the tt and 3He3He spectra are due to Coulomb effects.

  6. Wide Temperature Range Kinetics of Elementary Combustion Reactions for Army Models

    National Research Council Canada - National Science Library

    Fontijn, Arthur

    2002-01-01

    The goals of this program are to provide accurate kinetic data on isolated elementary reactions at temperatures relevant to Army combustion models, particularly for propellant combustion dark zones...

  7. Reaction Wheel Disturbance Model Extraction Software, Phase I

    Data.gov (United States)

    National Aeronautics and Space Administration — Reaction wheel disturbances are some of the largest sources of noise on sensitive telescopes. Such wheel-induced mechanical noises are not well characterized....

  8. Reaction Wheel Disturbance Model Extraction Software, Phase II

    Data.gov (United States)

    National Aeronautics and Space Administration — Reaction wheel mechanical noise is one of the largest sources of disturbance forcing on space-based observatories. Such noise arises from mass imbalance, bearing...

  9. An Immunofluorescence-Assisted Microfluidic Single Cell Quantitative Reverse Transcription Polymerase Chain Reaction Analysis of Tumour Cells Separated from Blood

    Directory of Open Access Journals (Sweden)

    Kazunori Hoshino

    2015-11-01

    Full Text Available Circulating tumour cells (CTCs are important indicators of metastatic cancer and may provide critical information for individualized treatment. As CTCs are usually very rare, the techniques to obtain information from very small numbers of cells are crucial. Here, we propose a method to perform a single cell quantitative reverse transcription polymerase chain reaction (qPCR analysis of rare tumour cells. We utilized a microfluidic immunomagnetic assay to separate cancer cells from blood. A combination of detailed immunofluorescence and laser microdissection enabled the precise selection of individual cells. Cancer cells that were spiked into blood were successfully separated and picked up for a single cell PCR analysis. The breast cancer cell lines MCF7, SKBR3 and MDAMB231 were tested with 10 different genes. The result of the single cell analysis matched the results from a few thousand cells. Some markers (e.g., ER, HER2 that are commonly used for cancer identification showed relatively large deviations in expression levels. However, others (e.g., GRB7 showed deviations that are small enough to supplement single cell disease profiling.

  10. Reaction of ethane with deuterium over platinum(111) single-crystal surfaces

    International Nuclear Information System (INIS)

    Zaera, F.; Somorhai, G.A.

    1985-01-01

    Deuterium exchange and hydrogenolysis of ethane were studied over (111) platinum surfaces under atmospheric pressures and a temperature range of 475-625 K. Activation energies of 19 kcal/mol for exchange and 34 kcal/mol for hydrogenolysis were obtained. The exchange reaction rates displayed kinetic orders with respect to deuterium and ethane partial pressures of -0.55 and 1.2, respectively. The exchange production distribution was U-shaped, peaking at one and six deuterium atoms per ethane molecule, similar to results reported for other forms of platinum, e.g., supported, films, and foils. The pressure of ethylidyne moieties on the surface was inferred from low-energy electron diffraction and thermal desorption spectroscopy. A mechanism is proposed to explain the experimental results, in which ethylidyne constitutes an intermediate in one of two competitive pathways. 31 references, 9 figures, 3 tables

  11. A bespoke single-band Hubbard model material

    Science.gov (United States)

    Griffin, S. M.; Staar, P.; Schulthess, T. C.; Troyer, M.; Spaldin, N. A.

    2016-02-01

    The Hubbard model, which augments independent-electron band theory with a single parameter to describe electron-electron correlations, is widely regarded to be the "standard model" of condensed-matter physics. The model has been remarkably successful at addressing a range of correlation phenomena in solids, but it neglects many behaviors that occur in real materials, such as phonons, long-range interactions, and, in its simplest form, multiorbital effects. Here, we use ab initio electronic structure methods to design a material whose Hamiltonian matches as closely as possible that of the single-band Hubbard model. Our motivation is to compare the measured properties of our new material to those predicted by reliable theoretical solutions of the Hubbard model to determine the relevance of the model in the description of real materials. After identifying an appropriate crystal class and several appropriate chemistries, we use density-functional theory and dynamical mean-field theory to screen for the desired electronic band structure and metal-insulator transition. We then explore the most promising candidates for structural stability and suitability for doping, and we propose specific materials for subsequent synthesis. Finally, we identify a regime—that should manifest in our bespoke material—in which the single-band Hubbard model on a triangular lattice exhibits exotic d -wave superconductivity.

  12. Modelling the intra-particle transport phenomena and chemical reactions of olive kernel fast pyrolysis

    Energy Technology Data Exchange (ETDEWEB)

    Zabaniotou, A.; Damartzis, Th. [Department of Chemical Engineering, Aristotle University of Thessaloniki, University Box 455, 24154 Thessaloniki (Greece)

    2007-08-15

    In the present study, the development of a mathematical model for the description of the pyrolysis of a single solid olive kernel particle and the prediction of the fast pyrolysis product yields, is presented. Kinetic model is coupled with heat transfer model. The global degradation of biomass is based on Koufopanos et al. mechanism and described by two parallel 1-order reactions. The analysis is focused on primary degradation for small particle and simulations have been carried out for a spherical particle, with radius of 175 {mu}m. The model has been validated against experiments carried out in a laboratory wire mesh reactor, for temperature range from 573 K to 873 K and a heating rate of 200 K/s. The results of the simulation are in good agreement with the experimental data, regarding temperature, conversion histories and product distribution of olive kernel fast pyrolysis. The numerical method applied was finite difference for the heat transfer model and Runge-Kutta 4th order method for chemical kinetics model equations. (author)

  13. Evaluation of Chemical Kinetic for Mathematics Model Reduction of Cadmium Reaction Rate, Constant and Reaction Orde in to Electrochemical Process

    International Nuclear Information System (INIS)

    Prayitno

    2007-01-01

    The experiment was reduction of cadmium rate with electrochemical influenced by time process, concentration, current strength and type of electrode plate. The aim of the experiment was to know the influence, mathematic model reduction of cadmium the reaction rate, reaction rate constant and reaction orde influenced by time process, concentration, current strength and type of electrode plate. Result of research indicate the time processing if using plate of copper electrode is during 30 minutes and using plate of aluminium electrode is during 20 minutes. Condition of strong current that used in process of electrochemical is only 0.8 ampere and concentration effective is 5.23 mg/l. The most effective type Al of electrode plate for reduction from waste and the efficiency of reduction is 98 %. (author)

  14. Model tests on single piles in soft clay

    Energy Technology Data Exchange (ETDEWEB)

    Pan, J.L. [Durham Univ., Durham, (United Kingdom). School of Engineering; Goh, A.T.C.; Wong, K.S.; Teh, C.I. [Nanyang Technological Univ., (Singapore). Geotechnical Research Centre

    2000-08-04

    The behaviour of single stainless steel piles subjected to lateral soft clay soil movement was investigated in laboratory model tests in an effort to determine the ultimate soil pressure acting along the pile shaft. A custom designed apparatus was manufactured and calibrated for the test which measured the limiting soil pressures acting along the model pile shaft. The ultimate soil pressure was determined based on the maximum value of this measurement. The results show that the ultimate soil pressure for single passive piles was about 10 times the undrained shear strength, and the magnitude of the soil translation needed to fully mobilize the ultimate soil pressure on the single passive piles was about half the pile width. Further experimental study is needed to examine the effects of the pile end fixity, flexibility and shape and to confirm the effects of sample size and the disturbance due to soil sample preparation. 17 refs., 10 figs.

  15. On the Predictiveness of Single-Field Inflationary Models

    CERN Document Server

    Burgess, C.P.; Trott, Michael

    2014-01-01

    We re-examine the predictiveness of single-field inflationary models and discuss how an unknown UV completion can complicate determining inflationary model parameters from observations, even from precision measurements. Besides the usual naturalness issues associated with having a shallow inflationary potential, we describe another issue for inflation, namely, unknown UV physics modifies the running of Standard Model (SM) parameters and thereby introduces uncertainty into the potential inflationary predictions. We illustrate this point using the minimal Higgs Inflationary scenario, which is arguably the most predictive single-field model on the market, because its predictions for $A_s$, $r$ and $n_s$ are made using only one new free parameter beyond those measured in particle physics experiments, and run up to the inflationary regime. We find that this issue can already have observable effects. At the same time, this UV-parameter dependence in the Renormalization Group allows Higgs Inflation to occur (in prin...

  16. A variable reaction rate model for chlorine decay in drinking water due to the reaction with dissolved organic matter.

    Science.gov (United States)

    Hua, Pei; Vasyukova, Ekaterina; Uhl, Wolfgang

    2015-05-15

    A second order kinetic model for simulating chlorine decay in bulk water due to the reaction with dissolved organic matter (DOM) was developed. It takes into account the decreasing reactivity of dissolved organic matter using a variable reaction rate coefficient (VRRC) which decreases with an increasing conversion. The concentration of reducing species is surrogated by the maximum chlorine demand. Temperature dependency, respectively, is described by the Arrhenius-relationship. The accuracy and adequacy of the proposed model to describe chlorine decay in bulk water were evaluated and shown for very different waters and different conditions such as water mixing or rechlorination by applying statistical tests. It is thus very well suited for application in water quality modeling for distribution systems. Copyright © 2015 Elsevier Ltd. All rights reserved.

  17. The reaction of lithium metal vapor with single walled carbon nanotubes of large diameters

    Czech Academy of Sciences Publication Activity Database

    Kalbáč, Martin; Kavan, Ladislav; Dunsch, L.

    2009-01-01

    Roč. 246, 11-12 (2009), s. 2428-2431 ISSN 0370-1972 R&D Projects: GA AV ČR IAA400400911; GA AV ČR KAN200100801; GA AV ČR IAA400400804; GA ČR GC203/07/J067; GA MŠk LC510 Institutional research plan: CEZ:AV0Z40400503 Keywords : lithium * single walled carbon nanotubes * Raman spectroscopy Subject RIV: CG - Electrochemistry Impact factor: 1.150, year: 2009

  18. Single-particle spectral density of the Hubbard model

    NARCIS (Netherlands)

    Mehlig, B.; Eskes, H.; Hayn, R.; Meinders, M.B.J.

    1995-01-01

    We calculate the single-particle spectral function for the Hubbard model within the framework of a projection technique equivalent to the two-pole approximation. We show that the two-pole approximation can be well understood as an average characterization of the upper and the lower Hubbard bands,

  19. SINGLE-PARTICLE SPECTRAL DENSITY OF THE HUBBARD-MODEL

    NARCIS (Netherlands)

    MEHLIG, B; ESKES, H; HAYN, R; MEINDERS, MBJ

    1995-01-01

    We calculate the single-particle spectral function for the Hubbard model within the framework of a projection technique equivalent to the two-pole approximation. We show that the two-pole approximation can be well understood as an average characterization of the upper and the lower Hubbard bands,

  20. A single product perishing inventory model with demand interaction ...

    African Journals Online (AJOL)

    The paper describes a single perishing product inventory model in which items deteriorate in two phases and then perish. An independent demand takes place at constant rates for items in both phases. A demand for an item in Phase I not satisfied may be satisfied by an item in Phase II, based on a probability measure.

  1. Effective single scattering albedo estimation using regional climate model

    CSIR Research Space (South Africa)

    Tesfaye, M

    2011-09-01

    Full Text Available In this study, by modifying the optical parameterization of Regional Climate model (RegCM), the authors have computed and compared the Effective Single-Scattering Albedo (ESSA) which is a representative of VIS spectral region. The arid, semi...

  2. Interpolation solution of the single-impurity Anderson model

    International Nuclear Information System (INIS)

    Kuzemsky, A.L.

    1990-10-01

    The dynamical properties of the single-impurity Anderson model (SIAM) is studied using a novel Irreducible Green's Function method (IGF). The new solution for one-particle GF interpolating between the strong and weak correlation limits is obtained. The unified concept of relevant mean-field renormalizations is indispensable for strong correlation limit. (author). 21 refs

  3. Ligand-tailored single-site silica supported titanium catalysts: Synthesis, characterization and towards cyanosilylation reaction

    Science.gov (United States)

    Xu, Wei; Li, Yani; Yu, Bo; Yang, Jindou; Zhang, Ying; Chen, Xi; Zhang, Guofang; Gao, Ziwei

    2015-01-01

    A successive anchoring of Ti(NMe2)4, cyclopentadiene and a O-donor ligand, 1-hydroxyethylbenzene (PEA), 1,1‧-bi-2-naphthol (Binol) or 2,3-dihydroxybutanedioic acid diethyl ester (Tartrate), on silica was conducted by SOMC strategy in moderate conditions. The silica, monitored by in-situ Fourier transform infrared spectroscopy (in-situ FT-IR), was pretreated at different temperatures (200, 500 and 800 °C). The ligand tailored silica-supported titanium complexes were characterized by in-situ FT-IR, 13C CP MAS-NMR, X-ray photoelectron spectroscopy (XPS), X-ray absorption near edge structure (XANES) and elemental analysis in detail, verifying that the surface titanium species are single sited. The catalytic activity of the ligand tailored single-site silica supported titanium complexes was evaluated by a cyanosilylation of benzaldehyde. The results showed that the catalytic activity is dependent strongly on the dehydroxylation temperatures of silica and the configuration of the ligands.

  4. Modeling Rabbit Responses to Single and Multiple Aerosol ...

    Science.gov (United States)

    Journal Article Survival models are developed here to predict response and time-to-response for mortality in rabbits following exposures to single or multiple aerosol doses of Bacillus anthracis spores. Hazard function models were developed for a multiple dose dataset to predict the probability of death through specifying dose-response functions and the time between exposure and the time-to-death (TTD). Among the models developed, the best-fitting survival model (baseline model) has an exponential dose-response model with a Weibull TTD distribution. Alternative models assessed employ different underlying dose-response functions and use the assumption that, in a multiple dose scenario, earlier doses affect the hazard functions of each subsequent dose. In addition, published mechanistic models are analyzed and compared with models developed in this paper. None of the alternative models that were assessed provided a statistically significant improvement in fit over the baseline model. The general approach utilizes simple empirical data analysis to develop parsimonious models with limited reliance on mechanistic assumptions. The baseline model predicts TTDs consistent with reported results from three independent high-dose rabbit datasets. More accurate survival models depend upon future development of dose-response datasets specifically designed to assess potential multiple dose effects on response and time-to-response. The process used in this paper to dev

  5. Versatile Gap Mode Plasmon under ATR Geometry towards Single Molecule Raman, Laser Trapping and Photocatalytic Reactions.

    Science.gov (United States)

    Futamata, Masayuki; Akai, Keitaro; Iida, Chiaki; Akiba, Natsumi

    2017-01-01

    We have investigated various aspects of a gap mode plasmon to establish it as an analytical tool. First, markedly large (10 7 - 10 9 ) enhancement factors for the Raman scattering intensity from a thiophenol (TP) monolayer sandwiched by Ag films on a prism and silver nanoparticles (AgNPs) were obtained under attenuated total reflection (ATR) geometry. Second, AgNPs with a radius of ∼20 nm were optically trapped and immobilized on TP-covered Ag films under a gap mode resonance with extremely weak laser power density of ∼1 μW/μm 2 at 532 nm. The observed optical trapping and immobilization were theoretically rationalized using a dipole-dipole coupling and van der Waals interaction between AgNPs and Ag films. Third, p-alkyl TP molecules such as p-methyl TP, p-ethyl TP, p-isopropyl TP, and p-tertiary butyl TP were photocatalytically oxidized into p-carboxyl TP, whereas o- and m-methyl TP did not show such reactions.

  6. Random incidence absorption coefficients of porous absorbers based on local and extended reaction models

    DEFF Research Database (Denmark)

    Jeong, Cheol-Ho

    2011-01-01

    resistivity and the absorber thickness on the difference between the two surface reaction models are examined and discussed. For a porous absorber backed by a rigid surface, the local reaction models give errors of less than 10% if the thickness exceeds 120 mm for a flow resistivity of 5000 Nm-4s. As the flow......Room surfaces have been extensively modeled as locally reacting in room acoustic predictions although such modeling could yield significant errors under certain conditions. Therefore, this study aims to propose a guideline for adopting the local reaction assumption by comparing predicted random...... incidence acoustical characteristics of typical building elements made of porous materials assuming extended and local reaction. For each surface reaction, five well-established wave propagation models, the Delany-Bazley, Miki, Beranek, Allard-Champoux, and Biot model, are employed. Effects of the flow...

  7. Single-site SBA-15 supported zirconium catalysts. Synthesis, characterization and toward cyanosilylation reaction

    International Nuclear Information System (INIS)

    Xu, Wei; Yu, Bo; Zhang, Ying; Chen, Xi; Zhang, Guofang; Gao, Ziwei

    2015-01-01

    Graphical abstract: Ligand-modified signal-site SBA-15 supported zirconium catalysts were synthesized by SOMC method and characterized by a variety of techniques. The zirconium surface complexes show high catalytic efficiency for cyanosilylation of benzaldehyde. - Highlights: • Some Zr active species have been anchored on the surface of SBA-15 by SOMC technique. • The structures of the Zr species have been characterized by a variety of techniques. • The anchored Zr species are single-sited surface complexes. • The Zr surface complexes are catalytic active for cyanosilylation of benzaldehyde. - Abstract: A successive anchoring of Zr(NMe 2 ) 4 , cyclopentadiene and a O-donor ligand, 1-hydroxyethylbenzene (PEA), 1,1′-bi-2-naphthol (Binol) or 2,3-dihydroxybutanedioic acid diethyl ester (Tartrate), on dehydroxylated SBA-15 pretreated at 500 °C for 16 h (SBA-15 -500 ) was conducted by SOMC strategy in moderate conditions. The dehydoxylation of SBA-15 was monitored by in situ Fourier transform infrared spectroscopy (in situ FT-IR). The ligand-modified SBA-15 -500 supported zirconium complexes were characterized by in situ FT-IR, 13 C CP MAS-NMR, X-ray photoelectron spectroscopy (XPS), inductively coupled plasma mass spectrometry (ICP-MAS) and elemental analysis in detail, verifying that the surface zirconium species are single-sited. The catalytic activity of these complexes was evaluated by cyanosilylation of benzaldehyde. The results showed that the catalytic activity is dependent strongly on the structure of surface species and the configuration of the ligands

  8. Single-site SBA-15 supported zirconium catalysts. Synthesis, characterization and toward cyanosilylation reaction

    Energy Technology Data Exchange (ETDEWEB)

    Xu, Wei; Yu, Bo; Zhang, Ying; Chen, Xi; Zhang, Guofang, E-mail: gfzhang@snnu.edu.cn; Gao, Ziwei, E-mail: zwgao@snnu.edu.cn

    2015-01-15

    Graphical abstract: Ligand-modified signal-site SBA-15 supported zirconium catalysts were synthesized by SOMC method and characterized by a variety of techniques. The zirconium surface complexes show high catalytic efficiency for cyanosilylation of benzaldehyde. - Highlights: • Some Zr active species have been anchored on the surface of SBA-15 by SOMC technique. • The structures of the Zr species have been characterized by a variety of techniques. • The anchored Zr species are single-sited surface complexes. • The Zr surface complexes are catalytic active for cyanosilylation of benzaldehyde. - Abstract: A successive anchoring of Zr(NMe{sub 2}){sub 4}, cyclopentadiene and a O-donor ligand, 1-hydroxyethylbenzene (PEA), 1,1′-bi-2-naphthol (Binol) or 2,3-dihydroxybutanedioic acid diethyl ester (Tartrate), on dehydroxylated SBA-15 pretreated at 500 °C for 16 h (SBA-15{sub -500}) was conducted by SOMC strategy in moderate conditions. The dehydoxylation of SBA-15 was monitored by in situ Fourier transform infrared spectroscopy (in situ FT-IR). The ligand-modified SBA-15{sub -500} supported zirconium complexes were characterized by in situ FT-IR, {sup 13}C CP MAS-NMR, X-ray photoelectron spectroscopy (XPS), inductively coupled plasma mass spectrometry (ICP-MAS) and elemental analysis in detail, verifying that the surface zirconium species are single-sited. The catalytic activity of these complexes was evaluated by cyanosilylation of benzaldehyde. The results showed that the catalytic activity is dependent strongly on the structure of surface species and the configuration of the ligands.

  9. Parameter Estimation for Single Diode Models of Photovoltaic Modules

    Energy Technology Data Exchange (ETDEWEB)

    Hansen, Clifford [Sandia National Lab. (SNL-NM), Albuquerque, NM (United States). Photovoltaic and Distributed Systems Integration Dept.

    2015-03-01

    Many popular models for photovoltaic system performance employ a single diode model to compute the I - V curve for a module or string of modules at given irradiance and temperature conditions. A single diode model requires a number of parameters to be estimated from measured I - V curves. Many available parameter estimation methods use only short circuit, o pen circuit and maximum power points for a single I - V curve at standard test conditions together with temperature coefficients determined separately for individual cells. In contrast, module testing frequently records I - V curves over a wide range of irradi ance and temperature conditions which, when available , should also be used to parameterize the performance model. We present a parameter estimation method that makes use of a fu ll range of available I - V curves. We verify the accuracy of the method by recov ering known parameter values from simulated I - V curves . We validate the method by estimating model parameters for a module using outdoor test data and predicting the outdoor performance of the module.

  10. Mechanistic modelling of the drying behaviour of single pharmaceutical granules

    DEFF Research Database (Denmark)

    Thérèse F.C. Mortier, Séverine; Beer, Thomas De; Gernaey, Krist

    2012-01-01

    The trend to move towards continuous production processes in pharmaceutical applications enhances the necessity to develop mechanistic models to understand and control these processes. This work focuses on the drying behaviour of a single wet granule before tabletting, using a six......-segmented fluidised bed drying system, which is part of a fully continuous from-powder-to-tablet manufacturing line. The drying model is based on a model described by Mezhericher et al. [1] and consists of two submodels. In the first drying phase (submodel 1), the surface water evaporates, while in the second drying...... phase (submodel 2), the water inside the granule evaporates. The second submodel contains an empirical power coefficient, b. A sensitivity analysis was performed to study the influence of parameters on the moisture content of single pharmaceutical granules, which clearly points towards the importance...

  11. Synthesis and ultrastructure of plate-like apatite single crystals as a model for tooth enamel

    Energy Technology Data Exchange (ETDEWEB)

    Zhuang, Zhi, E-mail: zhuang@meiji.ac.jp [Department of Applied Chemistry, School of Science and Technology, Meiji University, 1-1-1 Higashimita, Tama-ku, Kawasaki, Kanagawa 214-8571 (Japan); Yoshimura, Hideyuki, E-mail: hyoshi@isc.meiji.ac.jp [Department of Physics, School of Science and Technology, Meiji University, 1-1-1 Higashimita, Tama-ku, Kawasaki, Kanagawa 214-8571 (Japan); Aizawa, Mamoru, E-mail: mamorua@isc.meiji.ac.jp [Department of Applied Chemistry, School of Science and Technology, Meiji University, 1-1-1 Higashimita, Tama-ku, Kawasaki, Kanagawa 214-8571 (Japan)

    2013-07-01

    Hydroxyapatite (HAp) is an inorganic constituent compound of human bones and teeth, with superior biocompatibility and bioactivity characteristics. Its crystal structure is hexagonal, characterized by a(b)- and c-planes. In vertebrate long bones, HAp crystals have a c-axis orientation, while in tooth enamel, they have an a(b)-axis orientation. Many methods can be used to synthesize c-axis oriented HAp single crystals; however, to the best of our knowledge, there have been no reports on a synthesis method for a(b)-axis oriented HAp single crystals. In this study, we successfully synthesized plate-like HAp crystals at the air–liquid interface of a starting solution via an enzyme reaction of urea with urease. Crystal phase analysis and ultrastructure observations were carried out, and the results indicated that the particles were single crystals, with almost the same a(b)-axis orientation as tooth enamel. It is hoped that by utilizing their unique surface charge and atomic arrangement, the resulting particles can be used as a high-performance biomaterial, capable of adsorbing bio-related substances and a model for tooth enamel. - Highlights: ► Synthesis of plate-like hydroxyapatite crystals at air–liquid interface ► Ultrastructural analysis of plate-like hydroxyapatite crystals ► Plate-like hydroxyapatite single crystals with a high a(b)-axis orientation ► Plate-like hydroxyapatite single crystals as a model for tooth enamel.

  12. Quantum chemical investigation of the thermal pyrolysis reactions of the carboxylic group in a brown coal model.

    Science.gov (United States)

    Liu, Shengyu; Zhang, Zhiqiang; Wang, Huifang

    2012-01-01

    Different reaction pathways of the carboxylic group in a brown coal model were investigated by applying density function quantum chemical theory, examining the possible cross-linking and decomposition reactions between the hydrogen bonded carboxylic group-carboxylic group and the carboxylic group-hydroxyl group during the thermal pyrolysis process. The results show that bimolecular dehydration and decarboxylation of hydrogen bonded carboxylic groups have distinctly lower activation barriers and therefore, proceed preferentially at low temperature. The esterification reaction between the hydrogen bonded carboxylic group and hydroxyl group, together with unimolecular decarboxylation of isolated single carboxylic groups were also possible at moderate temperature. Aryl-aryl coupling is thought to occur via radical pyrolysis and recombination at relatively high temperature.

  13. Computational models of the single substitutional nitrogen atom in diamond

    CERN Document Server

    Lombardi, E B; Osuch, K; Reynhardt, E C

    2003-01-01

    The single substitutional nitrogen atom in diamond is apparently a very simple defect in a very simple elemental solid. It has been modelled by a range of computational models, few of which either agree with each other, or with the experimental data on the defect. If the computational models of less well understood defects in this and more complex materials are to be reliable, we should understand why the discrepancies arise and how they can be avoided in future modelling. This paper presents an all-electron, augmented plane-wave (APW) density functional theory (DFT) calculation using the modern APW with local orbitals full potential periodic approximation. This is compared to DFT, finite cluster pseudopotential calculations and a semi-empirical Hartree-Fock model. Comparisons between the results of these and previous models allow us to discuss the reliability of computational methods of this and similar defects.

  14. Evaluation of the Cortical Bone Reaction Around of Implants Using a Single-Use Final Drill: A Histologic Study.

    Science.gov (United States)

    Gehrke, Sergio Alexandre

    2015-07-01

    This study was designed to compare the cortical bone reaction following traditional osteotomy or the use of a single-use final drill in the osseointegration of implants in the tibia of rabbits. For this study, 48 conical implants, of standard surface type and design and manufactured by the same company, were inserted into the tibiae of 12 rabbits and removed after 30 or 60 days for histologic analysis. Two test groups were prepared according to the drill sequence used for the osteotomy at the preparation sites: in the control group was used a conventional drill sequence with several uses, whereas the test group (tesG) used a single-use final drill. The bone-to-implant contact and qualitative factors of the resulting cortical bone were assessed. Both techniques produced good implant integration. Differences in the linear bone-to-implant contact were observed between the drilling procedures as time elapsed in vivo, with the tesG appearing to have clinical advantages. Both groups exhibited new bone in quantity and in quality; however, the tesG exhibited a higher level of new bone deposition than the control group. Within the limitations of this study, the findings suggest that the use of a single-use final drill leads to better and faster organization of the cortical bone area during the evaluated period and may avoid the possible problems that can be caused by worn drills.

  15. On-chip real-time single-copy polymerase chain reaction in picoliter droplets

    Energy Technology Data Exchange (ETDEWEB)

    Beer, N R; Hindson, B; Wheeler, E; Hall, S B; Rose, K A; Kennedy, I; Colston, B

    2007-04-20

    The first lab-on-chip system for picoliter droplet generation and PCR amplification with real-time fluorescence detection has performed PCR in isolated droplets at volumes 10{sup 6} smaller than commercial real-time PCR systems. The system utilized a shearing T-junction in a silicon device to generate a stream of monodisperse picoliter droplets that were isolated from the microfluidic channel walls and each other by the oil phase carrier. An off-chip valving system stopped the droplets on-chip, allowing them to be thermal cycled through the PCR protocol without droplet motion. With this system a 10-pL droplet, encapsulating less than one copy of viral genomic DNA through Poisson statistics, showed real-time PCR amplification curves with a cycle threshold of {approx}18, twenty cycles earlier than commercial instruments. This combination of the established real-time PCR assay with digital microfluidics is ideal for isolating single-copy nucleic acids in a complex environment.

  16. Single-site SBA-15 supported zirconium catalysts. Synthesis, characterization and toward cyanosilylation reaction

    Science.gov (United States)

    Xu, Wei; Yu, Bo; Zhang, Ying; Chen, Xi; Zhang, Guofang; Gao, Ziwei

    2015-01-01

    A successive anchoring of Zr(NMe2)4, cyclopentadiene and a O-donor ligand, 1-hydroxyethylbenzene (PEA), 1,1‧-bi-2-naphthol (Binol) or 2,3-dihydroxybutanedioic acid diethyl ester (Tartrate), on dehydroxylated SBA-15 pretreated at 500 °C for 16 h (SBA-15-500) was conducted by SOMC strategy in moderate conditions. The dehydoxylation of SBA-15 was monitored by in situ Fourier transform infrared spectroscopy (in situ FT-IR). The ligand-modified SBA-15-500 supported zirconium complexes were characterized by in situ FT-IR, 13C CP MAS-NMR, X-ray photoelectron spectroscopy (XPS), inductively coupled plasma mass spectrometry (ICP-MAS) and elemental analysis in detail, verifying that the surface zirconium species are single-sited. The catalytic activity of these complexes was evaluated by cyanosilylation of benzaldehyde. The results showed that the catalytic activity is dependent strongly on the structure of surface species and the configuration of the ligands.

  17. Evaluation of the single radiosensitivity in patients subjected to medical exposure that show severe skin reactions

    International Nuclear Information System (INIS)

    Di Giorgio, M.; Vallerga, M.B.; Portas, M.; Perez, M.R.

    2006-01-01

    The Burnt Hospital of the Buenos Aires City Government (HQGCBA) it is a hospital of reference of the Net of Medical Responses in Radiological Emergencies of the Argentine Republic. In the mark of an agreement among the HQGCBA and the Authority Regulatory Nuclear (ARN), it is in execution a study protocol for the one boarding diagnoses and therapeutic of radioinduced cutaneous leisure. They exist individual variations that can condition the response to the ionizing radiations (IR), so much in accidental exposures as having programmed (radiotherapy, radiology interventionist). In this context, the individual radiosensitivity is evaluated in the patients signed up in this protocol that presented sharp or late cutaneous reactions, with grades of severity 3-4 (approaches EORTC/RTOG). The capacity of repair of the DNA was evaluated in outlying blood lymphocytes irradiated in vitro (2 Gy, gamma of Co-60) by means of the micronucleus techniques and comet essay in alkaline conditions. In this work two cases in those that is applied this study protocol, the therapeutic answer and its correlate with the discoveries of the radiosensitivity tests is presented. Case 1: patient of feminine sex, subjected to external radiotherapy by a breast infiltrating ductal carcinoma; developed sharp cutaneous radiotoxicity grade 3 (confluent humid epithelitis) that motivate the interruption of the treatment. Case 2: patient of masculine sex, subjected to a coronary angioplasty (interventionist radiology); developed late cutaneous radiotoxicity grade 4 (ulceration in dorsal region). Both patients were treated with topical trolamine associated to systemic administration of pentoxiphiline and antioxidants. The therapeutic answer is evaluated by means of clinical pursuit, photographic serial register and complementary exams (thermography and ultrasonography of high frequency). In the case 1 the answer was very favorable, with precocious local improvement and complete remission of symptoms and

  18. Dynamic Model of Basic Oxygen Steelmaking Process Based on Multizone Reaction Kinetics: Modeling of Decarburization

    Science.gov (United States)

    Rout, Bapin Kumar; Brooks, Geoffrey; Akbar Rhamdhani, M.; Li, Zushu; Schrama, Frank N. H.; Overbosch, Aart

    2018-03-01

    In a previous study by the authors (Rout et al. in Metall Mater Trans B 49:537-557, 2018), a dynamic model for the BOF, employing the concept of multizone kinetics was developed. In the current study, the kinetics of decarburization reaction is investigated. The jet impact and slag-metal emulsion zones were identified to be primary zones for carbon oxidation. The dynamic parameters in the rate equation of decarburization such as residence time of metal drops in the emulsion, interfacial area evolution, initial size, and the effects of surface-active oxides have been included in the kinetic rate equation of the metal droplet. A modified mass-transfer coefficient based on the ideal Langmuir adsorption equilibrium has been proposed to take into account the surface blockage effects of SiO2 and P2O5 in slag on the decarburization kinetics of a metal droplet in the emulsion. Further, a size distribution function has been included in the rate equation to evaluate the effect of droplet size on reaction kinetics. The mathematical simulation indicates that decarburization of the droplet in the emulsion is a strong function of the initial size and residence time. A modified droplet generation rate proposed previously by the authors has been used to estimate the total decarburization rate by slag-metal emulsion. The model's prediction shows that about 76 pct of total carbon is removed by reactions in the emulsion, and the remaining is removed by reactions at the jet impact zone. The predicted bath carbon by the model has been found to be in good agreement with the industrially measured data.

  19. Computational Modeling of Photonic Crystal Microcavity Single-Photon Emitters

    Science.gov (United States)

    Saulnier, Nicole A.

    Conventional cryptography is based on algorithms that are mathematically complex and difficult to solve, such as factoring large numbers. The advent of a quantum computer would render these schemes useless. As scientists work to develop a quantum computer, cryptographers are developing new schemes for unconditionally secure cryptography. Quantum key distribution has emerged as one of the potential replacements of classical cryptography. It relics on the fact that measurement of a quantum bit changes the state of the bit and undetected eavesdropping is impossible. Single polarized photons can be used as the quantum bits, such that a quantum system would in some ways mirror the classical communication scheme. The quantum key distribution system would include components that create, transmit and detect single polarized photons. The focus of this work is on the development of an efficient single-photon source. This source is comprised of a single quantum dot inside of a photonic crystal microcavity. To better understand the physics behind the device, a computational model is developed. The model uses Finite-Difference Time-Domain methods to analyze the electromagnetic field distribution in photonic crystal microcavities. It uses an 8-band k · p perturbation theory to compute the energy band structure of the epitaxially grown quantum dots. We discuss a method that combines the results of these two calculations for determining the spontaneous emission lifetime of a quantum dot in bulk material or in a microcavity. The computational models developed in this thesis are used to identify and characterize microcavities for potential use in a single-photon source. The computational tools developed are also used to investigate novel photonic crystal microcavities that incorporate 1D distributed Bragg reflectors for vertical confinement. It is found that the spontaneous emission enhancement in the quasi-3D cavities can be significantly greater than in traditional suspended slab

  20. Delineating pMDI model reactions with loblolly pine via solution-state NMR spectroscopy. Part 1, Catalyzed reactions with wood models and wood polymers

    Science.gov (United States)

    Daniel J. Yelle; John Ralph; Charles R. Frihart

    2011-01-01

    To better understand adhesive interactions with wood, reactions between model compounds of wood and a model compound of polymeric methylene diphenyl diisocyanate (pMDI) were characterized by solution-state NMR spectroscopy. For comparison, finely ground loblolly pine sapwood, milled-wood lignin and holocellulose from the same wood were isolated and derivatized with...

  1. Kinetic modeling for thermal dehydration of ferrous oxalate dihydrate polymorphs: a combined model for induction period-surface reaction-phase boundary reaction.

    Science.gov (United States)

    Ogasawara, Haruka; Koga, Nobuyoshi

    2014-04-03

    In this study, ferrous oxalate dihydrate polymorph particles, α- and β-phases, with square bipyramidal and quadratic prismatic shapes, respectively, were synthesized. Thermal dehydration of the samples was subjected to kinetic study as a typical reaction that indicates a significant induction period and a sigmoidal mass-loss behavior. On the basis of the formal kinetic analysis of the mass-loss traces recorded under isothermal, nonisothermal, and constant transformation rate conditions and the morphological observations of the surface textures of the partially reacted sample particles, a combined kinetic model for the induction period-surface reaction-phase boundary reaction was developed. The sigmoidal mass-loss behavior after the significant induction period under isothermal conditions was satisfactorily simulated by the combined kinetic model. The kinetic parameters for the component processes of induction period, surface reaction, and phase boundary reaction were separately determined from the kinetic simulation. The differences in the kinetic behaviors of the induction period and the phase boundary reaction between α- and β-phase samples were well described by the kinetic parameters. The applicability of the combined kinetic model to practical systems was demonstrated through characterizing the physicogeometrical kinetics of the thermal dehydration of ferrous oxalate dihydrate polymorphs.

  2. Modeling of Chemical Reactions in Afterburning for the Reduction of N2O

    DEFF Research Database (Denmark)

    Gustavsson, Lennart; Glarborg, Peter; Leckner, Bo

    1996-01-01

    Full scale tests in a 12 MW fluidized bed combustor on reduction of N2O by secondary fuel injection are analyzed in terms a model that involves a detailed reaction mechanism for the gas phase chemistry as well as a description of gas-solid reactions.......Full scale tests in a 12 MW fluidized bed combustor on reduction of N2O by secondary fuel injection are analyzed in terms a model that involves a detailed reaction mechanism for the gas phase chemistry as well as a description of gas-solid reactions....

  3. Single-Index Additive Vector Autoregressive Time Series Models

    KAUST Repository

    LI, YEHUA

    2009-09-01

    We study a new class of nonlinear autoregressive models for vector time series, where the current vector depends on single-indexes defined on the past lags and the effects of different lags have an additive form. A sufficient condition is provided for stationarity of such models. We also study estimation of the proposed model using P-splines, hypothesis testing, asymptotics, selection of the order of the autoregression and of the smoothing parameters and nonlinear forecasting. We perform simulation experiments to evaluate our model in various settings. We illustrate our methodology on a climate data set and show that our model provides more accurate yearly forecasts of the El Niño phenomenon, the unusual warming of water in the Pacific Ocean. © 2009 Board of the Foundation of the Scandinavian Journal of Statistics.

  4. Bayesian analysis of inflation: Parameter estimation for single field models

    International Nuclear Information System (INIS)

    Mortonson, Michael J.; Peiris, Hiranya V.; Easther, Richard

    2011-01-01

    Future astrophysical data sets promise to strengthen constraints on models of inflation, and extracting these constraints requires methods and tools commensurate with the quality of the data. In this paper we describe ModeCode, a new, publicly available code that computes the primordial scalar and tensor power spectra for single-field inflationary models. ModeCode solves the inflationary mode equations numerically, avoiding the slow roll approximation. It is interfaced with CAMB and CosmoMC to compute cosmic microwave background angular power spectra and perform likelihood analysis and parameter estimation. ModeCode is easily extendable to additional models of inflation, and future updates will include Bayesian model comparison. Errors from ModeCode contribute negligibly to the error budget for analyses of data from Planck or other next generation experiments. We constrain representative single-field models (φ n with n=2/3, 1, 2, and 4, natural inflation, and 'hilltop' inflation) using current data, and provide forecasts for Planck. From current data, we obtain weak but nontrivial limits on the post-inflationary physics, which is a significant source of uncertainty in the predictions of inflationary models, while we find that Planck will dramatically improve these constraints. In particular, Planck will link the inflationary dynamics with the post-inflationary growth of the horizon, and thus begin to probe the ''primordial dark ages'' between TeV and grand unified theory scale energies.

  5. Geometrical Models of the Phase Space Structures Governing Reaction Dynamics

    Science.gov (United States)

    2009-08-01

    of Mathematical Sciences . Springer, Berlin. [Child & Pollak(1980)] Child, M. S. & Pollak, E. (1980). Analytical reaction dynamics: Origin and implica...state region, i.e. the phase space point at which a trajectory enters the transition state region can be mapped analytically to the phase space point...Neishtadt, A. I. (1988). Mathematical aspects of classical and celestial mechanics. In V. I. Arnol’d, editor, Dynamical Systems III, volume 3 of Encyclopaedia

  6. Compact Ag@Fe3O4 Core-shell Nanoparticles by Means of Single-step Thermal Decomposition Reaction

    Science.gov (United States)

    Brollo, Maria Eugênia F.; López-Ruiz, Román; Muraca, Diego; Figueroa, Santiago J. A.; Pirota, Kleber R.; Knobel, Marcelo

    2014-10-01

    A temperature pause introduced in a simple single-step thermal decomposition of iron, with the presence of silver seeds formed in the same reaction mixture, gives rise to novel compact heterostructures: brick-like Ag@Fe3O4 core-shell nanoparticles. This novel method is relatively easy to implement, and could contribute to overcome the challenge of obtaining a multifunctional heteroparticle in which a noble metal is surrounded by magnetite. Structural analyses of the samples show 4 nm silver nanoparticles wrapped within compact cubic external structures of Fe oxide, with curious rectangular shape. The magnetic properties indicate a near superparamagnetic like behavior with a weak hysteresis at room temperature. The value of the anisotropy involved makes these particles candidates to potential applications in nanomedicine.

  7. Meaurement of the target single-spin asymmetry in quasi-elastic region from the reaction {sup 3}He{up_arrow}(e,e')

    Energy Technology Data Exchange (ETDEWEB)

    Zhang, Yawei [Rutgers

    2013-10-01

    A measurement of the inclusive target single-spin asymmetry has been performed using the quasi-elastic {sup 3}He{up_arrow}(e,e') reaction with a vertically polarized {sup 3}He target at Q{sup 2} values of 0.13, 0.46 and 0.97 GeV{sup 2}. This asymmetry vanishes under the one photon exchange assumption. But the interference between two-photon exchange and one-photon exchange gives rise to an imaginary amplitude, so that a non-zero A{sub y} is allowed. The experiment, conducted in Hall A of Jefferson Laboratory in 2009, used two independent spectrometers to simultaneously measure the target single-spin asymmetry. Using the effective polarization approximation, the neutron single-spin asymmetries were extracted from the measured {sup 3}He asymmetries. The measurement is to establish a non-vanishing A{sub y}. Non-zero asymmetries were observed at all Q{sup 2} points, and the overall precision is an order of magnitude improved over the existing proton data. The data provide new constraints on Generalized Parton Distribution (GPD) models and new information on the dynamics of the two-photon exchange process.

  8. Study of single particle properties of nuclei in the region of the "island of inversion" by means of neutron-transfer reactions

    CERN Multimedia

    Kruecken, R; Voulot, D

    2007-01-01

    We are aiming at the investigation of single particle properties of neutron-rich nuclei in the region of the "island of inversion" where intruder states from the $\\{fp}$-shell favour deformed ground states instead of the normal spherical $\\textit{sd}$-shell states. As first experiment, we propose to study single particle states in the neutron-rich isotope $^{31}$Mg. The nucleus will be populated by a one-neutron transfer reaction with a $^{30}$Mg beam at 3 MeV/u obtained from REX-ISOLDE impinging on a CD$_{2}$ target. The $\\gamma$-rays will be detected by the MINIBALL array and the particles by a newly built set-up of segmented Si detectors with a angular coverage of nearly 4$\\pi$. Relative spectroscopic factors extracted from the cross sections will enable us to pin down the configurations of the populated states. These will be compared to recent shell model calculations involving new residual interactions. This will shed new light on the evolution of single particle structure leading to the breaking of the ...

  9. A macroscopic model for magnetic shape-memory single crystals

    Czech Academy of Sciences Publication Activity Database

    Bessoud, A. L.; Kružík, Martin; Stefanelli, U.

    2013-01-01

    Roč. 64, č. 2 (2013), s. 343-359 ISSN 0044-2275 R&D Projects: GA AV ČR IAA100750802; GA ČR GAP201/10/0357 Institutional support: RVO:67985556 Keywords : magneto striction * evolution Subject RIV: BA - General Mathematics Impact factor: 1.214, year: 2013 http://library.utia.cas.cz/separaty/2012/MTR/kruzik-a macroscopic model for magnetic shape-memory single crystals.pdf

  10. Unified Model of Dynamic Forced Barrier Crossing in Single Molecules

    Energy Technology Data Exchange (ETDEWEB)

    Friddle, R W

    2007-06-21

    Thermally activated barrier crossing in the presence of an increasing load can reveal kinetic rate constants and energy barrier parameters when repeated over a range of loading rates. Here we derive a model of the mean escape force for all relevant loading rates--the complete force spectrum. Two well-known approximations emerge as limiting cases; one of which confirms predictions that single-barrier spectra should converge to a phenomenological description in the slow loading limit.

  11. An atomic model for neutral and singly ionized uranium

    Science.gov (United States)

    Maceda, E. L.; Miley, G. H.

    1979-01-01

    A model for the atomic levels above ground state in neutral, U(0), and singly ionized, U(+), uranium is described based on identified atomic transitions. Some 168 states in U(0) and 95 in U(+) are found. A total of 1581 atomic transitions are used to complete this process. Also discussed are the atomic inverse lifetimes and line widths for the radiative transitions as well as the electron collisional cross sections.

  12. Fully automated radiosynthesis of [18F]Fluoromisonidazole with single neutral alumina column purification: optimization of reaction parameters

    International Nuclear Information System (INIS)

    Nandy, S.K.; Rajan, M.G.R.

    2010-01-01

    1-H-1-(3-[ 18 F]fluoro-2-hydroxypropyl)-2-nitroimidazole ([ 18 F]FMISO), is the most used hypoxia-imaging agent in oncology and we have recently reported a fully automated procedure for its synthesis using the Nuclear Interface FDG module and a single neutral alumina column for purification. Using 1-(2'-nitro-1'-imidazolyl)-2-O-tetra-hydropyranyl-3-O- toluenesulfonylpropanediol (NITTP) as the precursor, we have investigated the yield of [ 18 F]FMISO using different reaction times, temperatures, and the amount of precursor. The overall yield was 48.4 ± 1.2% (n = 3), (without decay correction) obtained using 10 mg NITTP with the radio-fluorination carried out at 145 deg C for 3 min followed by acid hydrolysis for 3 min at 125 deg C in a total synthesis time of 32 ± 1 min. Increasing the precursor amount to 25 mg did not improve the overall yield under identical reaction conditions, with the decay uncorrected yield being 46.8 ± 1.6% (n = 3), but rather made the production less economical. It was also observed that the yield increased linearly with the amount of NITTP used, from 2.5 to 10 mg and plateaued from 10 to 25 mg. Radio-fluorination efficiency at four different conditions was also compared. It was also observed by radio thin layer chromatography (radio-TLC) that the duration of radio-fluorination of NITTP, not the radio-fluorination temperature favoured the formation of labeled thermally degraded product, but the single neutral alumina column purification was sufficient enough to obtain [ 18 F]FMISO devoid of any radiochemical as well as cold impurities. (author)

  13. Electrochemistry of single nanobubbles. Estimating the critical size of bubble-forming nuclei for gas-evolving electrode reactions.

    Science.gov (United States)

    German, Sean R; Edwards, Martin A; Chen, Qianjin; Liu, Yuwen; Luo, Long; White, Henry S

    2016-12-12

    In this article, we address the fundamental question: "What is the critical size of a single cluster of gas molecules that grows and becomes a stable (or continuously growing) gas bubble during gas evolving reactions?" Electrochemical reactions that produce dissolved gas molecules are ubiquitous in electrochemical technologies, e.g., water electrolysis, photoelectrochemistry, chlorine production, corrosion, and often lead to the formation of gaseous bubbles. Herein, we demonstrate that electrochemical measurements of the dissolved gas concentration, at the instant prior to nucleation of an individual nanobubble of H 2 , N 2 , or O 2 at a Pt nanodisk electrode, can be analyzed using classical thermodynamic relationships (Henry's law and the Young-Laplace equation - including non-ideal corrections) to provide an estimate of the size of the gas bubble nucleus that grows into a stable bubble. We further demonstrate that this critical nucleus size is independent of the radius of the Pt nanodisk employed (gas. For example, the measured critical surface concentration of H 2 of ∼0.23 M at the instant of bubble formation corresponds to a critical H 2 nucleus that has a radius of ∼3.6 nm, an internal pressure of ∼350 atm, and contains ∼1700 H 2 molecules. The data are consistent with stochastic fluctuations in the density of dissolved gas, at or near the Pt/solution interface, controlling the rate of bubble nucleation. We discuss the growth of the nucleus as a diffusion-limited process and how that process is affected by proximity to an electrode producing ∼10 11 gas molecules per second. Our study demonstrates the advantages of studying a single-entity, i.e., an individual nanobubble, in understanding and quantifying complex physicochemical phenomena.

  14. Stochastic models for spike trains of single neurons

    CERN Document Server

    Sampath, G

    1977-01-01

    1 Some basic neurophysiology 4 The neuron 1. 1 4 1. 1. 1 The axon 7 1. 1. 2 The synapse 9 12 1. 1. 3 The soma 1. 1. 4 The dendrites 13 13 1. 2 Types of neurons 2 Signals in the nervous system 14 2. 1 Action potentials as point events - point processes in the nervous system 15 18 2. 2 Spontaneous activi~ in neurons 3 Stochastic modelling of single neuron spike trains 19 3. 1 Characteristics of a neuron spike train 19 3. 2 The mathematical neuron 23 4 Superposition models 26 4. 1 superposition of renewal processes 26 4. 2 Superposition of stationary point processe- limiting behaviour 34 4. 2. 1 Palm functions 35 4. 2. 2 Asymptotic behaviour of n stationary point processes superposed 36 4. 3 Superposition models of neuron spike trains 37 4. 3. 1 Model 4. 1 39 4. 3. 2 Model 4. 2 - A superposition model with 40 two input channels 40 4. 3. 3 Model 4. 3 4. 4 Discussion 41 43 5 Deletion models 5. 1 Deletion models with 1nd~endent interaction of excitatory and inhibitory sequences 44 VI 5. 1. 1 Model 5. 1 The basic de...

  15. Ligase-free subcloning: a versatile method to subclone polymerase chain reaction (PCR) products in a single day.

    Science.gov (United States)

    Shuldiner, A R; Tanner, K; Scott, L A; Moore, C A; Roth, J

    1991-04-01

    Often, it is convenient to subclone polymerase chain reaction (PCR) products into a plasmid vector for subsequent replication in bacteria, but conventional subcloning methods often fail. We report a rapid and versatile method to subclone PCR products directionally into a specific site of virtually any plasmid vector. The procedure requires only four primers, does not require DNA ligase, and may be accomplished in a single day. Ligase-free subcloning is performed by incorporating into the PCR primers sequences at the 5' ends that result in PCR products whose 3' ends are complementary to the 3' ends of the recipient linearized plasmid. The PCR product and the linearized plasmid are spliced together in a second PCR reaction in which Taq polymerase extends the complementary overlapping 3' ends (ligation by overlap extension). Denaturation followed by heterologous reannealing and cyclization results in a cyclic recombinant plasmid with two nicks that may be used directly to transform competent Escherichia coli. In our hands, ligase-free subcloning is rapid, and offers many advantages over existing strategies.

  16. High-Pressure Catalytic Reactions of C6 Hydrocarbons on PlatinumSingle-Crystals and nanoparticles: A Sum Frequency Generation VibrationalSpectroscopic and Kinetic Study

    Energy Technology Data Exchange (ETDEWEB)

    Bratlie, Kaitlin [Univ. of California, Berkeley, CA (United States)

    2007-01-01

    Catalytic reactions of cyclohexene, benzene, n-hexane, 2-methylpentane, 3-methylpentane, and 1-hexene on platinum catalysts were monitored in situ via sum frequency generation (SFG) vibrational spectroscopy and gas chromatography (GC). SFG is a surface specific vibrational spectroscopic tool capable of monitoring submonolayer coverages under reaction conditions without gas-phase interference. SFG was used to identify the surface intermediates present during catalytic processes on Pt(111) and Pt(100) single-crystals and on cubic and cuboctahedra Pt nanoparticles in the Torr pressure regime and at high temperatures (300K-450K). At low pressures (<10-6 Torr), cyclohexene hydrogenated and dehydrogenates to form cyclohexyl (C6H11) and π-allyl C6H9, respectively, on Pt(100). Increasing pressures to 1.5 Torr form cyclohexyl, π-allyl C6H9, and 1,4-cyclohexadiene, illustrating the necessity to investigate catalytic reactions at high-pressures. Simultaneously, GC was used to acquire turnover rates that were correlated to reactive intermediates observed spectroscopically. Benzene hydrogenation on Pt(111) and Pt(100) illustrated structure sensitivity via both vibrational spectroscopy and kinetics. Both cyclohexane and cyclohexene were produced on Pt(111), while only cyclohexane was formed on Pt(100). Additionally, π-allyl c-C6H9 was found only on Pt(100), indicating that cyclohexene rapidly dehydrogenates on the (100) surface. The structure insensitive production of cyclohexane was found to exhibit a compensation effect and was analyzed using the selective energy transfer (SET) model. The SET model suggests that the Pt-H system donates energy to the E2u mode of free benzene, which leads to catalysis. Linear C6 (n-hexane, 2-methylpentane, 3-methylpentane, and 1-hexene) hydrocarbons were also investigated in the presence and absence of excess hydrogen on Pt

  17. Dynamic disorder in single-molecule Michaelis-Menten kinetics: The reaction-diffusion formalism in the Wilemski-Fixman approximation

    Science.gov (United States)

    Chaudhury, Srabanti; Cherayil, Binny J.

    2007-09-01

    Single-molecule equations for the Michaelis-Menten [Biochem. Z. 49, 333 (1913)] mechanism of enzyme action are analyzed within the Wilemski-Fixman [J. Chem. Phys. 58, 4009 (1973); 60, 866 (1974)] approximation after the effects of dynamic disorder—modeled by the anomalous diffusion of a particle in a harmonic well—are incorporated into the catalytic step of the reaction. The solution of the Michaelis-Menten equations is used to calculate the distribution of waiting times between successive catalytic turnovers in the enzyme β-galactosidase. The calculated distribution is found to agree qualitatively with experimental results on this enzyme obtained at four different substrate concentrations. The calculations are also consistent with measurements of correlations in the fluctuations of the fluorescent light emitted during the course of catalysis, and with measurements of the concentration dependence of the randomness parameter.

  18. Characterization of biomass combustion at high temperatures based on an upgraded single particle model

    International Nuclear Information System (INIS)

    Li, Jun; Paul, Manosh C.; Younger, Paul L.; Watson, Ian; Hossain, Mamdud; Welch, Stephen

    2015-01-01

    Highlights: • High temperature rapid biomass combustion is studied based on single particle model. • Particle size changes in devolatilization and char oxidation models are addressed. • Time scales of various thermal sub-processes are compared and discussed. • Potential solutions are suggested to achieve better biomass co-firing performances. - Abstract: Biomass co-firing is becoming a promising solution to reduce CO 2 emissions, due to its renewability and carbon neutrality. Biomass normally has high moisture and volatile contents, complicating its combustion behavior, which is significantly different from that of coal. A computational fluid dynamics (CFD) combustion model of a single biomass particle is employed to study high-temperature rapid biomass combustion. The two-competing-rate model and kinetics/diffusion model are used to model biomass devolatilization reaction and char burnout process, respectively, in which the apparent kinetics used for those two models were from high temperatures and high heating rates tests. The particle size changes during the devolatilization and char burnout are also considered. The mass loss properties and temperature profile during the biomass devolatilization and combustion processes are predicted; and the timescales of particle heating up, drying, devolatilization, and char burnout are compared and discussed. Finally, the results shed light on the effects of particle size on the combustion behavior of biomass particle

  19. Connecting single-stock assessment models through correlated survival

    DEFF Research Database (Denmark)

    Albertsen, Christoffer Moesgaard; Nielsen, Anders; Thygesen, Uffe Høgsbro

    2017-01-01

    the corresponding partial correlations. We consider six models where the partial correlation matrix between stocks follows a band structure ranging from independent assessments to complex correlation structures. Further, a simulation study illustrates the importance of handling correlated data sufficiently...... times. We propose a simple alternative. In three case studies each with two stocks, we improve the single-stock models, as measured by Akaike information criterion, by adding correlation in the cohort survival. To limit the number of parameters, the correlations are parameterized through...

  20. Stepwise kinetic equilibrium models of quantitative polymerase chain reaction

    OpenAIRE

    Cobbs, Gary

    2012-01-01

    Abstract Background Numerous models for use in interpreting quantitative PCR (qPCR) data are present in recent literature. The most commonly used models assume the amplification in qPCR is exponential and fit an exponential model with a constant rate of increase to a select part of the curve. Kinetic theory may be used to model the annealing phase and does not assume constant efficiency of amplification. Mechanistic models describing the annealing phase with kinetic theory offer the most pote...

  1. Modelling of the spallation reaction: analysis and testing of nuclear models

    International Nuclear Information System (INIS)

    Toccoli, C.

    2000-01-01

    The spallation reaction is considered as a 2-step process. First a very quick stage (10 -22 , 10 -29 s) which corresponds to the individual interaction between the incident projectile and nucleons, this interaction is followed by a series of nucleon-nucleon collisions (intranuclear cascade) during which fast particles are emitted, the nucleus is left in a strongly excited level. Secondly a slower stage (10 -18 , 10 -19 s) during which the nucleus is expected to de-excite completely. This de-excitation is performed by evaporation of light particles (n, p, d, t, 3 He, 4 He) or/and fission or/and fragmentation. The HETC code has been designed to simulate spallation reactions, this simulation is based on the 2-steps process and on several models of intranuclear cascades (Bertini model, Cugnon model, Helder Duarte model), the evaporation model relies on the statistical theory of Weiskopf-Ewing. The purpose of this work is to evaluate the ability of the HETC code to predict experimental results. A methodology about the comparison of relevant experimental data with results of calculation is presented and a preliminary estimation of the systematic error of the HETC code is proposed. The main problem of cascade models originates in the difficulty of simulating inelastic nucleon-nucleon collisions, the emission of pions is over-estimated and corresponding differential spectra are badly reproduced. The inaccuracy of cascade models has a great impact to determine the excited level of the nucleus at the end of the first step and indirectly on the distribution of final residual nuclei. The test of the evaporation model has shown that the emission of high energy light particles is under-estimated. (A.C.)

  2. Dynamic Human Body Modeling Using a Single RGB Camera.

    Science.gov (United States)

    Zhu, Haiyu; Yu, Yao; Zhou, Yu; Du, Sidan

    2016-03-18

    In this paper, we present a novel automatic pipeline to build personalized parametric models of dynamic people using a single RGB camera. Compared to previous approaches that use monocular RGB images, our system can model a 3D human body automatically and incrementally, taking advantage of human motion. Based on coarse 2D and 3D poses estimated from image sequences, we first perform a kinematic classification of human body parts to refine the poses and obtain reconstructed body parts. Next, a personalized parametric human model is generated by driving a general template to fit the body parts and calculating the non-rigid deformation. Experimental results show that our shape estimation method achieves comparable accuracy with reconstructed models using depth cameras, yet requires neither user interaction nor any dedicated devices, leading to the feasibility of using this method on widely available smart phones.

  3. A Gibbs Energy Minimization Approach for Modeling of Chemical Reactions in a Basic Oxygen Furnace

    Science.gov (United States)

    Kruskopf, Ari; Visuri, Ville-Valtteri

    2017-12-01

    In modern steelmaking, the decarburization of hot metal is converted into steel primarily in converter processes, such as the basic oxygen furnace. The objective of this work was to develop a new mathematical model for top blown steel converter, which accounts for the complex reaction equilibria in the impact zone, also known as the hot spot, as well as the associated mass and heat transport. An in-house computer code of the model has been developed in Matlab. The main assumption of the model is that all reactions take place in a specified reaction zone. The mass transfer between the reaction volume, bulk slag, and metal determine the reaction rates for the species. The thermodynamic equilibrium is calculated using the partitioning of Gibbs energy (PGE) method. The activity model for the liquid metal is the unified interaction parameter model and for the liquid slag the modified quasichemical model (MQM). The MQM was validated by calculating iso-activity lines for the liquid slag components. The PGE method together with the MQM was validated by calculating liquidus lines for solid components. The results were compared with measurements from literature. The full chemical reaction model was validated by comparing the metal and slag compositions to measurements from industrial scale converter. The predictions were found to be in good agreement with the measured values. Furthermore, the accuracy of the model was found to compare favorably with the models proposed in the literature. The real-time capability of the proposed model was confirmed in test calculations.

  4. Single-shot characterization of enzymatic reaction constants Km and kcat by an acoustic-driven, bubble-based fast micromixer

    Science.gov (United States)

    Xie, Yuliang; Ahmed, Daniel; Lapsley, Michael Ian; Lin, Sz-Chin Steven; Nawaz, Ahmad Ahsan; Wang, Lin; Huang, Tony Jun

    2014-01-01

    In this work we present an acoustofluidic approach for rapid, single-shot characterization of enzymatic reaction constants Km and kcat. The acoustofluidic design involves a bubble anchored in a horseshoe structure which can be stimulated by a piezoelectric transducer to generate vortices in the fluid. The enzyme and substrate can thus be mixed rapidly, within 100 ms, by the vortices to yield the product. Enzymatic reaction constants Km and kcat can then be obtained from the reaction rate curves for different concentrations of substrate while holding the enzyme concentration constant. We studied the enzymatic reaction for β-galactosidase and its substrate (resorufin β-D-galactopyranoside) and found Km and kcat to be 333±130 =M and 64±8 s−1 respectively, which are in agreement with published data. Our approach is valuable for studying the kinetics of high-speed enzymatic reactions and other chemical reactions. PMID:22880882

  5. Low-temperature synthesis of single-domain Sr-hexaferrite particles by solid-state reaction route

    Energy Technology Data Exchange (ETDEWEB)

    Soezeri, Hueseyin [TUBITAK-UME, National Metrology Institute, PO Box 54, 41470, Gebze-Kocaeli (Turkey); Baykal, Abduelhadi [Department of Chemistry, Fatih University, B. Cekmece, 34500 Istanbul (Turkey); BioNanoTechnology R and D Center, Fatih University, B. Cekmece, 34500 Istanbul (Turkey); Uenal, Bayram [BioNanoTechnology R and D Center, Fatih University, B. Cekmece, 34500 Istanbul (Turkey); Department of Electrical and Electronics Engineering, Fatih University, B. Cekmece, 34500 Istanbul (Turkey)

    2012-10-15

    Sr-hexaferrite particles have been synthesized by conventional solid-state reaction route at low temperatures by boron addition that is used as an inhibitor for crystal growth. The effect of boron concentration on the structural, magnetic and electrical properties of Sr-hexaferrite particles are investigated by X-ray crystallography, scanning electron microscopy, magnetization and conductivity measurements. Saturation magnetization of Sr-hexaferrite increases up to 1 wt% boron addition, while coercivity becomes maximum with a boron amount of 2 wt%. Then, both magnetic parameters start to decrease with higher boron concentrations. Single-domain and single-phase powders have been obtained in the sample containing 1 wt% of boron that is sintered at 1050 C. Impedance spectroscopies reveal that the dc conductivity increases tremendously with boron addition, while the ac conductivity increases with elevated temperature. The ac conductivity obeys roughly the power law of angular frequency in which tendencies change with temperature at low and medium temperature. Furthermore, higher contents of the dopant over approximately 2.0 wt% cause its temperature independency at higher frequencies. These are due to the grain size and secondary phase of hexaferrites that increases with the increase in boron amount. (Copyright copyright 2012 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

  6. Single-Atom Au/NiFe Layered Double Hydroxide Electrocatalyst: Probing the Origin of Activity for Oxygen Evolution Reaction.

    Science.gov (United States)

    Zhang, Jingfang; Liu, Jieyu; Xi, Lifei; Yu, Yifu; Chen, Ning; Sun, Shuhui; Wang, Weichao; Lange, Kathrin M; Zhang, Bin

    2018-03-21

    A fundamental understanding of the origin of oxygen evolution reaction (OER) activity of transition-metal-based electrocatalysts, especially for single precious metal atoms supported on layered double hydroxides (LDHs), is highly required for the design of efficient electrocatalysts toward further energy conversion technologies. Here, we aim toward single-atom Au supported on NiFe LDH ( s Au/NiFe LDH) to clarify the activity origin of LDHs system and a 6-fold OER activity enhancement by 0.4 wt % s Au decoration. Combining with theoretical calculations, the active behavior of NiFe LDH results from the in situ generated NiFe oxyhydroxide from LDH during the OER process. With the presence of s Au, s Au/NiFe LDH possesses an overpotential of 0.21 V in contrast to the calculated result (0.18 V). We ascribe the excellent OER activity of s Au/NiFe LDH to the charge redistribution of active Fe as well as its surrounding atoms causing by the neighboring s Au on NiFe oxyhydroxide stabilized by interfacial CO 3 2- and H 2 O interfacing with LDH.

  7. Single and double polymerase chain reaction for detection of bovine viral diarrhea virus in tissue culture and sera.

    Science.gov (United States)

    Alansari, H; Brock, K V; Potgieter, L N

    1993-04-01

    Bovine viral diarrhea virus (BVDV) is an ubiquitous pathogen of cattle and has been reported in other ruminants. It is also frequently present in laboratory and biological materials as an adventitious agent. This virus is difficult to detect in some specimens, especially in the presence of specific antibody and when the virus is present in low concentrations. In this paper, we describe a single polymerase chain reaction (PCR) to amplify virus sequences from infected cell culture and a nested double PCR to detect small concentrations of several virus strains in sera. Total cellular RNA was extracted from cell cultures infected with the cytopathic strain 72 and noncytopathic strain 2724 of BVDV. Ten different genomic sequences along the length of the viral RNA ranging in size from 397 to 1,016 base pairs (bp) were successfully amplified by PCR. A 404-bp probe made from amplified product from the 3' end hybridized specifically with the RNA of several BVDV strains blotted on nylon filters. Viral RNA was extracted from serum and amplified using 2 sets of degenerate nested primers designed from the 3' end of the viral genome in a double PCR protocol. Double amplification of the viral sequences greatly enhanced the sensitivity of the detection of many strains present in serum. Advantages of using double PCR over single PCR and virus isolation is discussed.

  8. Kinematic arguments against single relativistic shell models for GRBs

    Science.gov (United States)

    Fenimore, Edward E.; Ramirez, E.; Sumner, M. C.

    1997-01-01

    Two main types of models have been suggested to explain the long durations and multiple peaks of Gamma Ray Bursts (GRBs). In one, there is a very quick release of energy at a central site resulting in a single relativistic shell that produces peaks in the time history through its interactions with the ambient material. In the other, the central site sporadically releases energy over hundreds of seconds forming a peak with each burst of energy. The authors show that the average envelope of emission and the presence of gaps in GRBs are inconsistent with a single relativistic shell. They estimate that the maximum fraction of a single shell that can produce gamma-rays in a GRB with multiple peaks is 10(exp (minus)3), implying that single relativistic shells require 10(exp 3) times more energy than previously thought. They conclude that either the central site of a GRB must produce (approx)10(exp 51) erg/s(exp (minus)1) for hundreds of seconds, or the relativistic shell must have structure on a scales the order of (radical)(epsilon)(Gamma)(exp (minus)1), where (Gamma) is the bulk Lorentz factor ((approximately)10(exp 2) to 10(exp 3)) and (epsilon) is the efficiency.

  9. Thermal asymmetry model of single slope single basin solar still with sponge liner

    Directory of Open Access Journals (Sweden)

    Shanmugan Sengottain

    2014-01-01

    Full Text Available An attempt has been made to propose a thermal asymmetry model for single slope basin type solar still with sponge liner of different thickness (3cm, 5cm, and 10cm in the basin. Two different color sponge liners have been used i.e., yellow and black. In the proposed design, a suitable dripping arrangement has been designed and used to pour water drop by drop over the sponge liner instead of sponge liner in stagnant saline water in the basin. The special arrangement overcomes the dryness of the sponge during peak sunny hours. The performance of the system with black color sponge of 3cm thickness shows better result with an output of 5.3 kg/m2 day and the proposed model have used to find the thermal asymmetries during the working hours of the still.

  10. Structure-reactivity modeling using mixture-based representation of chemical reactions.

    Science.gov (United States)

    Polishchuk, Pavel; Madzhidov, Timur; Gimadiev, Timur; Bodrov, Andrey; Nugmanov, Ramil; Varnek, Alexandre

    2017-09-01

    We describe a novel approach of reaction representation as a combination of two mixtures: a mixture of reactants and a mixture of products. In turn, each mixture can be encoded using an earlier reported approach involving simplex descriptors (SiRMS). The feature vector representing these two mixtures results from either concatenated product and reactant descriptors or the difference between descriptors of products and reactants. This reaction representation doesn't need an explicit labeling of a reaction center. The rigorous "product-out" cross-validation (CV) strategy has been suggested. Unlike the naïve "reaction-out" CV approach based on a random selection of items, the proposed one provides with more realistic estimation of prediction accuracy for reactions resulting in novel products. The new methodology has been applied to model rate constants of E2 reactions. It has been demonstrated that the use of the fragment control domain applicability approach significantly increases prediction accuracy of the models. The models obtained with new "mixture" approach performed better than those required either explicit (Condensed Graph of Reaction) or implicit (reaction fingerprints) reaction center labeling.

  11. PhreeqcRM: A reaction module for transport simulators based on the geochemical model PHREEQC

    Science.gov (United States)

    Parkhurst, David L.; Wissmeier, Laurin

    2015-09-01

    PhreeqcRM is a geochemical reaction module designed specifically to perform equilibrium and kinetic reaction calculations for reactive transport simulators that use an operator-splitting approach. The basic function of the reaction module is to take component concentrations from the model cells of the transport simulator, run geochemical reactions, and return updated component concentrations to the transport simulator. If multicomponent diffusion is modeled (e.g., Nernst-Planck equation), then aqueous species concentrations can be used instead of component concentrations. The reaction capabilities are a complete implementation of the reaction capabilities of PHREEQC. In each cell, the reaction module maintains the composition of all of the reactants, which may include minerals, exchangers, surface complexers, gas phases, solid solutions, and user-defined kinetic reactants. PhreeqcRM assigns initial and boundary conditions for model cells based on standard PHREEQC input definitions (files or strings) of chemical compositions of solutions and reactants. Additional PhreeqcRM capabilities include methods to eliminate reaction calculations for inactive parts of a model domain, transfer concentrations and other model properties, and retrieve selected results. The module demonstrates good scalability for parallel processing by using multiprocessing with MPI (message passing interface) on distributed memory systems, and limited scalability using multithreading with OpenMP on shared memory systems. PhreeqcRM is written in C++, but interfaces allow methods to be called from C or Fortran. By using the PhreeqcRM reaction module, an existing multicomponent transport simulator can be extended to simulate a wide range of geochemical reactions. Results of the implementation of PhreeqcRM as the reaction engine for transport simulators PHAST and FEFLOW are shown by using an analytical solution and the reactive transport benchmark of MoMaS.

  12. A single-phase model for liquid-feed DMFCs with non-Tafel kinetics

    Science.gov (United States)

    Vera, Marcos

    An isothermal single-phase 3D/1D model for liquid-feed direct methanol fuel cells (DMFC) is presented. Three-dimensional (3D) mass, momentum and species transport in the anode channels and gas diffusion layer is modeled using a commercial, finite-volume based, computational fluid dynamics (CFD) software complemented with user supplied subroutines. The 3D model is locally coupled to a one-dimensional (1D) model accounting for the electrochemical reactions in both the anode and the cathode, which provides a physically sound boundary condition for the velocity and methanol concentration fields at the anode gas diffusion layer/catalyst interface. The 1D model - comprising the membrane-electrode assembly, cathode gas diffusion layer, and cathode channel - assumes non-Tafel kinetics to describe the complex kinetics of the multi-step methanol oxidation reaction at the anode, and accounts for the mixed potential associated with methanol crossover, induced both by diffusion and electro-osmotic drag. Polarization curves computed for various methanol feed concentrations, temperatures, and methanol feed velocities show good agreement with recent experimental results. The spatial distribution of methanol in the anode channels, together with the distributions of current density, methanol crossover and fuel utilization at the anode catalyst layer, are also presented for different opperating conditions.

  13. A single-phase model for liquid-feed DMFCs with non-Tafel kinetics

    Energy Technology Data Exchange (ETDEWEB)

    Vera, Marcos [Area de Mecanica de Fluidos, Universidad Carlos III de Madrid, Avda. de la Universidad 30, 28911 Leganes (Spain)

    2007-09-27

    An isothermal single-phase 3D/1D model for liquid-feed direct methanol fuel cells (DMFC) is presented. Three-dimensional (3D) mass, momentum and species transport in the anode channels and gas diffusion layer is modeled using a commercial, finite-volume based, computational fluid dynamics (CFD) software complemented with user supplied subroutines. The 3D model is locally coupled to a one-dimensional (1D) model accounting for the electrochemical reactions in both the anode and the cathode, which provides a physically sound boundary condition for the velocity and methanol concentration fields at the anode gas diffusion layer/catalyst interface. The 1D model - comprising the membrane-electrode assembly, cathode gas diffusion layer, and cathode channel - assumes non-Tafel kinetics to describe the complex kinetics of the multi-step methanol oxidation reaction at the anode, and accounts for the mixed potential associated with methanol crossover, induced both by diffusion and electro-osmotic drag. Polarization curves computed for various methanol feed concentrations, temperatures, and methanol feed velocities show good agreement with recent experimental results. The spatial distribution of methanol in the anode channels, together with the distributions of current density, methanol crossover and fuel utilization at the anode catalyst layer, are also presented for different opperating conditions. (author)

  14. Reaction Automata

    OpenAIRE

    Okubo, Fumiya; Kobayashi, Satoshi; Yokomori, Takashi

    2011-01-01

    Reaction systems are a formal model that has been introduced to investigate the interactive behaviors of biochemical reactions. Based on the formal framework of reaction systems, we propose new computing models called reaction automata that feature (string) language acceptors with multiset manipulation as a computing mechanism, and show that reaction automata are computationally Turing universal. Further, some subclasses of reaction automata with space complexity are investigated and their la...

  15. Spin models for the single molecular magnet Mn12-AC

    Science.gov (United States)

    Al-Saqer, Mohamad A.

    2005-11-01

    The single molecular magnet (SMM) Mn12-AC attracted the attention of scientists since the discovery of its magnetic hystereses which are accompanied by sudden jumps in magnetic moments at low temperature. Unlike conventional bulk magnets, hysteresis in SMMs is of molecular origin. This qualifies them as candidates for next generation of high density storage media where a molecule which is at most few nanometers in size can be used to store a bit of information. However, the jumps in these hystereses, due to spin tunneling, can lead to undesired loss of information. Mn12-AC molecule contains twelve magnetic ions antiferromagnetically coupled by exchanges leading to S = 10 ground state manifold. The magnetic ions are surrounded by ligands which isolate them magnetically from neighboring molecules. The lowest state of S = 9 manifold is believed to lie at about 40 K above the ground state. Therefore, at low temperatures, the molecule is considered as a single uncoupled moment of spin S = 10. Such model has been used widely to understand phenomena exhibited by the molecule at low temperatures including the tunneling of its spin, while a little attention has been paid for the multi-spin nature of the molecule. Using the 8-spin model, we demonstrate that in order to understand the phenomena of tunneling, a full spin description of the molecule is required. We utilized a calculation scheme where a fraction of energy levels are used in the calculations and the influence of levels having higher energy is neglected. From the dependence of tunnel splittings on the number of states include, we conclude that models based on restricting the number of energy levels (single-spin and 8-spin models) lead to unreliable results of tunnel splitting calculations. To attack the full 12-spin model, we employed the Davidson algorithm to calculated lowest energy levels produced by exchange interactions and single ion anisotropies. The model reproduces the anisotropy properties at low

  16. Dynamic Modeling of LD Converter Steelmaking: Reaction Modeling Using Gibbs' Free Energy Minimization

    Science.gov (United States)

    Sarkar, Rahul; Gupta, Pramod; Basu, Somnath; Ballal, Nidambur Bharath

    2015-04-01

    Slag-metal emulsion plays an important role in the oxidation kinetics of metalloids in oxygen steelmaking. The importance of droplet generation rate, droplet size, and its residence time in the slag-metal emulsion on the overall reaction kinetics has become evident in recent times. Residence times of the droplets are strongly dependent on the decarburization rate, the CO bubbles giving a buoyant force to the droplets. The present work aims at developing a mathematical model for predicting the composition evolutions of the slag and the metal phases as the blow proceeds in an LD converter. The process dynamics are modeled by dividing the LD convertor into three separate continuous stirred tank reactors. Oxidation reactions are assumed to be primarily taking place at the interface between the slag and the metal phases in the emulsion. Among the different mass transfer and reaction steps controlling the kinetics, the mass transfer of FeO in the slag phase and that of the metalloids within the metal droplet are assumed to be rate-controlling. For a Fe-C-X (X = Mn, Si etc.) droplet, simultaneous removal of elements have been modeled by Gibbs' free energy minimization at the slag-metal interface. Effects of droplet size, mass transfer coefficient, and initial carbon content on the mean residence time of metal droplets in the slag-metal emulsion have also been identified. Mixing in the metal phase is simulated in terms of metal exchange rate and the reactor weight ratio between the upper and the lower parts of the bath.

  17. Steepest-entropy-ascent nonequilibrium quantum thermodynamic framework to model chemical reaction rates at an atomistic level.

    Science.gov (United States)

    Beretta, G P; Al-Abbasi, Omar; von Spakovsky, M R

    2017-04-01

    The steepest entropy ascent (SEA) dynamical principle provides a general framework for modeling the dynamics of nonequilibrium (NE) phenomena at any level of description, including the atomistic one. It has recently been shown to provide a precise implementation and meaning to the maximum entropy production principle and to encompass many well-established theories of nonequilibrium thermodynamics into a single unifying geometrical framework. Its original formulation in the framework of quantum thermodynamics (QT) assumes the simplest and most natural Fisher-Rao metric to geometrize from a dynamical standpoint the manifold of density operators, which represent the thermodynamic NE states of the system. This simplest SEAQT formulation is used here to develop a general mathematical framework for modeling the NE time evolution of the quantum state of a chemically reactive mixture at an atomistic level. The method is illustrated for a simple two-reaction kinetic scheme of the overall reaction F+H_{2}⇔HF+F in an isolated tank of fixed volume. However, the general formalism is developed for a reactive system subject to multiple reaction mechanisms. To explicitly implement the SEAQT nonlinear law of evolution for the density operator, both the energy and the particle number eigenvalue problems are set up and solved analytically under the dilute gas approximation. The system-level energy and particle number eigenvalues and eigenstates are used in the SEAQT equation of motion to determine the time evolution of the density operator, thus effectively describing the overall kinetics of the reacting system as it relaxes toward stable chemical equilibrium. The predicted time evolution in the near-equilibrium limit is compared to the reaction rates given by a standard detailed kinetic model so as to extract the single time constant needed by the present SEA model.

  18. Optimization of Maillard Reaction in Model System of Glucosamine and Cysteine Using Response Surface Methodology

    Science.gov (United States)

    Arachchi, Shanika Jeewantha Thewarapperuma; Kim, Ye-Joo; Kim, Dae-Wook; Oh, Sang-Chul; Lee, Yang-Bong

    2017-01-01

    Sulfur-containing amino acids play important roles in good flavor generation in Maillard reaction of non-enzymatic browning, so aqueous model systems of glucosamine and cysteine were studied to investigate the effects of reaction temperature, initial pH, reaction time, and concentration ratio of glucosamine and cysteine. Response surface methodology was applied to optimize the independent reaction parameters of cysteine and glucosamine in Maillard reaction. Box-Behnken factorial design was used with 30 runs of 16 factorial levels, 8 axial levels and 6 central levels. The degree of Maillard reaction was determined by reading absorption at 425 nm in a spectrophotometer and Hunter’s L, a, and b values. ΔE was consequently set as the fifth response factor. In the statistical analyses, determination coefficients (R2) for their absorbance, Hunter’s L, a, b values, and ΔE were 0.94, 0.79, 0.73, 0.96, and 0.79, respectively, showing that the absorbance and Hunter’s b value were good dependent variables for this model system. The optimum processing parameters were determined to yield glucosamine-cysteine Maillard reaction product with higher absorbance and higher colour change. The optimum estimated absorbance was achieved at the condition of initial pH 8.0, 111°C reaction temperature, 2.47 h reaction time, and 1.30 concentration ratio. The optimum condition for colour change measured by Hunter’s b value was 2.41 h reaction time, 114°C reaction temperature, initial pH 8.3, and 1.26 concentration ratio. These results can provide the basic information for Maillard reaction of aqueous model system between glucosamine and cysteine. PMID:28401086

  19. Optimization of Maillard Reaction in Model System of Glucosamine and Cysteine Using Response Surface Methodology.

    Science.gov (United States)

    Arachchi, Shanika Jeewantha Thewarapperuma; Kim, Ye-Joo; Kim, Dae-Wook; Oh, Sang-Chul; Lee, Yang-Bong

    2017-03-01

    Sulfur-containing amino acids play important roles in good flavor generation in Maillard reaction of non-enzymatic browning, so aqueous model systems of glucosamine and cysteine were studied to investigate the effects of reaction temperature, initial pH, reaction time, and concentration ratio of glucosamine and cysteine. Response surface methodology was applied to optimize the independent reaction parameters of cysteine and glucosamine in Maillard reaction. Box-Behnken factorial design was used with 30 runs of 16 factorial levels, 8 axial levels and 6 central levels. The degree of Maillard reaction was determined by reading absorption at 425 nm in a spectrophotometer and Hunter's L, a, and b values. ΔE was consequently set as the fifth response factor. In the statistical analyses, determination coefficients (R 2 ) for their absorbance, Hunter's L, a, b values, and ΔE were 0.94, 0.79, 0.73, 0.96, and 0.79, respectively, showing that the absorbance and Hunter's b value were good dependent variables for this model system. The optimum processing parameters were determined to yield glucosamine-cysteine Maillard reaction product with higher absorbance and higher colour change. The optimum estimated absorbance was achieved at the condition of initial pH 8.0, 111°C reaction temperature, 2.47 h reaction time, and 1.30 concentration ratio. The optimum condition for colour change measured by Hunter's b value was 2.41 h reaction time, 114°C reaction temperature, initial pH 8.3, and 1.26 concentration ratio. These results can provide the basic information for Maillard reaction of aqueous model system between glucosamine and cysteine.

  20. Modeling of the symmetry factor of electrochemical proton discharge via the Volmer reaction

    DEFF Research Database (Denmark)

    Björketun, Mårten E.; Tripkovic, Vladimir; Skúlason, Egill

    2013-01-01

    A scheme for evaluating symmetry factors of elementary electrode reactions using a density functional theory (DFT) based model of the electrochemical double layer is presented. As an illustration, the symmetry factor is determined for hydrogen adsorption via the electrochemical Volmer reaction...

  1. Modeling Proton- and Light Ion-Induced Reactions at Low Energies in the MARS15 Code

    Energy Technology Data Exchange (ETDEWEB)

    Rakhno, I. L. [Fermi National Accelerator Lab. (FNAL), Batavia, IL (United States); Mokhov, N. V. [Fermi National Accelerator Lab. (FNAL), Batavia, IL (United States); Gudima, K. K. [National Academy of Sciences, Cisineu (Moldova)

    2015-04-25

    An implementation of both ALICE code and TENDL evaluated nuclear data library in order to describe nuclear reactions induced by low-energy projectiles in the Monte Carlo code MARS15 is presented. Comparisons between results of modeling and experimental data on reaction cross sections and secondary particle distributions are shown.

  2. Testing an explanatory model of nurses' intention to report adverse drug reactions in hospital settings.

    Science.gov (United States)

    Angelis, Alessia De; Pancani, Luca; Steca, Patrizia; Colaceci, Sofia; Giusti, Angela; Tibaldi, Laura; Alvaro, Rosaria; Ausili, Davide; Vellone, Ercole

    2017-05-01

    To test an explanatory model of nurses' intention to report adverse drug reactions in hospital settings, based on the theory of planned behaviour. Under-reporting of adverse drug reactions is an important problem among nurses. A cross-sectional design was used. Data were collected with the adverse drug reporting nurses' questionnaire. Confirmatory factor analysis was performed to test the factor validity of the adverse drug reporting nurses' questionnaire, and structural equation modelling was used to test the explanatory model. The convenience sample comprised 500 Italian hospital nurses (mean age = 43.52). Confirmatory factor analysis supported the factor validity of the adverse drug reporting nurses' questionnaire. The structural equation modelling showed a good fit with the data. Nurses' intention to report adverse drug reactions was significantly predicted by attitudes, subjective norms and perceived behavioural control (R² = 0.16). The theory of planned behaviour effectively explained the mechanisms behind nurses' intention to report adverse drug reactions, showing how several factors come into play. In a scenario of organisational empowerment towards adverse drug reaction reporting, the major predictors of the intention to report are support for the decision to report adverse drug reactions from other health care practitioners, perceptions about the value of adverse drug reaction reporting and nurses' favourable self-assessment of their adverse drug reaction reporting skills. © 2017 John Wiley & Sons Ltd.

  3. New tools in modulating Maillard reaction from model systems to food

    NARCIS (Netherlands)

    Troise, A.D.

    2015-01-01

    New tools in modulating Maillard reaction from model systems to food
    The Maillard reaction (MR) supervises the final quality of foods and occupies a prominent place in food science. The first stable compounds, the Amadori rearrangement products

  4. Modeling multi-component transport and enhanced anaerobic dechlorination processes in a single fracture-clay matrix system

    DEFF Research Database (Denmark)

    Chambon, Julie Claire Claudia; Broholm, Mette Martina; Binning, Philip John

    2010-01-01

    Clayey tills contaminated with chlorinated solvents are a threat to groundwater and are difficult to remediate. A numerical model is developed for assessing leaching processes and for simulating the remediation via enhanced anaerobic dechlorination. The model simulates the transport...... of a contaminant in a single fracture-clay matrix system coupled with a reactive model for anaerobic dechlorination. The model takes into account microbially driven anaerobic dechlorination, where sequential Monod kinetics with competitive inhibition is used to model the reaction rates, and degradation...... to the physical processes, mainly diffusion in the matrix, than to the biogeochemical processes, when dechlorination is assumed to take place in a limited reaction zone only. The inclusion of sequential dechlorination in clay fracture transport models is crucial, as the contaminant flux to the aquifer...

  5. Modeling thermal spike driven reactions at low temperature and application to zirconium carbide radiation damage

    Science.gov (United States)

    Ulmer, Christopher J.; Motta, Arthur T.

    2017-11-01

    The development of TEM-visible damage in materials under irradiation at cryogenic temperatures cannot be explained using classical rate theory modeling with thermally activated reactions since at low temperatures thermal reaction rates are too low. Although point defect mobility approaches zero at low temperature, the thermal spikes induced by displacement cascades enable some atom mobility as it cools. In this work a model is developed to calculate "athermal" reaction rates from the atomic mobility within the irradiation-induced thermal spikes, including both displacement cascades and electronic stopping. The athermal reaction rates are added to a simple rate theory cluster dynamics model to allow for the simulation of microstructure evolution during irradiation at cryogenic temperatures. The rate theory model is applied to in-situ irradiation of ZrC and compares well at cryogenic temperatures. The results show that the addition of the thermal spike model makes it possible to rationalize microstructure evolution in the low temperature regime.

  6. Scaling properties in single collision model of light ion reflection

    International Nuclear Information System (INIS)

    Vukanic, J.; Simovic, R.

    2004-01-01

    Light ion reflection from solids in the keV energy region has been studied within the single collision model. Particle and energy reflection coefficients as functions of the scaled transport cross section have been calculated numerically by utilizing the exact scattering function for the Kr-C potential and analytically with an effective power approximation for the same potential. The obtained analytical formulae approximate very accurately to the numerical results. Comparison of the calculated reflection coefficients with the experimental data and computer simulations for different light ion-heavy target combinations shows that the scaled transport cross section remains a convenient scaling parameter in the single collision domain, as adopted previously in multiple collision theory

  7. Multiscale modeling and surgical planning for single ventricle heart patients

    Science.gov (United States)

    Marsden, Alison

    2011-11-01

    Single ventricle heart patients are among the most challenging for pediatric cardiologists to treat, and typically undergo a palliative course of three open-heart surgeries starting immediately after birth. We will present recent tools for modeling blood flow in single ventricle heart patients using a multiscale approach that couples a 3D Navier-Stokes domain to a 0D closed loop lumped parameter network comprised of circuit elements. This coupling allows us to capture the effect of changes in local geometry, such as shunt sizes, on global circulatory dynamics, such as cardiac output. A semi-implicit numerical method is formulated to solve the coupled system in which flow and pressure information is passed between the two domains at the inlets and outlets of the model. A finite element method with outflow stabilization is applied in the 3D Navier-Stokes domain, and the LPN system of ordinary differential equations is solved numerically using a Runge-Kutta method. These tools are coupled via automated scripts to a derivative-free optimization method. Optimization is used to systematically explore surgical designs using clinically relevant cost functions for two stages of single ventricle repair. First, we will present results from optimization of the first stage Blalock Taussig Shunt. Second, we will present results from optimization of a new Y-graft design for the third stage of single ventricle repair called the Fontan surgery. The Y-graft is shown, in simulations, to successfully improve hepatic flow distribution, a known clinical problem. Preliminary clinical experience with the Y-graft will be discussed.

  8. The Sugar Model: Autocatalytic Activity of the Triose-Ammonia Reaction

    Science.gov (United States)

    Weber, Arthur L.

    2006-01-01

    Reaction of triose sugars with ammonia under anaerobic conditions yielded autocatalytic products. The autocatalytic behavior of the products was examined by measuring the effect of the crude triose-ammonia reaction product on the kinetics of a second identical triose-ammonia reaction. The reaction product showed autocatalytic activity by increasing both the rate of disappearance of triose and the rate formation of pyruvaldehyde, the product of triose dehydration. This synthetic process is considered a reasonable model of origin-of-life chemistry because it uses plausible prebiotic substrates, and resembles modern biosynthesis by employing the energized carbon groups of sugars to drive the synthesis of autocatalytic molecules.

  9. Modeling the Electrochemical Hydrogen Oxidation and Evolution Reactions on the Basis of Density Functional Theory Calculations

    DEFF Research Database (Denmark)

    Skulason, Egill; Tripkovic, Vladimir; Björketun, Mårten

    2010-01-01

    Density functional theory calculations have been performed for the three elementary steps―Tafel, Heyrovsky, and Volmer―involved in the hydrogen oxidation reaction (HOR) and its reverse, the hydrogen evolution reaction (HER). For the Pt(111) surface a detailed model consisting of a negatively...... charged Pt(111) slab and solvated protons in up to three water bilayers is considered and reaction energies and activation barriers are determined by using a newly developed computational scheme where the potential can be kept constant during a charge transfer reaction. We determine the rate limiting...

  10. A self-organising model of market with single commodity

    Science.gov (United States)

    Chakraborti, Anirban; Pradhan, Srutarshi; Chakrabarti, Bikas K.

    2001-08-01

    We have studied here the self-organising features of the dynamics of a model market, where the agents ‘trade’ for a single commodity with their money. The model market consists of fixed numbers of economic agents, money supply and commodity. We demonstrate that the model, apart from showing a self-organising behaviour, indicates a crucial role for the money supply in the market and also its self-organising behaviour is seen to be significantly affected when the money supply becomes less than the optimum. We also observed that this optimal money supply level of the market depends on the amount of ‘frustration’ or scarcity in the commodity market.

  11. A kinetic reaction model for biomass pyrolysis processes in Aspen Plus

    International Nuclear Information System (INIS)

    Peters, Jens F.; Banks, Scott W.; Bridgwater, Anthony V.; Dufour, Javier

    2017-01-01

    Highlights: • Predictive kinetic reaction model applicable to any lignocellulosic feedstock. • Calculates pyrolysis yields and product composition as function of reactor conditions. • Detailed modelling of product composition (33 model compounds for the bio-oil). • Good agreement with literature regarding yield curves and product composition. • Successful validation with pyrolysis experiments in bench scale fast pyrolysis rig. - Abstract: This paper presents a novel kinetic reaction model for biomass pyrolysis processes. The model is based on the three main building blocks of lignocellulosic biomass, cellulose, hemicellulose and lignin and can be readily implemented in Aspen Plus and easily adapted to other process simulation software packages. It uses a set of 149 individual reactions that represent the volatilization, decomposition and recomposition processes of biomass pyrolysis. A linear regression algorithm accounts for the secondary pyrolysis reactions, thus allowing the calculation of slow and intermediate pyrolysis reactions. The bio-oil is modelled with a high level of detail, using up to 33 model compounds, which allows for a comprehensive estimation of the properties of the bio-oil and the prediction of further upgrading reactions. After showing good agreement with existing literature data, our own pyrolysis experiments are reported for validating the reaction model. A beech wood feedstock is subjected to pyrolysis under well-defined conditions at different temperatures and the product yields and compositions are determined. Reproducing the experimental pyrolysis runs with the simulation model, a high coincidence is found for the obtained fraction yields (bio-oil, char and gas), for the water content and for the elemental composition of the pyrolysis products. The kinetic reaction model is found to be suited for predicting pyrolysis yields and product composition for any lignocellulosic biomass feedstock under typical pyrolysis conditions

  12. Attractor for a Reaction-Diffusion System Modeling Cancer Network

    Directory of Open Access Journals (Sweden)

    Xueyong Chen

    2014-01-01

    Full Text Available A reaction-diffusion cancer network regulated by microRNA is considered in this paper. We study the asymptotic behavior of solution and show the existence of global uniformly bounded solution to the system in a bounded domain Ω⊂Rn. Some estimates and asymptotic compactness of the solutions are proved. As a result, we establish the existence of the global attractor in L2(Ω×L2(Ω and prove that the solution converges to stable steady states. These results can help to understand the dynamical character of cancer network and propose a new insight to study the mechanism of cancer. In the end, the numerical simulation shows that the analytical results agree with numerical simulation.

  13. Investigations of Spectroscopic Factors and Sum Rules from the Single Neutron Transfer Reaction 111Cd(d→$\\overrightarrow {\\rm{d}} $,p112Cd

    Directory of Open Access Journals (Sweden)

    Jamieson D.S.

    2014-03-01

    Full Text Available Cadmium isotopes have been presented for decades as excellent examples of vibrational nuclei, with low-lying levels interpreted as multi-phonon quadrupole, octupole, and mixed-symmetry states. A large amount of spectroscopic data has been obtained through various experimental studies of cadmiumisotopes. In the present work, the 111Cd(d→$\\overrightarrow {\\rm{d}} $,p112Cd reaction was used to investigate the single-particle structure of the 112Cd nucleus. A 22 MeV beam of polarized deuterons was obtained at the Maier-Leibnitz laboratory in Garching, Germany. The reaction ejectiles were momentum analyzed using a Q3D spectrograph, and 130 levels have been identified up to 4.2 MeV of excitation energy. Using DWBA analysis with optical model calculations, spin-parity assignments have been made for observed levels, and spectroscopic factors have been extracted from the experimental angular distributions of differential cross section and analyzing power. In this high energy resolution investigation, many additional levels have been observed compared with the previous (d,p study using 8 MeV deuterons [1]. There were a total of 44 new levels observed, and the parity assignments of 34 levels were improved.

  14. Stochastic modeling and simulation of reaction-diffusion system with Hill function dynamics.

    Science.gov (United States)

    Chen, Minghan; Li, Fei; Wang, Shuo; Cao, Young

    2017-03-14

    Stochastic simulation of reaction-diffusion systems presents great challenges for spatiotemporal biological modeling and simulation. One widely used framework for stochastic simulation of reaction-diffusion systems is reaction diffusion master equation (RDME). Previous studies have discovered that for the RDME, when discretization size approaches zero, reaction time for bimolecular reactions in high dimensional domains tends to infinity. In this paper, we demonstrate that in the 1D domain, highly nonlinear reaction dynamics given by Hill function may also have dramatic change when discretization size is smaller than a critical value. Moreover, we discuss methods to avoid this problem: smoothing over space, fixed length smoothing over space and a hybrid method. Our analysis reveals that the switch-like Hill dynamics reduces to a linear function of discretization size when the discretization size is small enough. The three proposed methods could correctly (under certain precision) simulate Hill function dynamics in the microscopic RDME system.

  15. On the single-mass model of the vocal folds

    International Nuclear Information System (INIS)

    Howe, M S; McGowan, R S

    2010-01-01

    An analysis is made of the fluid-structure interactions necessary to support self-sustained oscillations of a single-mass mechanical model of the vocal folds subject to a nominally steady subglottal overpressure. The single-mass model of Fant and Flanagan is re-examined and an analytical representation of vortex shedding during 'voiced speech' is proposed that promotes cooperative, periodic excitation of the folds by the glottal flow. Positive feedback that sustains glottal oscillations is shown to occur during glottal contraction, when the flow separates from the 'trailing edge' of the glottis producing a low-pressure 'suction' force that tends to pull the folds together. Details are worked out for flow that can be regarded as locally two-dimensional in the glottal region. Predictions of free-streamline theory are used to model the effects of quasi-static variations in the separation point on the glottal wall. Numerical predictions are presented to illustrate the waveform of the sound radiated towards the mouth from the glottis. The theory is easily modified to include feedback on the glottal flow of standing acoustic waves, both in the vocal tract beyond the glottis and in the subglottal region. (invited paper)

  16. Single-image-based Modelling Architecture from a Historical Photograph

    Science.gov (United States)

    Dzwierzynska, Jolanta

    2017-10-01

    Historical photographs are proved to be very useful to provide a dimensional and geometrical analysis of buildings as well as to generate 3D reconstruction of the whole structure. The paper addresses the problem of single historical photograph analysis and modelling of an architectural object from it. Especially, it focuses on reconstruction of the original look of New-Town synagogue from the single historic photograph, when camera calibration is completely unknown. Due to the fact that the photograph faithfully followed the geometric rules of perspective, it was possible to develop and apply the method to obtain a correct 3D reconstruction of the building. The modelling process consisted of a series of familiar steps: feature extraction, determination of base elements of perspective, dimensional analyses and 3D reconstruction. Simple formulas were proposed in order to estimate location of characteristic points of the building in 3D Cartesian system of axes on the base of their location in 2D Cartesian system of axes. The reconstruction process proceeded well, although slight corrections were necessary. It was possible to reconstruct the shape of the building in general, and two of its facades in detail. The reconstruction of the other two facades requires some additional information or the additional picture. The success of the presented reconstruction method depends on the geometrical content of the photograph as well as quality of the picture, which ensures the legibility of building edges. The presented method of reconstruction is a combination of the descriptive method of reconstruction and computer aid; therefore, it seems to be universal. It can prove useful for single-image-based modelling architecture.

  17. Replica Analysis for Portfolio Optimization with Single-Factor Model

    Science.gov (United States)

    Shinzato, Takashi

    2017-06-01

    In this paper, we use replica analysis to investigate the influence of correlation among the return rates of assets on the solution of the portfolio optimization problem. We consider the behavior of an optimal solution for the case where the return rate is described with a single-factor model and compare the findings obtained from our proposed methods with correlated return rates with those obtained with independent return rates. We then analytically assess the increase in the investment risk when correlation is included. Furthermore, we also compare our approach with analytical procedures for minimizing the investment risk from operations research.

  18. Gravity research on plants: use of single cell experimental models

    Directory of Open Access Journals (Sweden)

    Youssef eChebli

    2011-09-01

    Full Text Available Future space missions and implementation of permanent bases on Moon and Mars will greatly depend on the availability of ambient air and sustainable food supply. Therefore, understanding the effects of altered gravity conditions on plant metabolism and growth is vital for space missions and extra-terrestrial human existence. In this mini-review we summarize how plant cells are thought to perceive changes in magnitude and orientation of the gravity vector. The particular advantages of several single celled model systems for gravity research are explored and an overview over recent advancements and potential use of these systems is provided.

  19. Linear dynamic models for classification of single-trial EEG.

    Science.gov (United States)

    Samdin, S Balqis; Ting, Chee-Ming; Salleh, Sh-Hussain; Ariff, A K; Mohd Noor, A B

    2013-01-01

    This paper investigates the use of linear dynamic models (LDMs) to improve classification of single-trial EEG signals. Existing dynamic classification of EEG uses discrete-state hidden Markov models (HMMs) based on piecewise-stationary assumption, which is inadequate for modeling the highly non-stationary dynamics underlying EEG. The continuous hidden states of LDMs could better describe this continuously changing characteristic of EEG, and thus improve the classification performance. We consider two examples of LDM: a simple local level model (LLM) and a time-varying autoregressive (TVAR) state-space model. AR parameters and band power are used as features. Parameter estimation of the LDMs is performed by using expectation-maximization (EM) algorithm. We also investigate different covariance modeling of Gaussian noises in LDMs for EEG classification. The experimental results on two-class motor-imagery classification show that both types of LDMs outperform the HMM baseline, with the best relative accuracy improvement of 14.8% by LLM with full covariance for Gaussian noises. It may due to that LDMs offer more flexibility in fitting the underlying dynamics of EEG.

  20. Single-molecule Imaging Analysis of Elementary Reaction Steps of Trichoderma reesei Cellobiohydrolase I (Cel7A) Hydrolyzing Crystalline Cellulose Iα and IIII*

    Science.gov (United States)

    Shibafuji, Yusuke; Nakamura, Akihiko; Uchihashi, Takayuki; Sugimoto, Naohisa; Fukuda, Shingo; Watanabe, Hiroki; Samejima, Masahiro; Ando, Toshio; Noji, Hiroyuki; Koivula, Anu; Igarashi, Kiyohiko; Iino, Ryota

    2014-01-01

    Trichoderma reesei cellobiohydrolase I (TrCel7A) is a molecular motor that directly hydrolyzes crystalline celluloses into water-soluble cellobioses. It has recently drawn attention as a tool that could be used to convert cellulosic materials into biofuel. However, detailed mechanisms of action, including elementary reaction steps such as binding, processive hydrolysis, and dissociation, have not been thoroughly explored because of the inherent challenges associated with monitoring reactions occurring at the solid/liquid interface. The crystalline cellulose Iα and IIII were previously reported as substrates with different crystalline forms and different susceptibilities to hydrolysis by TrCel7A. In this study, we observed that different susceptibilities of cellulose Iα and IIII are highly dependent on enzyme concentration, and at nanomolar enzyme concentration, TrCel7A shows similar rates of hydrolysis against cellulose Iα and IIII. Using single-molecule fluorescence microscopy and high speed atomic force microscopy, we also determined kinetic constants of the elementary reaction steps for TrCel7A against cellulose Iα and IIII. These measurements were performed at picomolar enzyme concentration in which density of TrCel7A on crystalline cellulose was very low. Under this condition, TrCel7A displayed similar binding and dissociation rate constants for cellulose Iα and IIII and similar fractions of productive binding on cellulose Iα and IIII. Furthermore, once productively bound, TrCel7A processively hydrolyzes and moves along cellulose Iα and IIII with similar translational rates. With structural models of cellulose Iα and IIII, we propose that different susceptibilities at high TrCel7A concentration arise from surface properties of substrate, including ratio of hydrophobic surface and number of available lanes. PMID:24692563

  1. Efficiency of alternative MCMC strategies illustrated using the reaction norm model.

    Science.gov (United States)

    Shariati, M; Sorensen, D

    2008-06-01

    The Markov chain Monte Carlo (MCMC) strategy provides remarkable flexibility for fitting complex hierarchical models. However, when parameters are highly correlated in their posterior distributions and their number is large, a particular MCMC algorithm may perform poorly and the resulting inferences may be affected. The objective of this study was to compare the efficiency (in terms of the asymptotic variance of features of posterior distributions of chosen parameters, and in terms of computing cost) of six MCMC strategies to sample parameters using simulated data generated with a reaction norm model with unknown covariates as an example. The six strategies are single-site Gibbs updates (SG), single-site Gibbs sampler for updating transformed (a priori independent) additive genetic values (TSG), pairwise Gibbs updates (PG), blocked (all location parameters are updated jointly) Gibbs updates (BG), Langevin-Hastings (LH) proposals, and finally Langevin-Hastings proposals for updating transformed additive genetic values (TLH). The ranking of the methods in terms of asymptotic variance is affected by the degree of the correlation structure of the data and by the true values of the parameters, and no method comes out as an overall winner across all parameters. TSG and BG show very good performance in terms of asymptotic variance especially when the posterior correlation between genetic effects is high. In terms of computing cost, TSG performs best except for dispersion parameters in the low correlation scenario where SG was the best strategy. The two LH proposals could not compete with any of the Gibbs sampling algorithms. In this study it was not possible to find an MCMC strategy that performs optimally across the range of target distributions and across all possible values of parameters. However, when the posterior correlation between parameters is high, TSG, BG and even PG show better mixing than SG.

  2. Analyzing Reaction Rates with the Distortion/Interaction‐Activation Strain Model

    Science.gov (United States)

    2017-01-01

    Abstract The activation strain or distortion/interaction model is a tool to analyze activation barriers that determine reaction rates. For bimolecular reactions, the activation energies are the sum of the energies to distort the reactants into geometries they have in transition states plus the interaction energies between the two distorted molecules. The energy required to distort the molecules is called the activation strain or distortion energy. This energy is the principal contributor to the activation barrier. The transition state occurs when this activation strain is overcome by the stabilizing interaction energy. Following the changes in these energies along the reaction coordinate gives insights into the factors controlling reactivity. This model has been applied to reactions of all types in both organic and inorganic chemistry, including substitutions and eliminations, cycloadditions, and several types of organometallic reactions. PMID:28447369

  3. Analyzing Reaction Rates with the Distortion/Interaction-Activation Strain Model.

    Science.gov (United States)

    Bickelhaupt, F Matthias; Houk, Kendall N

    2017-08-14

    The activation strain or distortion/interaction model is a tool to analyze activation barriers that determine reaction rates. For bimolecular reactions, the activation energies are the sum of the energies to distort the reactants into geometries they have in transition states plus the interaction energies between the two distorted molecules. The energy required to distort the molecules is called the activation strain or distortion energy. This energy is the principal contributor to the activation barrier. The transition state occurs when this activation strain is overcome by the stabilizing interaction energy. Following the changes in these energies along the reaction coordinate gives insights into the factors controlling reactivity. This model has been applied to reactions of all types in both organic and inorganic chemistry, including substitutions and eliminations, cycloadditions, and several types of organometallic reactions. © 2017 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA.

  4. BGK-type models in strong reaction and kinetic chemical equilibrium regimes

    International Nuclear Information System (INIS)

    Monaco, R; Bianchi, M Pandolfi; Soares, A J

    2005-01-01

    A BGK-type procedure is applied to multi-component gases undergoing chemical reactions of bimolecular type. The relaxation process towards local Maxwellians, depending on mass and numerical densities of each species as well as common velocity and temperature, is investigated in two different cases with respect to chemical regimes. These cases are related to the strong reaction regime characterized by slow reactions, and to the kinetic chemical equilibrium regime where fast reactions take place. The consistency properties of both models are stated in detail. The trend to equilibrium is numerically tested and comparisons for the two regimes are performed within the hydrogen-air and carbon-oxygen reaction mechanism. In the spatial homogeneous case, it is also shown that the thermodynamical equilibrium of the models recovers satisfactorily the asymptotic equilibrium solutions to the reactive Euler equations

  5. Modeling bacterial population growth from stochastic single-cell dynamics.

    Science.gov (United States)

    Alonso, Antonio A; Molina, Ignacio; Theodoropoulos, Constantinos

    2014-09-01

    A few bacterial cells may be sufficient to produce a food-borne illness outbreak, provided that they are capable of adapting and proliferating on a food matrix. This is why any quantitative health risk assessment policy must incorporate methods to accurately predict the growth of bacterial populations from a small number of pathogens. In this aim, mathematical models have become a powerful tool. Unfortunately, at low cell concentrations, standard deterministic models fail to predict the fate of the population, essentially because the heterogeneity between individuals becomes relevant. In this work, a stochastic differential equation (SDE) model is proposed to describe variability within single-cell growth and division and to simulate population growth from a given initial number of individuals. We provide evidence of the model ability to explain the observed distributions of times to division, including the lag time produced by the adaptation to the environment, by comparing model predictions with experiments from the literature for Escherichia coli, Listeria innocua, and Salmonella enterica. The model is shown to accurately predict experimental growth population dynamics for both small and large microbial populations. The use of stochastic models for the estimation of parameters to successfully fit experimental data is a particularly challenging problem. For instance, if Monte Carlo methods are employed to model the required distributions of times to division, the parameter estimation problem can become numerically intractable. We overcame this limitation by converting the stochastic description to a partial differential equation (backward Kolmogorov) instead, which relates to the distribution of division times. Contrary to previous stochastic formulations based on random parameters, the present model is capable of explaining the variability observed in populations that result from the growth of a small number of initial cells as well as the lack of it compared to

  6. Factors associated with acute oral mucosal reaction induced by radiotherapy in head and neck squamous cell carcinoma: A retrospective single-center experience.

    Science.gov (United States)

    Tao, Zhenchao; Gao, Jin; Qian, Liting; Huang, Yifan; Zhou, Yan; Yang, Liping; He, Jian; Yang, Jing; Wang, Ru; Zhang, Yangyang

    2017-12-01

    To investigate risk factors for acute oral mucosal reaction during head and neck squamous cell carcinoma radiotherapy.A retrospective study of patients with head and neck squamous cell carcinoma who underwent radiotherapy from November 2013 to May 2016 in Anhui Provincial Cancer Hospital was conducted. Data on the occurrence and severity of acute oral mucositis were extracted from clinical records. Based on the Radiation Therapy Oncology Group (RTOG) grading of acute radiation mucosal injury, the patients were assigned into acute reaction (grades 2-4) and minimum reaction (grades 0-1) groups. Preradiotherapy characteristics and treatment factors were compared between the 2 groups. Multivariate logistic regression analysis was used to detect the independent factors associated with acute oral mucosal reactions.Eighty patients completed radiotherapy during the study period. Oral mucosal reactions were recorded as 25, 31, and 24 cases of grades 1, 2, and 3 injuries, respectively. Significant differences between acute reaction and minimum reaction groups were detected in cancer lymph node (N) staging, smoking and diabetes history, pretreatment platelet count and T-Helper/T-Suppressor lymphocyte (Th/Ts) ratio, concurrent chemotherapy, and total and single irradiation doses.Multivariate analysis showed that N stage, smoking history, single dose parapharyngeal irradiation, and pretreatment platelet count were independent risk factors for acute radiation induced oral mucosal reaction. Smoking history, higher grading of N stage, higher single dose irradiation, and lower preirradiation platelet count may increase the risk and severity of acute radiation oral mucosal reaction in radiotherapy of head and neck cancer patients. Copyright © 2017 The Authors. Published by Wolters Kluwer Health, Inc. All rights reserved.

  7. New model of chlorine-wall reaction for simulating chlorine concentration in drinking water distribution systems.

    Science.gov (United States)

    Fisher, Ian; Kastl, George; Sathasivan, Arumugam

    2017-11-15

    Accurate modelling of chlorine concentrations throughout a drinking water system needs sound mathematical descriptions of decay mechanisms in bulk water and at pipe walls. Wall-reaction rates along pipelines in three different systems were calculated from differences between field chlorine profiles and accurately modelled bulk decay. Lined pipes with sufficiently large diameters (>500 mm) and higher chlorine concentrations (>0.5 mg/L) had negligible wall-decay rates, compared with bulk-decay rates. Further downstream, wall-reaction rate consistently increased (peaking around 0.15 mg/dm 2 /h) as chlorine concentration decreased, until mass-transport to the wall was controlling wall reaction. These results contradict wall-reaction models, including those incorporated in the EPANET software, which assume wall decay is of either zero-order (constant decay rate) or first-order (wall-decay rate reduces with chlorine concentration). Instead, results are consistent with facilitation of the wall reaction by biofilm activity, rather than surficial chemical reactions. A new model of wall reaction combines the effect of biofilm activity moderated by chlorine concentration and mass-transport limitation. This wall reaction model, with an accurate bulk chlorine decay model, is essential for sufficiently accurate prediction of chlorine residuals towards the end of distribution systems and therefore control of microbial contamination. Implementing this model in EPANET-MSX (or similar) software enables the accurate chlorine modelling required for improving disinfection strategies in drinking water networks. New insight into the effect of chlorine on biofilm can also assist in controlling biofilm to maintain chlorine residuals. Copyright © 2017 Elsevier Ltd. All rights reserved.

  8. The PLP cofactor: lessons from studies on model reactions.

    Science.gov (United States)

    Richard, John P; Amyes, Tina L; Crugeiras, Juan; Rios, Ana

    2011-11-01

    Experimental probes of the acidity of weak carbon acids have been developed and used to determine the carbon acid pK(a)s of glycine, glycine derivatives and iminium ion adducts of glycine to the carbonyl group, including 5'-deoxypyridoxal (DPL). The high reactivity of the DPL-stabilized glycyl carbanion towards nucleophilic addition to both DPL and the glycine-DPL iminium ion favors the formation of Claisen condensation products at enzyme active sites. The formation of the iminium ion between glycine and DPL is accompanied by a 12-unit decrease in the pK(a) of 29 for glycine. The complicated effects of formation of glycine iminium ions to DPL and other aromatic and aliphatic aldehydes and ketones on carbon acid pK(a) are discussed. These data provide insight into the contribution of the individual pyridine ring substituents to the catalytic efficiency of DPL. It is suggested that the 5'-phosphodianion group of PLP may play an important role in enzymatic catalysis of carbon deprotonation by providing up to 12 kcal/mol of binding energy that is utilized to stabilize the transition state for the enzymatic reaction. This article is part of a Special Issue entitled: Pyridoxal Phospate Enzymology. Copyright © 2010 Elsevier B.V. All rights reserved.

  9. Some Calculated (p,α Cross-Sections Using the Alpha Particle Knock-On and Triton Pick-Up Reaction Mechanisms: An Optimisation of the Single-Step Feshbach–Kerman–Koonin (FKK Theory

    Directory of Open Access Journals (Sweden)

    Felix S. Olise

    2016-04-01

    Full Text Available The Feshbach–Kerman–Koonin (FKK multi-step direct (MSD theory of pre-equilibrium reactions has been used to compute the single-step cross-sections for some (p,α reactions using the knock-on and pick-up reaction mechanisms at two incident proton energies. For the knock-on mechanism, the reaction was assumed to have taken place by the direct ejection of a preformed alpha cluster in a shell-model state of the target. But the reaction was assumed to have taken place by the pick-up of a preformed triton cluster (also bound in a shell-model state of the target core by the incident proton for the pick-up mechanism. The Yukawa forms of potential were used for the proton-alpha (for the knock-on process and proton-triton (for the pick-up process interaction and several parameter sets for the proton and alpha-particle optical potentials. The calculated cross-sections for both mechanisms gave satisfactory fits to the experimental data. Furthermore, it has been shown that some combinations of the calculated distorted wave Born approximation cross-sections for the two reaction mechanisms in the FKK MSD theory are able to give better fits to the experimental data, especially in terms of range of agreement. In addition, the theory has been observed to be valid over a wider range of energy.

  10. A simple recipe for modeling reaction-rate in flows with turbulent-combustion

    Science.gov (United States)

    Girimaji, Sharath S.

    1991-01-01

    A computationally viable scheme to account for chemical reaction in turbulent flows is presented. The multivariate beta-pdf model for multiple scalar mixing forms the basis of this scheme. Using the model scalar joint pdf and a general form of the instantaneous reaction-rate, the unclosed chemical reaction terms are expressed as simple functions of scalar means and the turbulent scalar energy. The calculation procedure requires that the mean scalar equations and only one other transport equation - for the turbulent scalar energy - be solved.

  11. Study of single particle properties of neutron-rich Na isotopes on the "shore of the island of inversion" by means of neutron-transfer reactions

    CERN Multimedia

    Reiter, P; Blazhev, A A; Riisager, K; Bastin, B; Tengborn, E A; Kruecken, R; Voulot, D; Jeppesen, H B; Hadinia, B; Gernhaeuser, R A; Fynbo, H O U; Georgiev, G P; Habs, D; Fraile prieto, L M; Chapman, R; Nilsson, T; Diriken, J V J; Jenkins, D G; Kroell, T; Leske, J; Huyse, M L; Patronis, N

    We aim at the investigation of single particle properties of neutron-rich Na isotopes around the "shore of the island of inversion". As first experiment of this programme, we propose to study excited states in the isotope $^{29}$Na by a one-neutron transfer reaction with a $^{28}$Na beam at 3 MeV/u obtained from REX-ISOLDE impinging on a CD$_{2}$-target. The $\\gamma$-rays will be detected by the MINIBALL array and the particles by the T-REX array of segmented Si detectors. The main physics aims are to extract from the relative spectroscopic factors information on the configurations contributing to the wave functions of the populated states and, secondly, to identify and characterize negative parity states whose excitation energies reflect directly the N= 28 gap in this region. The results will be compared to recent shell model calculations involving new residual interactions. This will shed new light on the evolution of single particle structure and help to understand the underlying physics relevant for the f...

  12. Nuclear spin dependence of the reaction of H(3)+ with H2. I. Kinetics and modeling.

    Science.gov (United States)

    Crabtree, Kyle N; Tom, Brian A; McCall, Benjamin J

    2011-05-21

    The chemical reaction H(3)(+) + H(2) → H(2) + H(3)(+) is the simplest bimolecular reaction involving a polyatomic, yet is complex enough that exact quantum mechanical calculations to adequately model its dynamics are still unfeasible. In particular, the branching fractions for the "identity," "proton hop," and "hydrogen exchange" reaction pathways are unknown, and to date, experimental measurements of this process have been limited. In this work, the nuclear-spin-dependent steady-state kinetics of the H(3)(+) + H(2) reaction is examined in detail, and employed to generate models of the ortho:para ratio of H(3)(+) formed in plasmas of varying ortho:para H(2) ratios. One model is based entirely on nuclear spin statistics, and is appropriate for temperatures high enough to populate a large number of H(3)(+) rotational states. Efforts are made to include the influence of three-body collisions in this model by deriving nuclear spin product branching fractions for the H(5)(+) + H(2) reaction. Another model, based on rate coefficients calculated using a microcanonical statistical approach, is appropriate for lower-temperature plasmas in which energetic considerations begin to compete with the nuclear spin branching fractions. These models serve as a theoretical framework for interpreting the results of laboratory studies on the reaction of H(3)(+) with H(2). © 2011 American Institute of Physics.

  13. Modeling of a single-phase photovoltaic inverter

    Energy Technology Data Exchange (ETDEWEB)

    Maris, T.I. [Department of Electrical Engineering, Technological Educational Institute of Chalkida, 334 40 Psachna Evias (Greece); Kourtesi, St. [Hellenic Public Power Corporation S.A., 22 Chalcocondyli Str., 104 32 Athens (Greece); Ekonomou, L. [Hellenic American University, 12 Kaplanon Str., 106 80 Athens (Greece); Fotis, G.P. [National Technical University of Athens, School of Electrical and Computer Engineering, High Voltage Laboratory, 9 Iroon Politechniou St., Zografou, 157 80 Athens (Greece)

    2007-11-06

    The paper presents the design of a single-phase photovoltaic inverter model and the simulation of its performance. Furthermore, the concept of moving real and reactive power after coupling this inverter model with an a.c. source representing the main power distribution grid was studied. Brief technical information is given on the inverter design, with emphasis on the operation of the circuit used. In the technical information section, a description of real and reactive power components is given with special reference to the control of these power components by controlling the power angle or the difference in voltage magnitudes between two voltage sources. This a.c. converted voltage has practical interest, since it is useful for feeding small house appliances. (author)

  14. Age, double porosity, and simple reaction modifications for the MOC3D ground-water transport model

    Science.gov (United States)

    Goode, Daniel J.

    1999-01-01

    This report documents modifications for the MOC3D ground-water transport model to simulate (a) ground-water age transport; (b) double-porosity exchange; and (c) simple but flexible retardation, decay, and zero-order growth reactions. These modifications are incorporated in MOC3D version 3.0. MOC3D simulates the transport of a single solute using the method-ofcharacteristics numerical procedure. The age of ground water, that is the time since recharge to the saturated zone, can be simulated using the transport model with an additional source term of unit strength, corresponding to the rate of aging. The output concentrations of the model are in this case the ages at all locations in the model. Double porosity generally refers to a separate immobilewater phase within the aquifer that does not contribute to ground-water flow but can affect solute transport through diffusive exchange. The solute mass exchange rate between the flowing water in the aquifer and the immobile-water phase is the product of the concentration difference between the two phases and a linear exchange coefficient. Conceptually, double porosity can approximate the effects of dead-end pores in a granular porous media, or matrix diffusion in a fractured-rock aquifer. Options are provided for decay and zero-order growth reactions within the immobilewater phase. The simple reaction terms here extend the original model, which included decay and retardation. With these extensions, (a) the retardation factor can vary spatially within each model layer, (b) the decay rate coefficient can vary spatially within each model layer and can be different for the dissolved and sorbed phases, and (c) a zero-order growth reaction is added that can vary spatially and can be different in the dissolved and sorbed phases. The decay and growth reaction terms also can change in time to account for changing geochemical conditions during transport. The report includes a description of the theoretical basis of the model, a

  15. On the predictiveness of single-field inflationary models

    Science.gov (United States)

    Burgess, C. P.; Patil, Subodh P.; Trott, Michael

    2014-06-01

    We re-examine the predictiveness of single-field inflationary models and discuss how an unknown UV completion can complicate determining inflationary model parameters from observations, even from precision measurements. Besides the usual naturalness issues associated with having a shallow inflationary potential, we describe another issue for inflation, namely, unknown UV physics modifies the running of Standard Model (SM) parameters and thereby introduces uncertainty into the potential inflationary predictions. We illustrate this point using the minimal Higgs Inflationary scenario, which is arguably the most predictive single-field model on the market, because its predictions for A S , r and n s are made using only one new free parameter beyond those measured in particle physics experiments, and run up to the inflationary regime. We find that this issue can already have observable effects. At the same time, this UV-parameter dependence in the Renormalization Group allows Higgs Inflation to occur (in principle) for a slightly larger range of Higgs masses. We comment on the origin of the various UV scales that arise at large field values for the SM Higgs, clarifying cut off scale arguments by further developing the formalism of a non-linear realization of SU L (2) × U(1) in curved space. We discuss the interesting fact that, outside of Higgs Inflation, the effect of a non-minimal coupling to gravity, even in the SM, results in a non-linear EFT for the Higgs sector. Finally, we briefly comment on post BICEP2 attempts to modify the Higgs Inflation scenario.

  16. Development of the Automatic Modeling System for Reaction Mechanisms Using REX+JGG

    Science.gov (United States)

    Takahashi, Takahiro; Kawai, Kohei; Nakai, Hiroyuki; Ema, Yoshinori

    The identification of appropriate reaction models is very helpful for developing chemical vapor deposition (CVD) processes. In this study, we developed an automatic modeling system that analyzes experimental data on the cross- sectional shapes of films deposited on substrates with nanometer- or micrometer-sized trenches. The system then identifies a suitable reaction model to describe the film deposition. The inference engine used by the system to model the reaction mechanism was designed using real-coded genetic algorithms (RCGAs): a generation alternation model named "just generation gap" (JGG) and a real-coded crossover named "real-coded ensemble crossover" (REX). We studied the effect of REX+JGG on the system's performance, and found that the system with REX+JGG was the most accurate and reliable at model identification among the algorithms that we studied.

  17. Mechanical unfolding of proteins: reduction to a single-reaction coordinate unfolding potential, and an application of the Jarzynski Relation

    Science.gov (United States)

    Olmsted, Peter; West, Daniel; Paci, Emanuele

    2007-03-01

    Single molecule force spectroscopy (AFM, optical tweezers, etc) has revolutionized the study of many biopolymers, including DNA, RNA, and proteins. In this talk I will discuss recent work on modelling of mechanical unfolding of proteins, as often probed by AFM. I will address two issues in obtaining a coarse-grained description of protein unfolding: how to project the entire energy landscape onto an effective one dimensional unfolding potential, and how to apply the Jarzynski Relation to extract equilibrium free energies from nonequilibrium unfolding experiments.

  18. Rational Design of Single Molybdenum Atoms Anchored on N-Doped Carbon for Effective Hydrogen Evolution Reaction.

    Science.gov (United States)

    Chen, Wenxing; Pei, Jiajing; He, Chun-Ting; Wan, Jiawei; Ren, Hanlin; Zhu, Youqi; Wang, Yu; Dong, Juncai; Tian, Shubo; Cheong, Weng-Chon; Lu, Siqi; Zheng, Lirong; Zheng, Xusheng; Yan, Wensheng; Zhuang, Zhongbin; Chen, Chen; Peng, Qing; Wang, Dingsheng; Li, Yadong

    2017-12-11

    The highly efficient electrochemical hydrogen evolution reaction (HER) provides a promising pathway to resolve energy and environment problems. An electrocatalyst was designed with single Mo atoms (Mo-SAs) supported on N-doped carbon having outstanding HER performance. The structure of the catalyst was probed by aberration-corrected scanning transmission electron microscopy (AC-STEM) and X-ray absorption fine structure (XAFS) spectroscopy, indicating the formation of Mo-SAs anchored with one nitrogen atom and two carbon atoms (Mo 1 N 1 C 2 ). Importantly, the Mo 1 N 1 C 2 catalyst displayed much more excellent activity compared with Mo 2 C and MoN, and better stability than commercial Pt/C. Density functional theory (DFT) calculation revealed that the unique structure of Mo 1 N 1 C 2 moiety played a crucial effect to improve the HER performance. This work opens up new opportunities for the preparation and application of highly active and stable Mo-based HER catalysts. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  19. Predicting Complex Organic Mixture Atmospheric Chemistry Using Computer-Generated Reaction Models

    Science.gov (United States)

    Klein, M. T.; Broadbelt, L. J.; Mazurek, M. A.

    2001-12-01

    New measurement and chemical characterization technologies now offer unprecedented capabilities for detecting and describing atmospheric organic matter at the molecular level. As a result, very detailed and extensive chemical inventories are produced routinely in atmospheric field measurements of organic compounds found in the vapor and condensed phases (particles, cloud and fog droplets). Hundreds of organic compounds can constitute the complex chemical mixtures observed for these types of samples, exhibiting a wide spectrum of physical properties such as molecular weight, polarity, pH, and chemical reactivity. The central challenge is describing chemically the complex organic aerosol mixture in a useable fashion that can be linked to predictive models. However, the great compositional complexity of organic aerosols engenders a need for the modeling of the reaction chemistry of these compounds in atmospheric chemical models. On a mechanistic level, atmospheric reactions of organic compounds can involve a network of a very large number of chemical species and reactions. Deriving such large molecular kinetic models by hand is a tedious and time-consuming process. However, such models are usually built upon a few basic chemical principles tempered with the model builder's observations, experience, and intuition that can be summarized as a set of rules. This suggests that given an algorithmic framework, computers (information technology) may be used to apply these chemical principles and rules, thereby building a kinetic model. The framework for this model building process has been developed by means of graph theory. A molecule, which is a set of atoms connected by bonds, may be conceptualized as a set of vertices connected by edges, or to be more precise, a graph. The bond breaking and forming for a reaction can be represented compactly in the form of a matrix operator formally called the "reaction matrix". The addition of the reaction matrix operator to the reduced

  20. Genome-scale Metabolic Reaction Modeling: a New Approach to Geomicrobial Kinetics

    Science.gov (United States)

    McKernan, S. E.; Shapiro, B.; Jin, Q.

    2014-12-01

    Geomicrobial rates, rates of microbial metabolism in natural environments, are a key parameter of theoretical and practical problems in geobiology and biogeochemistry. Both laboratory- and field-based approaches have been applied to study rates of geomicrobial processes. Laboratory-based approaches analyze geomicrobial kinetics by incubating environmental samples under controlled laboratory conditions. Field methods quantify geomicrobial rates by observing the progress of geomicrobial processes. To take advantage of recent development in biogeochemical modeling and genome-scale metabolic modeling, we suggest that geomicrobial rates can also be predicted by simulating metabolic reaction networks of microbes. To predict geomicrobial rates, we developed a genome-scale metabolic model that describes enzyme reaction networks of microbial metabolism, and simulated the network model by accounting for the kinetics and thermodynamics of enzyme reactions. The model is simulated numerically to solve cellular enzyme abundance and hence metabolic rates under the constraints of cellular physiology. The new modeling approach differs from flux balance analysis of system biology in that it accounts for the thermodynamics and kinetics of enzymatic reactions. It builds on subcellular metabolic reaction networks, and hence also differs from classical biogeochemical reaction modeling. We applied the new approach to Methanosarcina acetivorans, an anaerobic, marine methanogen capable of disproportionating acetate to carbon dioxide and methane. The input of the new model includes (1) enzyme reaction network of acetoclastic methanogenesis, and (2) representative geochemical conditions of freshwater sedimentary environments. The output of the simulation includes the proteomics, metabolomics, and energy and matter fluxes of M. acetivorans. Our simulation results demonstrate the predictive power of the new modeling approach. Specifically, the results illustrate how methanogenesis rates vary

  1. A spectral geometric model for Compton single scatter in PET based on the single scatter simulation approximation

    Science.gov (United States)

    Kazantsev, I. G.; Olsen, U. L.; Poulsen, H. F.; Hansen, P. C.

    2018-02-01

    We investigate the idealized mathematical model of single scatter in PET for a detector system possessing excellent energy resolution. The model has the form of integral transforms estimating the distribution of photons undergoing a single Compton scattering with a certain angle. The total single scatter is interpreted as the volume integral over scatter points that constitute a rotation body with a football shape, while single scattering with a certain angle is evaluated as the surface integral over the boundary of the rotation body. The equations for total and sample single scatter calculations are derived using a single scatter simulation approximation. We show that the three-dimensional slice-by-slice filtered backprojection algorithm is applicable for scatter data inversion provided that the attenuation map is assumed to be constant. The results of the numerical experiments are presented.

  2. Modelling, Design, Operability and Analysis of Reaction-Separation Systems

    DEFF Research Database (Denmark)

    Jimenez, Edgar Ramirez

    2006-01-01

    Denne afhandling præsenterer en modelbaseret metode til design og analyse af kemiske processer som involverer en enhed for Reaktion-Separation med recycling (RSR). Det centrale i denne metode er at en modelbaseret analyse af (masse og energibalance) modeller af varierende kompleksitet identificer...

  3. Examining the rudimentary steps of the oxygen reduction reaction on single-atomic Pt using Ti-based non-oxide supports

    DEFF Research Database (Denmark)

    Tak, Young Joo; Yang, Sungeun; Lee, Hyunjoo

    2018-01-01

    In the attempt to reduce the high-cost and improve the overall durability of Pt-based electrocatalysts for the oxygen reduction reaction (ORR), density-functional theory (DFT) calculations have been performed to study the energetics of the elementary steps that occur during ORR on TiN(100)- and T...... of the single-atom Pt catalyst, and directly influences the rudimentary ORR steps on these single-atom platinized supports....

  4. Dynamic Characteristics and Model for Centralization Reaction of Acidic Tailings From Heap Leaching of Uranium Ore

    International Nuclear Information System (INIS)

    Ding Dexin; Liu Yulong; Li Guangyue; Wang Youtuan

    2010-01-01

    Centralization tests were carried out on acidic tailings from heap leaching of uranium ore by using CaO, NaOH and NH 4 OH. The variations of pH with time were measured for the three centralization systems and the dynamic models for the systems were set up by regressing the measured data. The centralization process consists of the fast reaction phase representing the reaction between the centralization agent and the acid on the surface of the tailing's particles and the slow diffusion-reaction phase representing the diffusion-reaction between the centralization agent and the acid within the tailing's particles. The non-linear coupling and feedback function model for the diffusion-reaction of the centralization agent can reflect the process and mode of the centralization reaction. There is a non-linear oscillation in the variation of pH within the centralization systems. The dynamic model for the tailing's centralization reaction can fit the pH variation within the centralization systems. (authors)

  5. Hopf bifurcation in a delayed reaction-diffusion-advection population model

    Science.gov (United States)

    Chen, Shanshan; Lou, Yuan; Wei, Junjie

    2018-04-01

    In this paper, we investigate a reaction-diffusion-advection model with time delay effect. The stability/instability of the spatially nonhomogeneous positive steady state and the associated Hopf bifurcation are investigated when the given parameter of the model is near the principle eigenvalue of an elliptic operator. Our results imply that time delay can make the spatially nonhomogeneous positive steady state unstable for a reaction-diffusion-advection model, and the model can exhibit oscillatory pattern through Hopf bifurcation. The effect of advection on Hopf bifurcation values is also considered, and our results suggest that Hopf bifurcation is more likely to occur when the advection rate increases.

  6. Nicotiana tabacum as model for ozone - plant surface reactions

    Science.gov (United States)

    Jud, Werner; Fischer, Lukas; Wohlfahrt, Georg; Tissier, Alain; Canaval, Eva; Hansel, Armin

    2015-04-01

    Elevated tropospheric ozone concentrations are considered a toxic threat to plants, responsible for global crop losses with associated economic costs of several billion dollars per year. The ensuing injuries have been related to the uptake of ozone through the stomatal pores and oxidative effects damaging the internal leaf tissue. A striking question of current research is the environment and plant specific partitioning of ozone loss between gas phase, stomatal or plant surface sink terms. Here we show results from ozone fumigation experiments using various Nicotiana Tabacum varieties, whose surfaces are covered with different amounts of unsaturated diterpenoids exuded by their glandular trichomes. Exposure to elevated ozone levels (50 to 150 ppbv) for 5 to 15 hours in an exceptionally clean cuvette system did neither result in a reduction of photosynthesis nor caused any visible leaf damage. Both these ozone induced stress effects have been observed previously in ozone fumigation experiments with the ozone sensitive tobacco line Bel-W3. In our case ozone fumigation was accompanied by a continuous release of oxygenated volatile organic compounds, which could be clearly associated to their condensed phase precursors for the first time. Gas phase reactions of ozone were avoided by choosing a high enough gas exchange rate of the plant cuvette system. In the case of the Ambalema variety, that is known to exude only the diterpenoid cis-abienol, ozone fumigation experiments yield the volatiles formaldehyde and methyl vinyl ketone (MVK). The latter could be unequivocally separated from isomeric methacrolein (MACR) by the aid of a Selective Reagent Ion Time-of-Flight Mass Spectrometer (SRI-ToF-MS), which was switched every six minutes from H3O+ to NO+ primary ion mode and vice versa. Consistent with the picture of an ozone protection mechanism caused by reactive diterpenoids at the leaf surface are the results from dark-light experiments. The ozone loss obtained from the

  7. Monte Carlo simulations of lattice models for single polymer systems

    International Nuclear Information System (INIS)

    Hsu, Hsiao-Ping

    2014-01-01

    Single linear polymer chains in dilute solutions under good solvent conditions are studied by Monte Carlo simulations with the pruned-enriched Rosenbluth method up to the chain length N∼O(10 4 ). Based on the standard simple cubic lattice model (SCLM) with fixed bond length and the bond fluctuation model (BFM) with bond lengths in a range between 2 and √(10), we investigate the conformations of polymer chains described by self-avoiding walks on the simple cubic lattice, and by random walks and non-reversible random walks in the absence of excluded volume interactions. In addition to flexible chains, we also extend our study to semiflexible chains for different stiffness controlled by a bending potential. The persistence lengths of chains extracted from the orientational correlations are estimated for all cases. We show that chains based on the BFM are more flexible than those based on the SCLM for a fixed bending energy. The microscopic differences between these two lattice models are discussed and the theoretical predictions of scaling laws given in the literature are checked and verified. Our simulations clarify that a different mapping ratio between the coarse-grained models and the atomistically realistic description of polymers is required in a coarse-graining approach due to the different crossovers to the asymptotic behavior

  8. MATHEMATICAL MODELING OF FLOW PARAMETERS FOR SINGLE WIND TURBINE

    Directory of Open Access Journals (Sweden)

    2016-01-01

    Full Text Available It is known that on the territory of the Russian Federation the construction of several large wind farms is planned. The tasks connected with design and efficiency evaluation of wind farm work are in demand today. One of the possible directions in design is connected with mathematical modeling. The method of large eddy simulation developed within the direction of computational hydrodynamics allows to reproduce unsteady structure of the flow in details and to determine various integrated values. The calculation of work for single wind turbine installation by means of large eddy simulation and Actuator Line Method along the turbine blade is given in this work. For problem definition the numerical method in the form of a box was considered and the adapted unstructured grid was used.The mathematical model included the main equations of continuity and momentum equations for incompressible fluid. The large-scale vortex structures were calculated by means of integration of the filtered equations. The calculation was carried out with Smagorinsky model for determination of subgrid scale turbulent viscosity. The geometrical parametersof wind turbine were set proceeding from open sources in the Internet.All physical values were defined at center of computational cell. The approximation of items in equations was ex- ecuted with the second order of accuracy for time and space. The equations for coupling velocity and pressure were solved by means of iterative algorithm PIMPLE. The total quantity of the calculated physical values on each time step was equal to 18. So, the resources of a high performance cluster were required.As a result of flow calculation in wake for the three-bladed turbine average and instantaneous values of velocity, pressure, subgrid kinetic energy and turbulent viscosity, components of subgrid stress tensor were worked out. The re- ceived results matched the known results of experiments and numerical simulation, testify the opportunity

  9. Toward a reaction rate model of condensed-phase RDX decomposition under high temperatures

    Science.gov (United States)

    Schweigert, Igor

    2015-06-01

    Shock ignition of energetic molecular solids is driven by microstructural heterogeneities, at which even moderate stresses can result in sufficiently high temperatures to initiate material decomposition and chemical energy release. Mesoscale modeling of these ``hot spots'' requires a reaction rate model that describes the energy release with a sub-microsecond resolution and under a wide range of temperatures. No such model is available even for well-studied energetic materials such as RDX. In this presentation, I will describe an ongoing effort to develop a reaction rate model of condensed-phase RDX decomposition under high temperatures using first-principles molecular dynamics, transition-state theory, and reaction network analysis. This work was supported by the Naval Research Laboratory, by the Office of Naval Research, and by the DoD High Performance Computing Modernization Program Software Application Institute for Multiscale Reactive Modeling of Insensitive Munitions.

  10. EQ6, a computer program for reaction path modeling of aqueous geochemical systems: Theoretical manual, user`s guide, and related documentation (Version 7.0); Part 4

    Energy Technology Data Exchange (ETDEWEB)

    Wolery, T.J.; Daveler, S.A.

    1992-10-09

    EQ6 is a FORTRAN computer program in the EQ3/6 software package (Wolery, 1979). It calculates reaction paths (chemical evolution) in reacting water-rock and water-rock-waste systems. Speciation in aqueous solution is an integral part of these calculations. EQ6 computes models of titration processes (including fluid mixing), irreversible reaction in closed systems, irreversible reaction in some simple kinds of open systems, and heating or cooling processes, as well as solve ``single-point`` thermodynamic equilibrium problems. A reaction path calculation normally involves a sequence of thermodynamic equilibrium calculations. Chemical evolution is driven by a set of irreversible reactions (i.e., reactions out of equilibrium) and/or changes in temperature and/or pressure. These irreversible reactions usually represent the dissolution or precipitation of minerals or other solids. The code computes the appearance and disappearance of phases in solubility equilibrium with the water. It finds the identities of these phases automatically. The user may specify which potential phases are allowed to form and which are not. There is an option to fix the fugacities of specified gas species, simulating contact with a large external reservoir. Rate laws for irreversible reactions may be either relative rates or actual rates. If any actual rates are used, the calculation has a time frame. Several forms for actual rate laws are programmed into the code. EQ6 is presently able to model both mineral dissolution and growth kinetics.

  11. EQ6, a computer program for reaction path modeling of aqueous geochemical systems: Theoretical manual, user's guide, and related documentation (Version 7.0)

    International Nuclear Information System (INIS)

    Wolery, T.J.; Daveler, S.A.

    1992-01-01

    EQ6 is a FORTRAN computer program in the EQ3/6 software package (Wolery, 1979). It calculates reaction paths (chemical evolution) in reacting water-rock and water-rock-waste systems. Speciation in aqueous solution is an integral part of these calculations. EQ6 computes models of titration processes (including fluid mixing), irreversible reaction in closed systems, irreversible reaction in some simple kinds of open systems, and heating or cooling processes, as well as solve ''single-point'' thermodynamic equilibrium problems. A reaction path calculation normally involves a sequence of thermodynamic equilibrium calculations. Chemical evolution is driven by a set of irreversible reactions (i.e., reactions out of equilibrium) and/or changes in temperature and/or pressure. These irreversible reactions usually represent the dissolution or precipitation of minerals or other solids. The code computes the appearance and disappearance of phases in solubility equilibrium with the water. It finds the identities of these phases automatically. The user may specify which potential phases are allowed to form and which are not. There is an option to fix the fugacities of specified gas species, simulating contact with a large external reservoir. Rate laws for irreversible reactions may be either relative rates or actual rates. If any actual rates are used, the calculation has a time frame. Several forms for actual rate laws are programmed into the code. EQ6 is presently able to model both mineral dissolution and growth kinetics

  12. Chaos and fractals in dynamical models of transport and reaction.

    Science.gov (United States)

    Gaspard, P; Claus, I

    2002-03-15

    This paper contains a discussion of dynamical randomness among the different methods of simulation of a fluid and its characterization by the concept of Kolmogorov-Sinai entropy per unit time. Moreover, a renormalization-group method is presented in order to construct the hydrodynamic and reactive modes of relaxation in chaotic models. The renormalization-group construction allows us to obtain the dispersion relation of these modes, i.e. their damping rate versus the wavenumber. Besides, these modes are characterized by a fractal dimension given in terms of a diffusion coefficient and a Lyapunov exponent.

  13. A GPU Reaction Diffusion Soil-Microbial Model

    Science.gov (United States)

    Falconer, Ruth; Houston, Alasdair; Schmidt, Sonja; Otten, Wilfred

    2014-05-01

    Parallelised algorithms are frequent in bioinformatics as a consequence of the close link to informatics - however in the field of soil science and ecology they are less prevalent. A current challenge in soil ecology is to link habitat structure to microbial dynamics. Soil science is therefore entering the 'big data' paradigm as a consequence of integrating data pertinent to the physical soil environment obtained via imaging and theoretical models describing growth and development of microbial dynamics permitting accurate analyses of spatio-temporal properties of different soil microenvironments. The microenvironment is often captured by 3D imaging (CT tomography) which yields large datasets and when used in computational studies the physical sizes of the samples that are amenable to computation are less than 1 cm3. Today's commodity graphics cards are programmable and possess a data parallel architecture that in many cases is capable of out-performing the CPU in terms of computational rates. The programmable aspect is achieved via a low-level parallel programming language (CUDA, OpenCL and DirectX). We ported a Soil-Microbial Model onto the GPU using the DirectX Compute API. We noted a significant computational speed up as well as an increase in the physical size that can be simulated. Some of the drawbacks of such an approach were concerned with numerical precision and the steep learning curve associated with GPGPU technologies.

  14. Reaction kinetics and reactor modeling for fuel processing of liquid hydrocarbons to produce hydrogen. Isooctane reforming

    Energy Technology Data Exchange (ETDEWEB)

    Pacheco, Manuel [Department of Refining and Petrochemicals, Center for Research and Development of the Venezuelan Oil Industry (PDVSA-Intevep), Sector el Tambor, P.O. Box 76343, Los Teques, Edo Miranda (Venezuela); Sira, Jorge [Department of Mechanical Engineering, Universidad de los Andes, Merida (Venezuela); Kopasz, John [US Department of Energy, Chemical Technology Division, Argonne National Laboratory, Argonne, IL 60439 (United States)

    2003-09-10

    A mathematical model was developed in the framework of the process simulator Aspen Plus in order to describe the reaction kinetics and performance of a fuel processor used for autothermal reforming of liquid hydrocarbons. Experimental results obtained in the facilities of Argonne National Laboratories (ANL) when reforming isooctane using a ceria-oxide catalyst impregnated with platinum were used in order to validate the reactor model. The reaction kinetics and reaction schemes were taken from published literature and most of the chemical reactions were modeled using the Langmuir-Hinshelwood-Hougen-Watson (LHHW) formulation to account for the effect of adsorption of reactants and products on the active sites of the catalyst. The water-gas-shift (WGS) reactor used to reduce the concentration of CO in the reformate was also modeled. Both reactor models use a simplified formulation for estimating the effectiveness factor of each chemical reaction in order to account for the effect of intraparticle mass transfer limitations on the reactor performance. Since the data in the literature on kinetics of autothermal reforming of liquid hydrocarbons using CeO{sub 2}-Pt catalyst is scarce, the proposed kinetic model for the reaction network was coupled to the sequential quadratic programming (SQP) algorithm implemented in Aspen Plus in order to regress the kinetic constants for the different reactions. The model describes the trend of the experimental data in terms of hydrogen yield and distribution of products with a relative deviation of {+-}15% for reforming temperatures between 600 and 800C and reactor space velocities between 15000 and 150000h{sup -1}.

  15. Developments in Analytical Chemistry: Acoustically Levitated Drop Reactors for Enzyme Reaction Kinetics and Single-Walled Carbon Nanotube-Based Sensors for Detection of Toxic Organic Phosphonates

    Science.gov (United States)

    Field, Christopher Ryan

    2009-01-01

    Developments in analytical chemistry were made using acoustically levitated small volumes of liquid to study enzyme reaction kinetics and by detecting volatile organic compounds in the gas phase using single-walled carbon nanotubes. Experience gained in engineering, electronics, automation, and software development from the design and…

  16. Modeling bidirectionally coupled single-mode semiconductor lasers

    International Nuclear Information System (INIS)

    Mulet, Josep; Masoller, Cristina; Mirasso, Claudio R.

    2002-01-01

    We develop a dynamical model suitable for the description of two mutually coupled semiconductor lasers in a face-to-face configuration. Our study considers the propagation of the electric field along the compound system as well as the evolution of the carrier densities within each semiconductor laser. Mutual injection, passive optical feedback, and multiple reflections are accounted for in this framework, although under weak to moderate coupling conditions. We systematically describe the effect of the coupling strength on the spectrum of monochromatic solutions and on the respective dynamical behavior. By assuming single-longitudinal-mode operation, weak mutual coupling and slowly varying approximation, the dynamical model can be reduced to rate equations describing the mutual injection from one laser to its counterpart and vice versa. A good agreement between the complete and simplified models is found for small coupling. For larger coupling, higher-order terms lead to a smaller threshold reduction, reflected itself in the spectrum of the monochromatic solutions and in the dynamics of the optical power

  17. Development of analysis model for mid and long-term effects of sodium water reaction event in LMR

    International Nuclear Information System (INIS)

    Eoh, Jae Hyuk; Sim, Yoon Sub; Kim, Seong O; Kim, Yeon Sik; Kim, Eui Kwang; Wi, Myung Hwan

    2002-04-01

    The Sodium-Water Reaction(SWR) is important in the design consideration of a LMR steam generator. To develop the analysis code for long-term effects of SWR, investigation on the characteristics of various SWR analysis code and the assessment of an analysis model for long term effects were performed. In an event of SWR, pressure spikes of wave propagation occur at its initial stage and last for a very short time, and then bulk motion of fluid and reaction products is progressed and lasts for a long time. In a case SWR occurs, a number of hydrogen bubbles produced and sodium is entrained into the bubbles through the gas-liquid bubble interfaces by evaporation or diffusion. The partial pressure of the sodium in a hydrogen bubble is determined as a function of the bubble size, temperature, and pressure, and is rapidly decreased as its size increased. From this, it can be considered that the bulk motion in the later phase of SWR is an axial motion caused by expansion of a single-phase hydrogen gas bubble produced by a reaction in the vicinity of the leak site. Through this investigation, a preliminary simple analysis model for long-term effects of SWR was set up and sensitivity study using the system design parameters such as pressure and temperature of IHTS for KALIMER was performed. Also, a simpler analysis model using the cover gas pressure change related to the production of a hydrogen bubble in a steam generator was developed from the analyses results. These simple analysis models of the reaction site and the pressure behavior with hydrogen production can be used to develop the mid and long-term analysis code for SWR in the KALIMER steam generator design

  18. 48Ca(d,n)49Sc reaction at E/sub d/=20 MeV; proton single-particle states in 49Sc

    International Nuclear Information System (INIS)

    Iwasaki, Y.; Galonsky, A.; Weber, D.J.

    1980-01-01

    The 48 Ca(d,n) 49 Sc reaction has been studied at E/sub d/=20 MeV. Angular distributions of differential cross sections have been obtained for 14 transitions to states in 49 Sc up to an excitation energy of 7.1 MeV. A distorted-wave Born-approximation analysis has been made of the experimental data. With respect to states corresponding to the same proton single-particle orbital, relative values of derived spectroscopic factors are generally in good agreement with those obtained from ( 3 He,d) reaction data. There are remarkable differences between the results from the 48 Ca(d,n) 49 Sc reaction and the 48 Ca( 3 He,d) 49 Sc, however, regarding the dependence of the relative spectroscopic factors on proton single-particle orbitals

  19. Model Based Control of Single-Phase Marine Cooling Systems

    DEFF Research Database (Denmark)

    Hansen, Michael

    2014-01-01

    these systems. Traditionally, control for this type of cooling system has been limited to open-loop control of pumps combined with a couple of local PID controllers for bypass valves to keep critical temperatures within design limits. This research considers improvements in a retrofit framework to the control...... linearization, an H∞-control design is applied to the resulting linear system. Disturbance rejection capabilities and robustness of performance for this control design methodology is compared to a baseline design derived from classical control theory. This shows promising results for the nonlinear robust design......This thesis is concerned with the problem of designing model-based control for a class of single-phase marine cooling systems. While this type of cooling system has been in existence for several decades, it is only recently that energy efficiency has become a focus point in the design and operation...

  20. A phenomenological model for particle retention in single, saturated fractures.

    Science.gov (United States)

    Rodrigues, Sandrina; Dickson, Sarah

    2014-01-01

    Fractured aquifers are some of the most poorly characterized subsurface environments despite posing one of the highest risks to the protection of potable groundwater. This research was designed to improve the understanding of the factors affecting particle transport through fractures by developing a phenomenological model based on laboratory-scale transport data. The model presented in this research employed data from over 70 particle tracer tests conducted in single, saturated, variable-aperture fractures that were obtained from the natural environment and fractured in the laboratory or cast from epoxy in the laboratory. The particles employed were Escherichia coli RS2-GFP and microspheres. The tracer experiments were conducted in natural (dolomitic limestone and granite) as well as epoxy replicas of the natural fractures. The multiple linear regression analysis revealed that the most important factors influencing particle retention in fractures are the ratio of the ionic strength of solution to collector charge, the ratio of particle to collector charge, and the ratio of advective to diffusive forces as described by the Peclet number. The model was able to reasonably (R(2)  = 0.64) predict the fraction of particles retained; however, it is evident that some factors not accounted for in the model also contributed to retention. This research presents a novel approach to understanding particle transport in fractures, and illustrates the relative importance of various factors affecting the transport mechanisms. The utility of this model lies in the increased understanding of particle transport in fractures, which is extremely useful for directing future research. © 2013, National Ground Water Association.

  1. Use of shell model calculations in R-matrix studies of neutron-induced reactions

    International Nuclear Information System (INIS)

    Knox, H.D.

    1986-01-01

    R-matrix analyses of neutron-induced reactions for many of the lightest p-shell nuclei are difficult due to a lack of distinct resonance structure in the reaction cross sections. Initial values for the required R-matrix parameters, E,sub(lambda) and γsub(lambdac) for states in the compound system, can be obtained from shell model calculations. In the present work, the results of recent shell model calculations for the lithium isotopes have been used in R-matrix analyses of 6 Li+n and 7 Li+n reactions for E sub(n) 7 Li and 8 Li on the 6 Li+n and 7 Li+n reaction mechanisms and cross sections are discussed. (author)

  2. KEMOD: A mixed chemical kinetic and equilibrium model of aqueous and solid phase geochemical reactions

    Energy Technology Data Exchange (ETDEWEB)

    Yeh, G.T.; Iskra, G.A. [Pennsylvania State Univ., University Park, PA (United States). Dept. of Civil Engineering; Szecsody, J.E.; Zachara, J.M.; Streile, G.P. [Pacific Northwest Lab., Richland, WA (United States)

    1995-01-01

    This report presents the development of a mixed chemical Kinetic and Equilibrium MODel in which every chemical species can be treated either as a equilibrium-controlled or as a kinetically controlled reaction. The reaction processes include aqueous complexation, adsorption/desorption, ion exchange, precipitation/dissolution, oxidation/reduction, and acid/base reactions. Further development and modification of KEMOD can be made in: (1) inclusion of species switching solution algorithms, (2) incorporation of the effect of temperature and pressure on equilibrium and rate constants, and (3) extension to high ionic strength.

  3. Mathematical Modeling Applied Transesterification Reaction Product of Synthesis from Animal Fats and Vegetable Oil

    OpenAIRE

    Letícia Thaís Chendynski; Universidade Estadual de Londrina; Karina G. Angilelli; Universidade Estadual de Londrina; Bruna A. D. Ferreira; Unversidade Esadual de Londrina; Dionisio Borsato; Universidade Estadual de Londrina

    2009-01-01

    The high availability and low cost of animal fat have promoted industrial interest as a partial substitute for soybean oil for transesterification reaction product of synthesis, to reduce costs and maximize profits. This study aimed to apply experimental design for biodiesel production from a mixture of soybean oil, poultry fat, beef tallow and pork lard in order to obtain predictive equations to model the transesterification reaction yield, cloud point, pour point and oxidative stability, wi...

  4. Disproportionation of rosin on an industrial Pd/C catalyst: reaction pathway and kinetic model discrimination.

    Science.gov (United States)

    Souto, Juan Carlos; Yustos, Pedro; Ladero, Miguel; Garcia-Ochoa, Felix

    2011-02-01

    In this work, a phenomenological study of the isomerisation and disproportionation of rosin acids using an industrial 5% Pd on charcoal catalyst from 200 to 240°C is carried out. Medium composition is determined by elemental microanalysis, GC-MS and GC-FID. Dehydrogenated and hydrogenated acid species molar amounts in the final product show that dehydrogenation is the main reaction. Moreover, both hydrogen and non-hydrogen concentration considering kinetic models are fitted to experimental data using a multivariable non-linear technique. Statistical discrimination among the proposed kinetic models lead to the conclusion hydrogen considering models fit much better to experimental results. The final kinetic model involves first-order isomerisation reactions of neoabietic and palustric acids to abietic acid, first-order dehydrogenation and hydrogenation of this latter acid, and hydrogenation of pimaric acids. Hydrogenation reactions are partial first-order regarding the acid and hydrogen. Copyright © 2010 Elsevier Ltd. All rights reserved.

  5. Effect of PVP as a capping agent in single reaction synthesis of nanocomposite soft/hard ferrite nanoparticles

    Energy Technology Data Exchange (ETDEWEB)

    Ahmad, H.A. [Department of Physics, Faculty of Science, Universiti Putra Malaysia, UPM, 43400 Serdang, Selangor (Malaysia); Saiden, N.M., E-mail: nlaily@upm.edu.my [Department of Physics, Faculty of Science, Universiti Putra Malaysia, UPM, 43400 Serdang, Selangor (Malaysia); Saion, E.; Azis, R.S.; Mamat, M.S. [Department of Physics, Faculty of Science, Universiti Putra Malaysia, UPM, 43400 Serdang, Selangor (Malaysia); Hashim, M. [Advanced Material and Nanotechnology Laboratory, Institute of Advanced Technology, Universiti Putra Malaysia, UPM, 43400 Serdang, Selangor (Malaysia)

    2017-04-15

    Nanocomposite magnets consist of soft and hard ferrite phases are known as an exchange spring magnet when they are sufficiently spin exchange coupled. Hard and soft ferrites offer high value of coercivity, H{sub c} and saturation magnetization, M{sub s} respectively. In order to obtain a better permanent magnet, both soft and hard ferrite phases need to be “exchange coupled”. The nanoparticles were prepared by a simple one-pot technique of 80% soft phase and 20% hard phase. This technique involves a single reaction mixture of metal nitrates and aqueous solution of varied amounts of polyvinylpyrrolidone (PVP). The heat treatment applied was at 800 °C for 3 h. The synthesized composites were characterized by Transmission Electron Microscope (TEM), Fourier Transform Infra-red (FT-IR), Energy Dispersive X-Ray (EDX), X-ray diffraction (XRD) and Vibrating sample magnetometer (VSM). The coexistence of two phases, Ni{sub 0.5}Zn{sub 0.5}Fe{sub 2}O{sub 4} and SrFe{sub 12}O{sub 19} were observed by XRD patterns. It also verified by the EDX that no impurities detected. The magnetic properties of nanocomposite ferrites for 0.06 g/ml PVP gives a better properties of H{sub c} 932 G and M{sub s} 39.0 emu/g with average particle size obtained from FESEM was 49.2 nm. The concentration of PVP used gives effect on the magnetic properties of the samples. - Highlights: • Amount of PVP play important roles in controlling the particle size distribution and magnetic properties. • This is a novel technique to produce nanocomposite ferrites effectively. • This study contributes better understanding on magnetic properties in nanoparticle composite magnets.

  6. The use of a single inertial sensor to estimate 3-dimensional ground reaction force during accelerative running tasks.

    Science.gov (United States)

    Gurchiek, Reed D; McGinnis, Ryan S; Needle, Alan R; McBride, Jeffrey M; van Werkhoven, Herman

    2017-08-16

    The purpose of this investigation was to determine the feasibility of using a single inertial measurement unit (IMU) placed on the sacrum to estimate 3-dimensional ground reaction force (F) during linear acceleration and change of direction tasks. Force plate measurements of F and estimates from the proposed IMU method were collected while subjects (n=15) performed a standing sprint start (SS) and a 45° change of direction task (COD). Error in the IMU estimate of step-averaged component and resultant F was quantified by comparison to estimates from the force plate using Bland-Altman 95% limits of agreement (LOA), root mean square error (RMSE), Pearson's product-moment correlation coefficient (r), and the effect size (ES) of the differences between the two systems. RMSE of the IMU estimate of step-average F ranged from 37.70 N to 77.05 N with ES between 0.04 and 0.47 for SS while for COD, RMSE was between 54.19 N to 182.92 N with ES between 0.08 and 1.69. Correlation coefficients between the IMU and force plate measurements were significant (p≤0.05) for all values (r=0.53 to 0.95) except the medio-lateral component of step-average F. The average angular error in the IMU estimate of the orientation of step-average F was ≤10° for all tasks. The results of this study suggest the proposed IMU method may be used to estimate sagittal plane components and magnitude of step-average F during a linear standing sprint start as well as the vertical component and magnitude of step-average F during a 45° change of direction task. Copyright © 2017 Elsevier Ltd. All rights reserved.

  7. Dynamic Analysis of a Reaction-Diffusion Rumor Propagation Model

    Science.gov (United States)

    Zhao, Hongyong; Zhu, Linhe

    2016-06-01

    The rapid development of the Internet, especially the emergence of the social networks, leads rumor propagation into a new media era. Rumor propagation in social networks has brought new challenges to network security and social stability. This paper, based on partial differential equations (PDEs), proposes a new SIS rumor propagation model by considering the effect of the communication between the different rumor infected users on rumor propagation. The stabilities of a nonrumor equilibrium point and a rumor-spreading equilibrium point are discussed by linearization technique and the upper and lower solutions method, and the existence of a traveling wave solution is established by the cross-iteration scheme accompanied by the technique of upper and lower solutions and Schauder’s fixed point theorem. Furthermore, we add the time delay to rumor propagation and deduce the conditions of Hopf bifurcation and stability switches for the rumor-spreading equilibrium point by taking the time delay as the bifurcation parameter. Finally, numerical simulations are performed to illustrate the theoretical results.

  8. Physics-Based Crystal Plasticity Modeling of Single Crystal Niobium

    Science.gov (United States)

    Maiti, Tias

    Crystal plasticity models based on thermally activated dislocation kinetics has been successful in predicting the deformation behavior of crystalline materials, particularly in face-centered cubic (fcc) metals. In body-centered cubic (bcc) metals success has been limited owing to ill-defined slip planes. The flow stress of a bcc metal is strongly dependent on temperature and orientation due to the non-planar splitting of a/2 screw dislocations. As a consequence of this, bcc metals show two unique deformation characteristics: (a) thermally-activated glide of screw dislocations--the motion of screw components with their non-planar core structure at the atomistic level occurs even at low stress through the nucleation (assisted by thermal activation) and lateral propagation of dislocation kink pairs; (b) break-down of the Schmid Law, where dislocation slip is driven only by the resolved shear stress. Since the split dislocation core has to constrict for a kink pair formation (and propagation), the non-planarity of bcc screw dislocation cores entails an influence of (shear) stress components acting on planes other than the primary glide plane on their mobility. Another consequence of the asymmetric core splitting on the glide plane is a direction-sensitive slip resistance, which is termed twinning/atwinning sense of shear and should be taken into account when developing constitutive models. Modeling thermally-activated flow including the above-mentioned non-Schmid effects in bcc metals has been the subject of much work, starting in the 1980s and gaining increased interest in recent times. The majority of these works focus on single crystal deformation of commonly used metals such as Iron (Fe), Molybdenum (Mo), and Tungsten (W), while very few published studies address deformation behavior in Niobium (Nb). Most of the work on Nb revolves around fitting parameters of phenomenological descriptions, which do not capture adequately the macroscopic multi-stage hardening

  9. The hydration of slag, part 2: reaction models for blended cement

    NARCIS (Netherlands)

    Chen, Wei; Brouwers, Jos

    2007-01-01

    The hydration of slag-blended cement is studied by considering the interaction between the hydrations of slag and Portland cement clinker. Three reaction models for the slag-blended cement are developed based on stoichiometric calculations. These models correlate the compositions of the unhydrated

  10. A simple model for chiral amplification in the aminoalcohol-catalyzed reaction of aldehydes with dialkylzinc

    Directory of Open Access Journals (Sweden)

    IVAN GUTMAN

    1999-08-01

    Full Text Available A simple explanation is offered for the recently discovered chiral amplification in the alkylation reaction of benzaldehyde by means of dialkylzinc, catalyzed by (dimethylaminoisoborneol. The model presentd is similar to, yet somewhat simpler than, the model put forward by Noyori et al.

  11. Bifurcation Analysis of Gene Propagation Model Governed by Reaction-Diffusion Equations

    Directory of Open Access Journals (Sweden)

    Guichen Lu

    2016-01-01

    Full Text Available We present a theoretical analysis of the attractor bifurcation for gene propagation model governed by reaction-diffusion equations. We investigate the dynamical transition problems of the model under the homogeneous boundary conditions. By using the dynamical transition theory, we give a complete characterization of the bifurcated objects in terms of the biological parameters of the problem.

  12. Models based on multichannel R-matrix theory for evaluating light element reactions

    International Nuclear Information System (INIS)

    Dodder, D.C.; Hale, G.M.; Nisley, R.A.; Witte, K.; Young, P.G.

    1975-01-01

    Multichannel R-matrix theory has been used as a basis for models for analysis and evaluation of light nuclear systems. These models have the characteristic that data predictions can be made utilizing information derived from other reactions related to the one of primary interest. Several examples are given where such an approach is valid and appropriate. (auth.)

  13. A kinetic model for the glucose/glycine Maillard reaction pathways

    NARCIS (Netherlands)

    Martins, S.I.F.S.; Boekel, van M.A.J.S.

    2005-01-01

    A comprehensive kinetic model for the glucose/glycine Maillard reaction is proposed based on an approach called multiresponse kinetic modelling. Special attention was paid to reactants, intermediates and end products: -fructose, N-(1-deoxy--fructos-1-yl)-glycine (DFG), 1-deoxy-2,3-hexodiulose and

  14. Aromatic products from reaction of lignin model compounds with UV-alkaline peroxide

    International Nuclear Information System (INIS)

    Sun, Y.P.; Wallis, A.F.A.; Nguyen, K.L.

    1997-01-01

    A series of guaiacyl and syringyl lignin model compounds and their methylated analogues were reacted with alkaline hydrogen peroxide while irradiating with UV light at 254 nm. The aromatic products obtained were investigated by gas chromatography-mass spectrometry (GC-MS). Guaiacol, syringol and veratrol gave no detectable aromatic products. However, syringol methyl ether gave small amounts of aromatic products, resulting from ring substitution and methoxyl displacement by hydroxyl radicals. Reaction of vanillin and syringaldehyde gave the Dakin reaction products, methoxy-1,4-hydroquinones, while reaction of their methyl ethers yielded benzoic acids. Acetoguaiacone, acetosyringone and their methyl ethers afforded several hydroxylated aromatic products, but no aromatic products were identified in the reaction mixtures from guaiacylpropane and syringylpropane. In contrast, veratrylpropane gave a mixture from which 17 aromatic hydroxylated compounds were identified. It is concluded that for phenolic lignin model compounds, particularly those possessing electrondonating aromatic ring substituents, ring-cleavage reactions involving superoxide radical anions are dominant, whereas for non-phenolic lignin models, hydroxylation reactions through attack of hydroxyl radicals prevail

  15. Modelling of chalcopyrite oxidation reactions in the Outokumpu flash smelting process

    Energy Technology Data Exchange (ETDEWEB)

    Ahokainen, T.; Jokilaakso, A. [Helsinki Univ. of Technology, Otaniemi (Finland)

    1996-12-31

    A mathematical model for simulating oxidation reactions of chalcopyrite particles together with momentum, heat and mass transfer between particle and gas phase in a flash smelting furnace reaction shaft is presented. In simulation, the equations governing the gas flow are solved numerically with a commercial fluid flow package, Phoenics. The particle phase is introduced into the gas flow by a Particle Source In Cell (PSIC) - technique, where a number of discrete particles is tracked in a gas flow and the relevant source terms for momentum, mass, and heat transfer are added to the gas phase equations. The gas phase equations used are elliptic in nature and the fluid turbulence is described by the (k-{epsilon}) -model. Thermal gas phase radiation is simulated with a six-flux radiation model. The chemical reactions of concentrate particles are assumed to happen at two sharp interfaces, and a shrinking core model is applied to describe the mass transfer of chemical species through the reaction product layer. In a molten state, the oxygen consumption is controlled by a film penetration concept. The reacting concentrate particles are a mixture of chalcopyrite and silica. Also a certain amount of pure inert silica is fed to the process as flux. In the simulations the calculation domain includes the concentrate burner and a cylindrical reaction shaft of an industrial scale flash smelting furnace. Some examples about the simulations carried out by the combustion model are presented. (author)

  16. Nanofaceted C/Re(1121): fabrication, structure, and template for synthesizing nanostructured model Pt electrocatalyst for hydrogen evolution reaction.

    Science.gov (United States)

    Yang, Xiaofang; Koel, Bruce E; Wang, Hao; Chen, Wenhua; Bartynski, Robert A

    2012-02-28

    We report the first observation of carbon-induced nanofaceting of a Re single crystal and its application in synthesizing a nanostructured model Pt electrocatalyst investigated using multiple surface science techniques, including low-energy electron diffraction, Auger electron spectroscopy, X-ray photoelectron spectroscopy, low-energy ion scattering, and scanning tunneling microscopy, combined with electrochemical reaction measurements. Upon annealing in acetylene at 700 K followed by annealing in vacuum at 1100 K, an initially planar Re(112̅1) surface becomes completely faceted and covered with three-sided nanopyramids exposing (011̅1), (101̅1), and (112̅0) faces. Using the faceted C/Re(112̅1) surface as a template, we have successfully fabricated a nanostructured Pt monolayer (ML) electrocatalyst. The Pt ML supported on the C/Re nanotemplate exhibits higher activity for the hydrogen evolution reaction than Pt(111). This is the first application of faceted metal surfaces as templates for synthesis of nanoscale model electrocatalyst with well-defined (facet) surface structure and controlled (facet) size on the nanometer scale, illustrating the potential for future studies of nanostructured bimetallic systems relevant to electrocatalytic reactions.

  17. Redox models in chemistry :  A depiction of the conceptions held by secondary school students of redox reactions

    OpenAIRE

    Österlund, Lise-Lotte

    2010-01-01

    According to previous research, students show difficulties in learning redox reactions. By the historical development different redox models exist to explain redox reactions, the oxygen model, the hydrogen model, the electron model and the oxidation number model. This thesis reports about three studies concerning conceptions held by secondary school students of redox reactions. A textbook analysis is also included in the thesis. The first study was an investigation of the students’ use of red...

  18. Primordial black holes from single field models of inflation

    CERN Document Server

    Garcia-Bellido, Juan

    Primordial black holes (PBH) have been shown to arise from high peaks in the matter power spectra of multi-field models of inflation. Here we show, with a simple toy model, that it is also possible to generate a peak in the curvature power spectrum of single-field inflation. We assume that the effective dynamics of the inflaton field presents a near-inflection point which slows down the field right before the end of inflation and gives rise to a prominent spike in the fluctuation power spectrum at scales much smaller than those probed by Cosmic Microwave Background (CMB) and Large Scale Structure (LSS) observations. This peak will give rise, upon reentry during the radiation era, to PBH via gravitational collapse. The mass and abundance of these PBH is such that they could constitute the totality of the Dark Matter today. We satisfy all CMB and LSS constraints and predict a very broad range of PBH masses. Some of these PBH are light enough that they will evaporate before structure formation, leaving behind a ...

  19. Generalized Functional Linear Models With Semiparametric Single-Index Interactions

    KAUST Repository

    Li, Yehua

    2010-06-01

    We introduce a new class of functional generalized linear models, where the response is a scalar and some of the covariates are functional. We assume that the response depends on multiple covariates, a finite number of latent features in the functional predictor, and interaction between the two. To achieve parsimony, the interaction between the multiple covariates and the functional predictor is modeled semiparametrically with a single-index structure. We propose a two step estimation procedure based on local estimating equations, and investigate two situations: (a) when the basis functions are pre-determined, e.g., Fourier or wavelet basis functions and the functional features of interest are known; and (b) when the basis functions are data driven, such as with functional principal components. Asymptotic properties are developed. Notably, we show that when the functional features are data driven, the parameter estimates have an increased asymptotic variance, due to the estimation error of the basis functions. Our methods are illustrated with a simulation study and applied to an empirical data set, where a previously unknown interaction is detected. Technical proofs of our theoretical results are provided in the online supplemental materials.

  20. Modelling Single Tree Structure with Terrestrial Laser Scanner

    Science.gov (United States)

    Yurtseven, H.; Akgül, M.; Gülci, S.

    2017-11-01

    Recent technological developments, which has reliable accuracy and quality for all engineering works, such as remote sensing tools have wide range use in forestry applications. Last decade, sustainable use and management opportunities of forest resources are favorite topics. Thus, precision of obtained data plays an important role in evaluation of current status of forests' value. The use of aerial and terrestrial laser technology has more reliable and effective models to advance the appropriate natural resource management. This study investigates the use of terrestrial laser scanner (TLS) technology in forestry, and also the methodological data processing stages for tree volume extraction is explained. Z+F Imager 5010C TLS system was used for measure single tree information such as tree height, diameter of breast height, branch volume and canopy closure. In this context more detailed and accurate data can be obtained than conventional inventory sampling in forestry by using TLS systems. However the accuracy of obtained data is up to the experiences of TLS operator in the field. Number of scan stations and its positions are other important factors to reduce noise effect and accurate 3D modelling. The results indicated that the use of point cloud data to extract tree information for forestry applications are promising methodology for precision forestry.

  1. A priori modeling of chemical reactions on computational grid platforms: Workflows and data models

    International Nuclear Information System (INIS)

    Rampino, S.; Monari, A.; Rossi, E.; Evangelisti, S.; Laganà, A.

    2012-01-01

    Graphical abstract: The quantum framework of the Grid Empowered Molecular Simulator GEMS assembled on the European Grid allows the ab initio evaluation of the dynamics of small systems starting from the calculation of the electronic properties. Highlights: ► The grid based GEMS simulator accurately models small chemical systems. ► Q5Cost and D5Cost file formats provide interoperability in the workflow. ► Benchmark runs on H + H 2 highlight the Grid empowering. ► O + O 2 and N + N 2 calculated k (T)’s fall within the error bars of the experiment. - Abstract: The quantum framework of the Grid Empowered Molecular Simulator GEMS has been assembled on the segment of the European Grid devoted to the Computational Chemistry Virtual Organization. The related grid based workflow allows the ab initio evaluation of the dynamics of small systems starting from the calculation of the electronic properties. Interoperability between computational codes across the different stages of the workflow was made possible by the use of the common data formats Q5Cost and D5Cost. Illustrative benchmark runs have been performed on the prototype H + H 2 , N + N 2 and O + O 2 gas phase exchange reactions and thermal rate coefficients have been calculated for the last two. Results are discussed in terms of the modeling of the interaction and advantages of using the Grid is highlighted.

  2. Golden rule kinetics of transfer reactions in condensed phase: The microscopic model of electron transfer reactions in disordered solid matrices

    Science.gov (United States)

    Basilevsky, M. V.; Odinokov, A. V.; Titov, S. V.; Mitina, E. A.

    2013-12-01

    The algorithm for a theoretical calculation of transfer reaction rates for light quantum particles (i.e., the electron and H-atom transfers) in non-polar solid matrices is formulated and justified. The mechanism postulated involves a local mode (an either intra- or inter-molecular one) serving as a mediator which accomplishes the energy exchange between the reacting high-frequency quantum mode and the phonon modes belonging to the environment. This approach uses as a background the Fermi golden rule beyond the usually applied spin-boson approximation. The dynamical treatment rests on the one-dimensional version of the standard quantum relaxation equation for the reduced density matrix, which describes the frequency fluctuation spectrum for the local mode under consideration. The temperature dependence of a reaction rate is controlled by the dimensionless parameter ξ0 = ℏω0/kBT where ω0 is the frequency of the local mode and T is the temperature. The realization of the computational scheme is different for the high/intermediate (ξ0 conduction in photosensitive organic materials is considered, based on the above techniques. The electron transfer (ET) in active centers of such systems proceeds via local intra- and intermolecular modes. The active modes, as a rule, operate beyond the kinetic regimes, which are usually postulated in the existing theories of the ET. Our alternative dynamic ET model for local modes immersed in the continuum harmonic medium is formulated for both classical and quantum regimes, and accounts explicitly for the mode/medium interaction. The kinetics of the energy exchange between the local ET subsystem and the surrounding environment essentially determine the total ET rate. The efficient computer code for rate computations is elaborated on. The computations are available for a wide range of system parameters, such as the temperature, external field, local mode frequency, and characteristics of mode/medium interaction. The relation of the

  3. Rigorous Multicomponent Reactive Separations Modelling: Complete Consideration of Reaction-Diffusion Phenomena

    International Nuclear Information System (INIS)

    Ahmadi, A.; Meyer, M.; Rouzineau, D.; Prevost, M.; Alix, P.; Laloue, N.

    2010-01-01

    This paper gives the first step of the development of a rigorous multicomponent reactive separation model. Such a model is highly essential to further the optimization of acid gases removal plants (CO 2 capture, gas treating, etc.) in terms of size and energy consumption, since chemical solvents are conventionally used. Firstly, two main modelling approaches are presented: the equilibrium-based and the rate-based approaches. Secondly, an extended rate-based model with rigorous modelling methodology for diffusion-reaction phenomena is proposed. The film theory and the generalized Maxwell-Stefan equations are used in order to characterize multicomponent interactions. The complete chain of chemical reactions is taken into account. The reactions can be kinetically controlled or at chemical equilibrium, and they are considered for both liquid film and liquid bulk. Thirdly, the method of numerical resolution is described. Coupling the generalized Maxwell-Stefan equations with chemical equilibrium equations leads to a highly non-linear Differential-Algebraic Equations system known as DAE index 3. The set of equations is discretized with finite-differences as its integration by Gear method is complex. The resulting algebraic system is resolved by the Newton- Raphson method. Finally, the present model and the associated methods of numerical resolution are validated for the example of esterification of methanol. This archetype non-electrolytic system permits an interesting analysis of reaction impact on mass transfer, especially near the phase interface. The numerical resolution of the model by Newton-Raphson method gives good results in terms of calculation time and convergence. The simulations show that the impact of reactions at chemical equilibrium and that of kinetically controlled reactions with high kinetics on mass transfer is relatively similar. Moreover, the Fick's law is less adapted for multicomponent mixtures where some abnormalities such as counter

  4. Phase transitions in a holographic s + p model with back-reaction

    Energy Technology Data Exchange (ETDEWEB)

    Nie, Zhang-Yu [Kunming University of Science and Technology, Kunming (China); Chinese Academy of Sciences, State Key Laboratory of Theoretical Physics, Institute of Theoretical Physics, Beijing (China); Shanghai Jiao Tong University, INPAC, Department of Physics, and Shanghai Key Laboratory of Particle Physics and Cosmology, Shanghai (China); Cai, Rong-Gen [Chinese Academy of Sciences, State Key Laboratory of Theoretical Physics, Institute of Theoretical Physics, Beijing (China); Gao, Xin [Virginia Tech, Department of Physics, Blacksburg, VA (United States); Li, Li [University of Crete, Department of Physics, Crete Center for Theoretical Physics, Heraklion (Greece); Zeng, Hui [Kunming University of Science and Technology, Kunming (China); Chinese Academy of Sciences, State Key Laboratory of Theoretical Physics, Institute of Theoretical Physics, Beijing (China)

    2015-11-15

    In a previous paper (Nie et al. in JHEP 1311:087, arXiv:1309.2204 [hep-th], 2013), we presented a holographic s + p superconductor model with a scalar triplet charged under an SU(2) gauge field in the bulk. We also study the competition and coexistence of the s-wave and p-wave orders in the probe limit. In this work we continue to study the model by considering the full back-reaction. The model shows a rich phase structure and various condensate behaviors such as the ''n-type'' and ''u-type'' ones, which are also known as reentrant phase transitions in condensed matter physics. The phase transitions to the p-wave phase or s + p coexisting phase become first order in strong back-reaction cases. In these first order phase transitions, the free energy curve always forms a swallow tail shape, in which the unstable s + p solution can also play an important role. The phase diagrams of this model are given in terms of the dimension of the scalar order and the temperature in the cases of eight different values of the back-reaction parameter, which show that the region for the s + p coexisting phase is enlarged with a small or medium back-reaction parameter but is reduced in the strong back-reaction cases. (orig.)

  5. Models of direct reactions and quantum pre-equilibrium for nucleon scattering on spherical nuclei

    International Nuclear Information System (INIS)

    Dupuis, M.

    2006-01-01

    When a nucleon collides with a target nucleus, several reactions may occur: elastic and inelastic scatterings, charge exchange... In order to describe these reactions, different models are involved: the direct reactions, pre-equilibrium and compound nucleus models. Our goal is to study, within a quantum framework and without any adjustable parameter, the direct and pre-equilibrium reactions for nucleons scatterings off double closed-shell nuclei. We first consider direct reactions: we are studying nucleon scattering with the Melbourne G-matrix, which represents the interaction between the projectile and one target nucleon, and with random phase approximation (RPA) wave functions which describe all target states. This is a fully microscopic approach since no adjustable parameters are involved. A second part is dedicated to the study of nucleon inelastic scattering for large energy transfer which necessarily involves the pre-equilibrium mechanism. Several models have been developed in the past to deal with pre-equilibrium. They start from the Born expansion of the transition amplitude which is associated to the inelastic process and they use several approximations which have not yet been tested. We have achieved some comparisons between second order cross sections which have been calculated with and without these approximations. Our results allow us to criticize some of these approximations and give several directions to improve the quantum pre-equilibrium models. (author)

  6. Descriptive models for single-jet sluicing of sludge waste

    International Nuclear Information System (INIS)

    Erian, F.F.; Mahoney, L.A.; Terrones, G.

    1997-12-01

    Mobilization of sludge waste stored in underground storage tanks can be achieved safely and reliably by sluicing. In the project discussed in this report, the waste in Hanford single-shell Tank 241-C-106 will be mobilized by sluicing, retrieved by a slurry retrieval pump, and transferred via an 1800-ft slurry pipeline to Tank 241-AY-102. A sluicing strategy must be developed that ensures efficient use of the deployed configuration of the sluicing system: the nozzle(s) and the retrieval pump(s). Given a sluicing system configuration in a particular tank, it is desirable to prescribe the sequential locations at which the sludge will be mobilized and retrieved and the rate at which these mobilization and retrieval processes take place. In addition, it is necessary to know whether the retrieved waste slurry meets the requirements for cross-site slurry transport. Some of the physical phenomena that take place during mobilization and retrieval and certain aspects of the sluicing process are described in this report. First, a mathematical model gives (1) an idealized geometrical representation of where, within the confines of a storage tank containing a certain amount of settled waste, sludge can be removed and mobilized; and (2) a quantitative measure of the amount of sludge that can be removed during a sluicing campaign. A model describing an idealized water jet issuing from a circular nozzle located at a given height above a flat surface is also presented in this report. This dynamic water-jet model provides the basis for improving the geometrical sluicing model presented next. In this model the authors assume that the water jet follows a straight trajectory toward a target point on a flat surface. However, the water jet does not follow a straight line in the actual tank, and using the true trajectory will allow a more accurate estimate of the amount of disturbed material. Also, the authors hope that developing accurate force and pressure fields will lead to a better

  7. Study of the Deformation/Interaction Model: How Interactions Increase the Reaction Barrier

    Directory of Open Access Journals (Sweden)

    Zhiling Liang

    2018-01-01

    Full Text Available The interactions (including weak interactions between dienophiles and dienes play an important role in the Diels-Alder reaction. To elucidate the influence of these interactions on the reactivity, a popular DFT functional and a variational DFT functional corrected with dispersion terms are used to investigate different substituent groups incorporated on the dienophiles and dienes. The bond order is used to track the trajectory of the cycloaddition reaction. The deformation/interaction model is used to obtain the interaction energy from the reactant complex to the inflection point until reaching the saddle point. The interaction energy initially increases with a decrease in the interatomic distance, reaching a maximum value, but then decreases when the dienophiles and dienes come closer. Reduced density gradient and chemical energy component analysis are used to analyse the interaction. Traditional transition state theory and variational transition state theory are used to obtain the reaction rates. The influence of tunneling on the reaction rate is also discussed.

  8. Modeling of mass transfer and chemical reactions in a bubble column reactor using a discrete bubble model

    NARCIS (Netherlands)

    Darmana, D.; Deen, N.G.; Kuipers, J.A.M.

    2004-01-01

    A 3D discrete bubble model is adopted to investigate complex behavior involving hydrodynamics, mass transfer and chemical reactions in a gas-liquid bubble column reactor. In this model a continuum description is adopted for the liquid phase and additionally each individual bubble is tracked in a

  9. STEPS: Modeling and Simulating Complex Reaction-Diffusion Systems with Python

    OpenAIRE

    Wils, Stefan; Schutter, Erik De

    2009-01-01

    We describe how the use of the Python language improved the user interface of the program STEPS. STEPS is a simulation platform for modeling and stochastic simulation of coupled reaction-diffusion systems with complex 3-dimensional boundary conditions. Setting up such models is a complicated process that consists of many phases. Initial versions of STEPS relied on a static input format that did not cleanly separate these phases, limiting modelers in how they could control the simulation and b...

  10. Nanolithographic Fabrication and Heterogeneous Reaction Studies ofTwo-Dimensional Platinum Model Catalyst Systems

    Energy Technology Data Exchange (ETDEWEB)

    Contreras, Anthony Marshall [Univ. of California, Berkeley, CA (United States)

    2006-05-20

    In order to better understand the fundamental components that govern catalytic activity, two-dimensional model platinum nanocatalyst arrays have been designed and fabricated. These catalysts arrays are meant to model the interplay of the metal and support important to industrial heterogeneous catalytic reactions. Photolithography and sub-lithographic techniques such as electron beam lithography, size reduction lithography and nanoimprint lithography have been employed to create these platinum nanoarrays. Both in-situ and ex-situ surface science techniques and catalytic reaction measurements were used to correlate the structural parameters of the system to catalytic activity.

  11. Equivalence of two models in single-phase multicomponent flow simulations

    KAUST Repository

    Wu, Yuanqing

    2016-02-28

    In this work, two models to simulate the single-phase multicomponent flow in reservoirs are introduced: single-phase multicomponent flow model and two-phase compositional flow model. Because the single-phase multicomponent flow is a special case of the two-phase compositional flow, the two-phase compositional flow model can also simulate the case. We compare and analyze the two models when simulating the single-phase multicomponent flow, and then demonstrate the equivalence of the two models mathematically. An experiment is also carried out to verify the equivalence of the two models.

  12. Inverse modeling of multicomponent reactive transport through single and dual porosity media

    Science.gov (United States)

    Samper, Javier; Zheng, Liange; Fernández, Ana María; Montenegro, Luis

    2008-06-01

    Compacted bentonite is foreseen as buffer material for high-level radioactive waste in deep geological repositories because it provides hydraulic isolation, chemical stability, and radionuclide sorption. A wide range of laboratory tests were performed within the framework of FEBEX ( Full-scale Engineered Barrier EXperiment) project to characterize buffer properties and develop numerical models for FEBEX bentonite. Here we present inverse single and dual-continuum multicomponent reactive transport models of a long-term permeation test performed on a 2.5 cm long sample of FEBEX bentonite. Initial saline bentonite porewater was flushed with 5.5 pore volumes of fresh granitic water. Water flux and chemical composition of effluent waters were monitored during almost 4 years. The model accounts for solute advection and diffusion and geochemical reactions such as aqueous complexation, acid-base, cation exchange, protonation/deprotonation by surface complexation and dissolution/precipitation of calcite, chalcedony and gypsum. All of these processes are assumed at local equilibrium. Similar to previous studies of bentonite porewater chemistry on batch systems which attest the relevance of protonation/deprotonation on buffering pH, our results confirm that protonation/deprotonation is a key process in maintaining a stable pH under dynamic transport conditions. Breakthrough curves of reactive species are more sensitive to initial porewater concentration than to effective diffusion coefficient. Optimum estimates of initial porewater chemistry of saturated compacted FEBEX bentonite are obtained by solving the inverse problem of multicomponent reactive transport. While the single-continuum model reproduces the trends of measured data for most chemical species, it fails to match properly the long tails of most breakthrough curves. Such limitation is overcome by resorting to a dual-continuum reactive transport model.

  13. Influence of diffusive porosity architecture on kinetically-controlled reactions in mobile-immobile models

    Science.gov (United States)

    Babey, T.; Ginn, T. R.; De Dreuzy, J. R.

    2014-12-01

    Solute transport in porous media may be structured at various scales by geological features, from connectivity patterns of pores to fracture networks. This structure impacts solute repartition and consequently reactivity. Here we study numerically the influence of the organization of porous volumes within diffusive porosity zones on different reactions. We couple a mobile-immobile transport model where an advective zone exchanges with diffusive zones of variable structure to the geochemical modeling software PHREEQC. We focus on two kinetically-controlled reactions, a linear sorption and a nonlinear dissolution of a mineral. We show that in both cases the structure of the immobile zones has an important impact on the overall reaction rates. Through the Multi-Rate Mass Transfer (MRMT) framework, we show that this impact is very well captured by residence times-based models for the kinetic linear sorption, as it is mathematically equivalent to a modification of the initial diffusive structure; Consequently, the overall reaction rate could be easily extrapolated from a conservative tracer experiment. The MRMT models however struggle to reproduce the non-linearity and the threshold effects associated with the kinetic dissolution. A slower reaction, by allowing more time for diffusion to smooth out the concentration gradients, tends to increase their relevance. Figure: Left: Representation of a mobile-immobile model with a complex immobile architecture. The mobile zone is indicated by an arrow. Right: Total remaining mass of mineral in mobile-immobile models and in their equivalent MRMT models during a flush by a highly under-saturated solution. The models only differ by the organization of their immobile porous volumes.

  14. Single bumps in a 2-population homogenized neuronal network model

    Science.gov (United States)

    Kolodina, Karina; Oleynik, Anna; Wyller, John

    2018-05-01

    We investigate existence and stability of single bumps in a homogenized 2-population neural field model, when the firing rate functions are given by the Heaviside function. The model is derived by means of the two-scale convergence technique of Nguetseng in the case of periodic microvariation in the connectivity functions. The connectivity functions are periodically modulated in both the synaptic footprint and in the spatial scale. The bump solutions are constructed by using a pinning function technique for the case where the solutions are independent of the local variable. In the weakly modulated case the generic picture consists of two bumps (one narrow and one broad bump) for each admissible set of threshold values for firing. In addition, a new threshold value regime for existence of bumps is detected. Beyond the weakly modulated regime the number of bumps depends sensitively on the degree of heterogeneity. For the latter case we present a configuration consisting of three coexisting bumps. The linear stability of the bumps is studied by means of the spectral properties of a Fredholm integral operator, block diagonalization of this operator and the Fourier decomposition method. In the weakly modulated regime, one of the bumps is unstable for all relative inhibition times, while the other one is stable for small and moderate values of this parameter. The latter bump becomes unstable as the relative inhibition time exceeds a certain threshold. In the case of the three coexisting bumps detected in the regime of finite degree of heterogeneity, we have at least one stable bump (and maximum two stable bumps) for small and moderate values of the relative inhibition time.

  15. A discrete dislocation dynamics model of creeping single crystals

    Science.gov (United States)

    Rajaguru, M.; Keralavarma, S. M.

    2018-04-01

    Failure by creep is a design limiting issue for metallic materials used in several high temperature applications. Current theoretical models of creep are phenomenological with little connection to the underlying microscopic mechanisms. In this paper, a bottom-up simulation framework based on the discrete dislocation dynamics method is presented for dislocation creep aided by the diffusion of vacancies, known to be the rate controlling mechanism at high temperature and stress levels. The time evolution of the creep strain and the dislocation microstructure in a periodic unit cell of a nominally infinite single crystal is simulated using the kinetic Monte Carlo method, together with approximate constitutive laws formulated for the rates of thermal activation of dislocations over local pinning obstacles. The deformation of the crystal due to dislocation glide between individual thermal activation events is simulated using a standard dislocation dynamics algorithm, extended to account for constant stress periodic boundary conditions. Steady state creep conditions are obtained in the simulations with the predicted creep rates as a function of stress and temperature in good agreement with experimentally reported values. Arrhenius scaling of the creep rates as a function of temperature and power-law scaling with the applied stress are also reproduced, with the values of the power-law exponents in the high stress regime in good agreement with experiments.

  16. Single-shot characterization of enzymatic reaction constants Km and kcat by an acoustic-driven, bubble-based fast micromixer.

    Science.gov (United States)

    Xie, Yuliang; Ahmed, Daniel; Lapsley, Michael Ian; Lin, Sz-Chin Steven; Nawaz, Ahmad Ahsan; Wang, Lin; Huang, Tony Jun

    2012-09-04

    In this work we present an acoustofluidic approach for rapid, single-shot characterization of enzymatic reaction constants K(m) and k(cat). The acoustofluidic design involves a bubble anchored in a horseshoe structure which can be stimulated by a piezoelectric transducer to generate vortices in the fluid. The enzyme and substrate can thus be mixed rapidly, within 100 ms, by the vortices to yield the product. Enzymatic reaction constants K(m) and k(cat) can then be obtained from the reaction rate curves for different concentrations of substrate while holding the enzyme concentration constant. We studied the enzymatic reaction for β-galactosidase and its substrate (resorufin-β-D-galactopyranoside) and found K(m) and k(cat) to be 333 ± 130 μM and 64 ± 8 s(-1), respectively, which are in agreement with published data. Our approach is valuable for studying the kinetics of high-speed enzymatic reactions and other chemical reactions.

  17. The ecology and evolution of temperature-dependent reaction norms for sex determination in reptiles: a mechanistic conceptual model.

    Science.gov (United States)

    Pezaro, Nadav; Doody, J Sean; Thompson, Michael B

    2017-08-01

    Sex-determining mechanisms are broadly categorised as being based on either genetic or environmental factors. Vertebrate sex determination exhibits remarkable diversity but displays distinct phylogenetic patterns. While all eutherian mammals possess XY male heterogamety and female heterogamety (ZW) is ubiquitous in birds, poikilothermic vertebrates (fish, amphibians and reptiles) exhibit multiple genetic sex-determination (GSD) systems as well as environmental sex determination (ESD). Temperature is the factor controlling ESD in reptiles and temperature-dependent sex determination (TSD) in reptiles has become a focal point in the study of this phenomenon. Current patterns of climate change may cause detrimental skews in the population sex ratios of reptiles exhibiting TSD. Understanding the patterns of variation, both within and among populations and linking such patterns with the selection processes they are associated with, is the central challenge of research aimed at predicting the capacity of populations to adapt to novel conditions. Here we present a conceptual model that innovates by defining an individual reaction norm for sex determination as a range of incubation temperatures. By deconstructing individual reaction norms for TSD and revealing their underlying interacting elements, we offer a conceptual solution that explains how variation among individual reaction norms can be inferred from the pattern of population reaction norms. The model also links environmental variation with the different patterns of TSD and describes the processes from which they may arise. Specific climate scenarios are singled out as eco-evolutionary traps that may lead to demographic extinction or a transition to either male or female heterogametic GSD. We describe how the conceptual principles can be applied to interpret TSD data and to explain the adaptive capacity of TSD to climate change as well as its limits and the potential applications for conservation and management

  18. Photon-by-Photon Hidden Markov Model Analysis for Microsecond Single-Molecule FRET Kinetics.

    Science.gov (United States)

    Pirchi, Menahem; Tsukanov, Roman; Khamis, Rashid; Tomov, Toma E; Berger, Yaron; Khara, Dinesh C; Volkov, Hadas; Haran, Gilad; Nir, Eyal

    2016-12-29

    The function of biological macromolecules involves large-scale conformational dynamics spanning multiple time scales, from microseconds to seconds. Such conformational motions, which may involve whole domains or subunits of a protein, play a key role in allosteric regulation. There is an urgent need for experimental methods to probe the fastest of these motions. Single-molecule fluorescence experiments can in principle be used for observing such dynamics, but there is a lack of analysis methods that can extract the maximum amount of information from the data, down to the microsecond time scale. To address this issue, we introduce H 2 MM, a maximum likelihood estimation algorithm for photon-by-photon analysis of single-molecule fluorescence resonance energy transfer (FRET) experiments. H 2 MM is based on analytical estimators for model parameters, derived using the Baum-Welch algorithm. An efficient and effective method for the calculation of these estimators is introduced. H 2 MM is shown to accurately retrieve the reaction times from ∼1 s to ∼10 μs and even faster when applied to simulations of freely diffusing molecules. We further apply this algorithm to single-molecule FRET data collected from Holliday junction molecules and show that at low magnesium concentrations their kinetics are as fast as ∼10 4 s -1 . The new algorithm is particularly suitable for experiments on freely diffusing individual molecules and is readily incorporated into existing analysis packages. It paves the way for the broad application of single-molecule fluorescence to study ultrafast functional dynamics of biomolecules.

  19. Development of a prediction model of severe reaction in boiled egg challenges.

    Science.gov (United States)

    Sugiura, Shiro; Matsui, Teruaki; Nakagawa, Tomoko; Sasaki, Kemal; Nakata, Joon; Kando, Naoyuki; Ito, Komei

    2016-07-01

    We have proposed a new scoring system (Anaphylaxis SCoring Aichi: ASCA) for a quantitative evaluation of the anaphylactic reaction that is observed in an oral food challenge (OFC). Furthermore, the TS/Pro (Total Score of ASCA/cumulative protein dose) can be a marker to represent the overall severity of a food allergy. We aimed to develop a prediction model for a severe allergic reaction that is provoked in a boiled egg white challenge. We used two separate datasets to develop and validate the prediction model, respectively. The development dataset included 198 OFCs, that tested positive. The validation dataset prospectively included 140 consecutive OFCs, irrespective of the result. A 'severe reaction' was defined as a TS/Pro higher than 31 (the median score of the development dataset). A multivariate logistic regression analysis was performed to identify the factors associated with a severe reaction and develop the prediction model. The following four factors were independently associated with a severe reaction: ovomucoid specific IgE class (OM-sIgE: 0-6), aged 5 years or over, a complete avoidance of egg, and a total IgE prediction model. The model showed good discrimination in a receiver operating characteristic analysis; area under the curve (AUC) = 0.84 in development dataset, AUC = 0.85 in validation dataset. The prediction model significantly improved the AUC in both datasets compared to OM-sIgE alone. This simple scoring prediction model was useful for avoiding risky OFC. Copyright © 2016 Japanese Society of Allergology. Production and hosting by Elsevier B.V. All rights reserved.

  20. Study of the reaction between methyl 4-nitrobenzenesulfonate and bromide ions in mixed single-chain-gemini micellar solutions: kinetic evidence for morphological transitions.

    Science.gov (United States)

    del Mar Graciani, María; Rodríguez, Amalia; Moyá, María Luisa

    2008-12-15

    The reaction between methyl 4-nitrobenzenesulfonate and bromide ions has been studied in mixed single-chain-gemini micellar solutions of n-dodecyltrimethylammonium bromide, DTAB, and dodecyl tricosaoxyethylene glycol ether, Brij(35), with alkanediyl-alpha-omega-bis(dodecyldimethylammonium) bromide, 12-s-12,2Br(-) (s=3,4,5). Kinetic micellar effects show that an increase in the solution mole fraction of the single-chain surfactant, X(single-chain), results in a diminution of the mixed micelles tendency to form spherocylindrical aggregates upon increasing surfactant concentration. The dependence of the surfactant concentration at which the sphere-to-rod transition occurs, C(*), on X(single-chain) showed through kinetic data was in agreement with results obtained by means of fluorescence measurements.

  1. A robust methodology for kinetic model parameter estimation for biocatalytic reactions

    DEFF Research Database (Denmark)

    Al-Haque, Naweed; Andrade Santacoloma, Paloma de Gracia; Lima Afonso Neto, Watson

    2012-01-01

    Effective estimation of parameters in biocatalytic reaction kinetic expressions are very important when building process models to enable evaluation of process technology options and alternative biocatalysts. The kinetic models used to describe enzyme-catalyzed reactions generally include several...... parameters, which are strongly correlated with each other. State-of-the-art methodologies such as nonlinear regression (using progress curves) or graphical analysis (using initial rate data, for example, the Lineweaver-Burke plot, Hanes plot or Dixon plot) often incorporate errors in the estimates and rarely...... lead to globally optimized parameter values. In this article, a robust methodology to estimate parameters for biocatalytic reaction kinetic expressions is proposed. The methodology determines the parameters in a systematic manner by exploiting the best features of several of the current approaches...

  2. A Series Solution of the Cauchy Problem for Turing Reaction-diffusion Model

    Directory of Open Access Journals (Sweden)

    L. Päivärinta

    2011-12-01

    Full Text Available In this paper, the series pattern solution of the Cauchy problem for Turing reaction-diffusion model is obtained by using the homotopy analysis method (HAM. Turing reaction-diffusion model is nonlinear reaction-diffusion system which usually has power-law nonlinearities or may be rewritten in the form of power-law nonlinearities. Using the HAM, it is possible to find the exact solution or an approximate solution of the problem. This technique provides a series of functions which converges rapidly to the exact solution of the problem. The efficiency of the approach will be shown by applying the procedure on two problems. Furthermore, the so-called homotopy-Pade technique (HPT is applied to enlarge the convergence region and rate of solution series given by the HAM.

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

    Science.gov (United States)

    Kocadağlı, Tolgahan; Gökmen, Vural

    2016-11-15

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

  4. How attention influences perceptual decision making: Single-trial EEG correlates of drift-diffusion model parameters.

    Science.gov (United States)

    Nunez, Michael D; Vandekerckhove, Joachim; Srinivasan, Ramesh

    2017-02-01

    Perceptual decision making can be accounted for by drift-diffusion models, a class of decision-making models that assume a stochastic accumulation of evidence on each trial. Fitting response time and accuracy to a drift-diffusion model produces evidence accumulation rate and non-decision time parameter estimates that reflect cognitive processes. Our goal is to elucidate the effect of attention on visual decision making. In this study, we show that measures of attention obtained from simultaneous EEG recordings can explain per-trial evidence accumulation rates and perceptual preprocessing times during a visual decision making task. Models assuming linear relationships between diffusion model parameters and EEG measures as external inputs were fit in a single step in a hierarchical Bayesian framework. The EEG measures were features of the evoked potential (EP) to the onset of a masking noise and the onset of a task-relevant signal stimulus. Single-trial evoked EEG responses, P200s to the onsets of visual noise and N200s to the onsets of visual signal, explain single-trial evidence accumulation and preprocessing times. Within-trial evidence accumulation variance was not found to be influenced by attention to the signal or noise. Single-trial measures of attention lead to better out-of-sample predictions of accuracy and correct reaction time distributions for individual subjects.

  5. Orientation dependence in the four-atom reaction of OH + HBr using the single-state oriented OH radical beam.

    Science.gov (United States)

    Tsai, Po-Yu; Che, Dock-Chil; Nakamura, Masaaki; Lin, King-Chuen; Kasai, Toshio

    2010-03-20

    The orientation dependence for the Br atom formation in the reaction of the oriented OH radicals with HBr molecules at 0.26 eV collision energy has been observed for the first time using the hexapole electric field, and we found that the reaction cross-section for O-end attack is more favorable than that for H-end attack by a factor of 3.4 +/- 2.3.

  6. Experimental and theoretical data on ion-molecule-reactions relevant for plasma modelling

    International Nuclear Information System (INIS)

    Hansel, A.; Praxmarer, C.; Lindinger, W.

    1995-01-01

    Despite the fact that the rate coefficients of hundreds of ion-molecule-reactions have been published in the literature, much more data are required for the purpose of plasma modelling. Many ion molecule reactions have rate coefficients, k, as large as the collisional limiting value, k c , i.e. the rate coefficients k c at which ion-neutral collision complexes are formed are close to the actual rate coefficients observed. In the case of the interaction of an ion with a non polar molecule, k c , is determined by the Langevin limiting value k L being typically 10 -9 cm 3 s -1 . However, when ions react with polar molecules k c is predicted by the average dipole orientation (ADO) theory. These classical theories yield accurate rate coefficients at thermal and elevated temperatures for practically all proton transfer as well as for many charge transfer and hydrogen abstraction reactions. The agreement between experimental and calculated values is usually better than ±20% and in the case of proton transfer reactions the agreement seems to be even better as recent investigations have shown. Even the interaction of the permanent ion dipole with non polar and polar neutrals can be taken into account to predict reaction rate coefficients as has been shown very recently in reactions of the highly polar ion ArH 3 + with various neutrals

  7. Spectroscopy of low-lying single-particle states in $^{81}$Zn populated in the $^{80}$Zn(d,p) reaction

    CERN Multimedia

    The aim of this proposal is the study of single-particle states of $^{81}$Zn via the $^{80}$Zn(d,p) reaction in inverse kinematics. $^{81}$Zn will be produced by means of a laser-ionized, 5.5 MeV/u HIE-Isolde $^{80}$Zn beam impinging on a deuterated-polyethylene target. The protons and $\\gamma$-rays emitted in the reaction will be studied using the Miniball + T-REX setup. This experiment will constitute the first spectroscopic study of $^{81}$Zn, which is critically important to determine the energy and ordering of neutron single-particle orbits above the N=50 gap and the properties of $^{78}$Ni.

  8. Randomised clinical trial on the effect of a single oral administration of l-tryptophan, at three dose rates, on reaction speed, plasma concentration and haemolysis in horses.

    Science.gov (United States)

    Noble, Glenys K; Li, Xiuhua; Zhang, Dagong; Sillence, Martin N

    2016-07-01

    Tryptophan (TRP) is marketed as a calmative for horses despite reservations about its efficacy. The aim of this study was to measure the effect of oral TRP administration on the reaction speed of horses. Sixty mature horses were used in a two stage randomised, blind, cross-over study, receiving a placebo and an oral dose of TRP (30, 60 or 120 mg/kg body weight), before undergoing a reaction speed test. Blood samples were taken up to 96 h after TRP administration, to identify signs of acute haemolytic anaemia. Plasma TRP concentrations were increased (P reaction speed of horses when startled. There was no evidence of alterations in clinical pathology parameters in 432 blood samples. While the safety of these doses of TRP can be confirmed, there was no evidence to suggest that a single dose of TRP is an effective calmative for horses. Copyright © 2016 Elsevier Ltd. All rights reserved.

  9. Experimental Determination of the Possible Deuterium - Deuterium Fusion Reaction Originated in a Single Cavitation Bubble Luminescence System Using CDCL3 and D2 O

    International Nuclear Information System (INIS)

    Barbaglia, Mario; Florido, Pablo; Mayer, Roberto; Bonetto, Fabian

    2003-01-01

    We focus this work on the measurement of the possible Deuterium - Deuterium reaction in a SCBL (Single Cavitation Bubble Luminescence) system.We measure the possible reaction at the bubble generation time and at the bubble collapse time. We use a Nd:YAG laser and CDCl 3 and D 2 O as a medium to generate the bubble. Since CDCl 3 accommodation coefficient is best than that of D 2 O, it is expected a greater collapse force than using D 2 O.To benefit the bubble collapse violence, we diminish the temperature of the liquids.To avoid false neutron detection, we developed a measuring system with high background reject using the characteristic experiment times.No neutrons attributable to Deuterium - Deuterium fusion reaction were measured

  10. Multiphasic Reaction Modeling for Polypropylene Production in a Pilot-Scale Catalytic Reactor

    Directory of Open Access Journals (Sweden)

    Mohammad Jakir Hossain Khan

    2016-06-01

    Full Text Available In this study, a novel multiphasic model for the calculation of the polypropylene production in a complicated hydrodynamic and the physiochemical environments has been formulated, confirmed and validated. This is a first research attempt that describes the development of the dual-phasic phenomena, the impact of the optimal process conditions on the production rate of polypropylene and the fluidized bed dynamic details which could be concurrently obtained after solving the model coupled with the CFD (computational fluid dynamics model, the basic mathematical model and the moment equations. Furthermore, we have established the quantitative relationship between the operational condition and the dynamic gas–solid behavior in actual reaction environments. Our results state that the proposed model could be applied for generalizing the production rate of the polymer from a chemical procedure to pilot-scale chemical reaction engineering. However, it was assumed that the solids present in the bubble phase and the reactant gas present in the emulsion phase improved the multiphasic model, thus taking into account that the polymerization took place mutually in the emulsion besides the bubble phase. It was observed that with respect to the experimental extent of the superficial gas velocity and the Ziegler-Natta feed rate, the ratio of the polymer produced as compared to the overall rate of production was approximately in the range of 9%–11%. This is a significant amount and it should not be ignored. We also carried out the simulation studies for comparing the data of the CFD-dependent dual-phasic model, the emulsion phase model, the dynamic bubble model and the experimental results. It was noted that the improved dual-phasic model and the CFD model were able to predict more constricted and safer windows at similar conditions as compared to the experimental results. Our work is unique, as the integrated developed model is able to offer clearer ideas

  11. Towards a unified model of neutrino-nucleus reactions for neutrino oscillation experiments

    Science.gov (United States)

    Nakamura, S. X.; Kamano, H.; Hayato, Y.; Hirai, M.; Horiuchi, W.; Kumano, S.; Murata, T.; Saito, K.; Sakuda, M.; Sato, T.; Suzuki, Y.

    2017-05-01

    A precise description of neutrino-nucleus reactions will play a key role in addressing fundamental questions such as the leptonic CP violation and the neutrino mass hierarchy through analyzing data from next-generation neutrino oscillation experiments. The neutrino energy relevant to the neutrino-nucleus reactions spans a broad range and, accordingly, the dominant reaction mechanism varies across the energy region from quasi-elastic scattering through nucleon resonance excitations to deep inelastic scattering. This corresponds to transitions of the effective degree of freedom for theoretical description from nucleons through meson-baryon to quarks. The main purpose of this review is to report our recent efforts towards a unified description of the neutrino-nucleus reactions over the wide energy range; recent overall progress in the field is also sketched. Starting with an overview of the current status of neutrino-nucleus scattering experiments, we formulate the cross section to be commonly used for the reactions over all the energy regions. A description of the neutrino-nucleon reactions follows and, in particular, a dynamical coupled-channels model for meson productions in and beyond the Δ (1232) region is discussed in detail. We then discuss the neutrino-nucleus reactions, putting emphasis on our theoretical approaches. We start the discussion with electroweak processes in few-nucleon systems studied with the correlated Gaussian method. Then we describe quasi-elastic scattering with nuclear spectral functions, and meson productions with a Δ -hole model. Nuclear modifications of the parton distribution functions determined through a global analysis are also discussed. Finally, we discuss issues to be addressed for future developments.

  12. The hydration of slag, part 1: reaction models for blended cement

    NARCIS (Netherlands)

    Chen, Wei; Brouwers, Jos

    2007-01-01

    Reaction models are proposed to quantify the hydration products and to determine the composition of C–S–H from alkali-activated slags (AAS). Products of the slag hydration are first summarized from observations in literature. The main hydration products include C–S–H, hydrotalcite, hydrogarnet, AFm

  13. Influence of heat and chemical reactions on the Sisko fluid model for ...

    African Journals Online (AJOL)

    The present article studies the effects of heat and chemical reactions on the blood flow through tapered artery with a stenosis. The model incorporates Sisko fluid representation for the blood flow through an axially non-symmetrical but radially symmetric stenosis. Symmetry of the distribution of the wall shearing stress and ...

  14. Relating Derived Relations as a Model of Analogical Reasoning: Reaction Times and Event-Related Potentials

    Science.gov (United States)

    Barnes-Holmes, Dermot; Regan, Donal; Barnes-Holmes, Yvonne; Commins, Sean; Walsh, Derek; Stewart, Ian; Smeets, Paul M.; Whelan, Robert; Dymond, Simon

    2005-01-01

    The current study aimed to test a Relational Frame Theory (RFT) model of analogical reasoning based on the relating of derived same and derived difference relations. Experiment 1 recorded reaction time measures of similar-similar (e.g., "apple is to orange as dog is to cat") versus different-different (e.g., "he is to his brother as…

  15. Molecular Modeling as a Self-Taught Component of a Conventional Undergraduate Chemical Reaction Engineering Course

    Science.gov (United States)

    Rothe, Erhard W.; Zygmunt, William E.

    2016-01-01

    We inserted a self-taught molecular modeling project into an otherwise conventional undergraduate chemical-reaction-engineering course. Our objectives were that students should (a) learn with minimal instructor intervention, (b) gain an appreciation for the relationship between molecular structure and, first, macroscopic state functions in…

  16. Modeling interfacial glass-water reactions: recent advances and current limitations

    International Nuclear Information System (INIS)

    Pierce, Eric M.; Frugier, Pierre; Criscenti, Louise J.; Kwon, Kideok D.; Kerisit, Sebastien N.

    2014-01-01

    Describing the reactions that occur at the glass-water interface and control the development of the altered layer constitutes one of the main scientific challenges impeding existing models from providing accurate radionuclide release estimates. Radionuclide release estimates are a critical component of the safety basis for geologic repositories. The altered layer (i.e., amorphous hydrated surface layer and crystalline reaction products) represents a complex region, both physically and chemically, sandwiched between two distinct boundaries-pristine glass surface at the inner most interface and aqueous solution at the outer most interface. Computational models, spanning different length and timescales, are currently being developed to improve our understanding of this complex and dynamic process with the goal of accurately describing the mesoscale changes that occur as the system evolves. These modeling approaches include geochemical simulations (i.e., classical reaction path simulations and glass reactivity in allowance for alteration layer simulations), Monte Carlo simulations, and molecular dynamics methods. Discussed in this manuscript are the advances and limitations of each modeling approach placed in the context of the glass-water reaction and how collectively these approaches provide insights into the mechanisms that control the formation and evolution of altered layers. New results are presented as examples of each approach. (authors)

  17. Toward a Kinetic Model for Acrylamide Formation in a Glucose-Asparagine Reaction System

    NARCIS (Netherlands)

    Knol, J.J.; Loon, W.A.M.; Linssen, J.P.H.; Ruck, A.L.; Boekel, van M.A.J.S.

    2005-01-01

    A kinetic model for the formation of acrylamide in a glucose-asparagine reaction system is pro-posed. Equimolar solutions (0.2 M) of glucose and asparagine were heated at different tempera-tures (120-200 C) at pH 6.8. Besides the reactants, acrylamide, fructose, and melanoidins were quantified after

  18. Population-reaction model and microbial experimental ecosystems for understanding hierarchical dynamics of ecosystems.

    Science.gov (United States)

    Hosoda, Kazufumi; Tsuda, Soichiro; Kadowaki, Kohmei; Nakamura, Yutaka; Nakano, Tadashi; Ishii, Kojiro

    2016-02-01

    Understanding ecosystem dynamics is crucial as contemporary human societies face ecosystem degradation. One of the challenges that needs to be recognized is the complex hierarchical dynamics. Conventional dynamic models in ecology often represent only the population level and have yet to include the dynamics of the sub-organism level, which makes an ecosystem a complex adaptive system that shows characteristic behaviors such as resilience and regime shifts. The neglect of the sub-organism level in the conventional dynamic models would be because integrating multiple hierarchical levels makes the models unnecessarily complex unless supporting experimental data are present. Now that large amounts of molecular and ecological data are increasingly accessible in microbial experimental ecosystems, it is worthwhile to tackle the questions of their complex hierarchical dynamics. Here, we propose an approach that combines microbial experimental ecosystems and a hierarchical dynamic model named population-reaction model. We present a simple microbial experimental ecosystem as an example and show how the system can be analyzed by a population-reaction model. We also show that population-reaction models can be applied to various ecological concepts, such as predator-prey interactions, climate change, evolution, and stability of diversity. Our approach will reveal a path to the general understanding of various ecosystems and organisms. Copyright © 2015 The Authors. Published by Elsevier Ireland Ltd.. All rights reserved.

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

    Energy Technology Data Exchange (ETDEWEB)

    Gong, R [Georgia Institute of Technology; Lu, C [Georgia Institute of Technology; Luo, Jian [Georgia Institute of Technology; Wu, Wei-min [Stanford University; Cheng, H. [Stanford University; Criddle, Craig [Stanford University; Kitanidis, Peter K. [Stanford University; Gu, Baohua [ORNL; Watson, David B [ORNL; Jardine, Philip M [ORNL; Brooks, Scott C [ORNL

    2011-03-01

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

  20. Self-Assembly of Single-Layer CoAl-Layered Double Hydroxide Nanosheets on 3D Graphene Network Used as Highly Efficient Electrocatalyst for Oxygen Evolution Reaction.

    Science.gov (United States)

    Ping, Jianfeng; Wang, Yixian; Lu, Qipeng; Chen, Bo; Chen, Junze; Huang, Ying; Ma, Qinglang; Tan, Chaoliang; Yang, Jian; Cao, Xiehong; Wang, Zhijuan; Wu, Jian; Ying, Yibin; Zhang, Hua

    2016-09-01

    A non-noble metal based 3D porous electrocatalyst is prepared by self-assembly of the liquid-exfoliated single-layer CoAl-layered double hydroxide nanosheets (CoAl-NSs) onto 3D graphene network, which exhibits higher catalytic activity and better stability for electrochemical oxygen evolution reaction compared to the commercial IrO2 nanoparticle-based 3D porous electrocatalyst. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  1. Reaction rates of ozone and terpenes adsorbed to model indoor surfaces.

    Science.gov (United States)

    Springs, M; Wells, J R; Morrison, G C

    2011-08-01

    Reaction rates and reaction probabilities have been quantified on model indoor surfaces for the reaction of ozone with two monoterpenes (Δ(3) -carene and d-limonene). Molar surface loadings were obtained by performing breakthrough experiments in a plug-flow reactor (PFR) packed with beads of glass, polyvinylchloride or zirconium silicate. Reaction rates and probabilities were determined by equilibrating the PFR with both the terpene and the ozone and measuring the ozone consumption rate. To mimic typical indoor conditions, temperatures of 20, 25, and 30°C were used in both types of experiments along with a relative humidity ranging from 10% to 80%. The molar surface loading decreased with increased relative humidity, especially on glass, suggesting that water competed with the terpenes for adsorption sites. The ozone reactivity experiments indicate that higher surface loadings correspond with higher ozone uptake. The reaction probability for Δ(3) -carene with ozone ranged from 2.9 × 10(-6) to 3.0 × 10(-5) while reaction probabilities for d-limonene ranged from 2.8 × 10(-5) to 3.0 × 10(-4) . These surface reaction probabilities are roughly 10-100 times greater than the corresponding gas-phase values. Extrapolation of these results to typical indoor conditions suggests that surface conversion rates may be substantial relative to gas-phase rates, especially for lower volatility terpenoids. At present, it is unclear how important heterogeneous reactions will be in influencing indoor concentrations of terpenes, ozone and their reaction products. We observe that surface reaction probabilities were 10 to 100 times greater than their corresponding gas-phase values. Thus indoor surfaces do enhance effective reaction rates and adsorption of terpenes will increase ozone flux to otherwise low-reactivity surfaces. Extrapolation of these results to typical indoor conditions suggests that surface conversion rates may be substantial relative to gas-phase rates, especially

  2. Flagellates as model system for gravity detection of single cells

    Science.gov (United States)

    Lebert, Michael; Richter, Peter; Daiker, Viktor; Schuster, Martin; Tebart, Jenny; Strauch, Sebastian M.; Donat-Peter, H.

    Euglena gracilis is a unicellular, photosynthetic organism which uses light and gravity as en-vironmental hints to reach and stay in horizons of the water column which are optimal for growth and reproduction. The orientation in respect to light (so called positive and nega-tive phototaxis, i.e. movement toward or away of a light source) was well known and fairly good understood. In contrast, knowledge about the movement away from the centre of gravity (negative gravitaxis) was rather scarce. Over a century it was unclear whether orientation in respect to the gravity vector is based on a physical or a physiological mechanism. Recent results clearly favour the latter. Knock-down mutants (RNAi) were characterized which define certain key components of the gravitactic signal transduction chain. These key components include a TRP-like channel, a gravitaxis-specific calmodulin and a protein kinase A. The molecular characterization of these components is currently performed and will be presented. Euglena is not only a model system for the close understanding of gravity detection in single cells, but can also be used as photosynthetic component, i.e. oxygen source and carbon dioxide as well as nitrogenic components sink in Closed Environmental Systems (CES). Due CES are systems of choice in times of scarce flight opportunities. They allow a massive sample sharing and combine possibilities to do microgravity research for biologists but also for engineers, physicists and material scientists. Recent attempts include Aquacells and Omegahab. In the near future miniaturized systems (Chinese ShenZhou) as well as advanced CES will be flown or tested, respectively. Current attempts and plans will be presented.

  3. Traveling Wave Solutions of Reaction-Diffusion Equations Arising in Atherosclerosis Models

    Directory of Open Access Journals (Sweden)

    Narcisa Apreutesei

    2014-05-01

    Full Text Available In this short review article, two atherosclerosis models are presented, one as a scalar equation and the other one as a system of two equations. They are given in terms of reaction-diffusion equations in an infinite strip with nonlinear boundary conditions. The existence of traveling wave solutions is studied for these models. The monostable and bistable cases are introduced and analyzed.

  4. A parametric duration model of the reaction times of drivers distracted by mobile phone conversations.

    Science.gov (United States)

    Haque, Md Mazharul; Washington, Simon

    2014-01-01

    The use of mobile phones while driving is more prevalent among young drivers-a less experienced cohort with elevated crash risk. The objective of this study was to examine and better understand the reaction times of young drivers to a traffic event originating in their peripheral vision whilst engaged in a mobile phone conversation. The CARRS-Q advanced driving simulator was used to test a sample of young drivers on various simulated driving tasks, including an event that originated within the driver's peripheral vision, whereby a pedestrian enters a zebra crossing from a sidewalk. Thirty-two licensed drivers drove the simulator in three phone conditions: baseline (no phone conversation), hands-free and handheld. In addition to driving the simulator each participant completed questionnaires related to driver demographics, driving history, usage of mobile phones while driving, and general mobile phone usage history. The participants were 21-26 years old and split evenly by gender. Drivers' reaction times to a pedestrian in the zebra crossing were modelled using a parametric accelerated failure time (AFT) duration model with a Weibull distribution. Also tested where two different model specifications to account for the structured heterogeneity arising from the repeated measures experimental design. The Weibull AFT model with gamma heterogeneity was found to be the best fitting model and identified four significant variables influencing the reaction times, including phone condition, driver's age, license type (provisional license holder or not), and self-reported frequency of usage of handheld phones while driving. The reaction times of drivers were more than 40% longer in the distracted condition compared to baseline (not distracted). Moreover, the impairment of reaction times due to mobile phone conversations was almost double for provisional compared to open license holders. A reduction in the ability to detect traffic events in the periphery whilst distracted

  5. A Geochemical Reaction Model for Titration of Contaminated Soil and Groundwater at the Oak Ridge Reservation

    Science.gov (United States)

    Zhang, F.; Parker, J. C.; Gu, B.; Luo, W.; Brooks, S. C.; Spalding, B. P.; Jardine, P. M.; Watson, D. B.

    2007-12-01

    This study investigates geochemical reactions during titration of contaminated soil and groundwater at the Oak Ridge Reservation in eastern Tennessee. The soils and groundwater exhibits low pH and high concentrations of aluminum, calcium, magnesium, manganese, various trace metals such as nickel and cobalt, and radionuclides such as uranium and technetium. The mobility of many of the contaminant species diminishes with increasing pH. However, base additions to increase pH are strongly buffered by various precipitation/dissolution and adsorption/desorption reactions. The ability to predict acid-base behavior and associated geochemical effects is thus critical to evaluate remediation performance of pH manipulation strategies. This study was undertaken to develop a practical but generally applicable geochemical model to predict aqueous and solid-phase speciation during soil and groundwater titration. To model titration in the presence of aquifer solids, an approach proposed by Spalding and Spalding (2001) was utilized, which treats aquifer solids as a polyprotic acid. Previous studies have shown that Fe and Al-oxyhydroxides strongly sorb dissolved Ni, U and Tc species. In this study, since the total Fe concentration is much smaller than that of Al, only ion exchange reactions associated with Al hydroxides are considered. An equilibrium reaction model that includes aqueous complexation, precipitation, ion exchange, and soil buffering reactions was developed and implemented in the code HydroGeoChem 5.0 (HGC5). Comparison of model results with experimental titration curves for contaminated groundwater alone and for soil- water systems indicated close agreement. This study is expected to facilitate field-scale modeling of geochemical processes under conditions with highly variable pH to develop practical methods to control contaminant mobility at geochemically complex sites.

  6. Influence of reactions heats on variation of radius, temperature, pressure and chemical species amounts within a single acoustic cavitation bubble.

    Science.gov (United States)

    Kerboua, Kaouther; Hamdaoui, Oualid

    2018-03-01

    The scientific interest toward the study of acoustic bubble is mainly explained by its practical benefit in providing a reactional media favorable to the rapid evolution of chemical mechanism. The evolution of this mechanism is related to the simultaneous and dependent variation of the volume, temperature and pressure within the bubble, retrieved by the resolution of a differential equations system, including among others the thermal balance. This last one is subject to different assumptions, some authors deem simply that the temperature varies adiabatically during the collapsing phase, without considering the reactions heat of the studied mechanism. This paper aims to evaluate the pertinence of neglecting reactions heats in the thermal balance, by analyzing their effect on the variation of radius, temperature, pressure and chemical species amounts. The results show that the introduction of reactions heats conducts to a decrease of the temperature, an increase of the pressure and a reduction of the bubble volume. As a consequence, this leads to a drop of the quantities of free radicals produced by the chemical mechanism evolving within the bubble. This paper also proved that the impact of the consideration of reactions heats is dependent of the frequency and the acoustic amplitude of the ultrasonic wave. Copyright © 2017 Elsevier B.V. All rights reserved.

  7. Reentry blackout prediction for atmospheric reentry demonstrator mission considering uncertainty in chemical reaction rate model

    Science.gov (United States)

    Jung, Minseok; Kihara, Hisashi; Abe, Ken-ichi; Takahashi, Yusuke

    2018-01-01

    A numerical simulation model of plasma flows and electromagnetic waves around a vehicle was developed to predict a radio frequency blackout. Plasma flows in the shock layer and the wake region were calculated using a computational fluid dynamics technique with a three-dimensional model. A finite-catalytic wall condition known to affect plasma properties, such as the number density of electrons, was considered for accurate prediction. A parametric study was performed to investigate the effect of uncertainty in the chemical reaction rate model on evaluating a radio frequency blackout. The behavior of electromagnetic waves in plasma was investigated using a frequency-dependent finite-difference time-domain method. Numerical simulations of reentry blackout were performed for the Atmospheric Reentry Demonstrator mission at various altitudes. The plasma flows and the complex movement of electromagnetic waves around the Atmospheric Reentry Demonstrator vehicle were clarified. The predicted signal loss profile was then directly compared with the experimental flight data to validate the present models. The numerical results generally reproduced the trends over altitudes of the measured data. It is suggested that the present simulation model can be used to investigate the radio frequency blackout and signal loss of electromagnetic waves in the communication of a reentry vehicle. It was confirmed that high associative ionization reaction rates contribute to reducing the electron density in the wake region and radio frequency blackout. It is suggested that the accuracy of predicting the signal loss improved when considering the uncertainty in the chemical reaction model for associative ionizations.

  8. Noise-and delay-induced phase transitions of the dimer–monomer surface reaction model

    International Nuclear Information System (INIS)

    Zeng Chunhua; Wang Hua

    2012-01-01

    Highlights: ► We study the dimer–monomer surface reaction model. ► We show that noise induces first-order irreversible phase transition (IPT). ► Combination of noise and time-delayed feedback induce first- and second-order IPT. ► First- and second-order IPT is viewed as noise-and delay-induced phase transitions. - Abstract: The effects of noise and time-delayed feedback in the dimer–monomer (DM) surface reaction model are investigated. Applying small delay approximation, we construct a stochastic delayed differential equation and its Fokker–Planck equation to describe the state evolution of the DM reaction model. We show that the noise can only induce first-order irreversible phase transition (IPT) characteristic of the DM model, however the combination of the noise and time-delayed feedback can simultaneously induce first- and second-order IPT characteristics of the DM model. Therefore, it is shown that the well-known first- and second-order IPT characteristics of the DM model may be viewed as noise-and delay-induced phase transitions.

  9. ANALYZING THE HYDRO DYNAMICS AND THE CHEMICAL REACTIONS IN PULP DIGESTER SYSTEMS USING CFD MODELLING

    OpenAIRE

    Pourian, Bijan

    2011-01-01

    The aim of this thesis is to use differential analysis and finite volume method (FVM) to model and analyze a continuous pulp digester in order to create a detailed picture of the flow behaviour and chemical reactions in the digester. This information will be used to optimize wood chip flow and reactions and to diagnose and avoid faults such as hang-ups and channelling. As digesters increase in size, the importance of control of the liquor flow in the wood chip bed also increases. Pulping reac...

  10. Mathematical modelling of light-induced electric reaction of Cucurbita pepo L. leaves

    Directory of Open Access Journals (Sweden)

    Jan Stolarek

    2014-01-01

    Full Text Available The bioelectRIc reactions of 14-16 day old plants of pumpkin (Cucurbita pepo L. and internodal cells of Nitellopsis obtusa to the action of visible and ultraviolet light (UV-C were studied. The possibility of analyzing the bioelectric reaction of pumpkin plants induced by visible light by means of mathematical modelling using a linear differential equation of the second order was considered. The solution of this equation (positive and negative functions can, in a sufficient way, reflect the participation of H+ and CI- ions in the generation of the photoelectric response in green plant cells.

  11. Chemical modelling of Alkali Silica reaction: Influence of the reactive aggregate size distribution

    International Nuclear Information System (INIS)

    Poyet, S.; Sellier, A.; Capra, B.; Foray, G.; Torrenti, J.M.; Cognon, H.; Bourdarot, E.

    2007-01-01

    This article presents a new model which aims at predicting the expansion induced by Alkali Silica Reaction (ASR) and describing the chemical evolution of affected concretes. It is based on the description of the transport and reaction of alkalis and calcium ions within a Relative Elementary Volume (REV). It takes into account the influence of the reactive aggregate size grading on ASR, i.e. the effect of the simultaneous presence of different sized reactive aggregates within concrete. The constitutive equations are detailed and fitted using experimental results. Results from numerical simulations are presented and compared with experiments. (authors)

  12. Modeling radical edge-site reactions of biochar in CO2/water solution under ultrasonic treatment

    Science.gov (United States)

    Zubatiuk, Tetiana; Sajjadi, Baharak; Hill, Glake; Leszczynska, Danuta; Chen, Wei-Yin; Leszczynski, Jerzy

    2017-12-01

    We report results of theoretical evaluation of the mechanisms of possible radical reactions on the edge-site of biochar with CO2,SUP>·-, OH ˙ , and H ˙ in irradiated aqueous solution. The computational studies were performed for model poly aromatic systems. Obtained mechanisms reflect one of the routes of the oxygen loss accompanied by increase of hydrogen content, as observed in photochemical experiment. The reaction of CO2·- with the edge site of biochar mainly leads to reduced rather than oxidized products. The mechanism of CO2 capturing is mapped by different routes of one-electron reduction and radical addition to the aromatic ring.

  13. Relationships among North American and Japanese Laetiporus isolates inferred from molecular phylogenetics and single-spore incompatibility reactions

    Science.gov (United States)

    Mark T. Banik; Daniel L. Lindner; Yuko Ota; Tsutomu. Hattori

    2010-01-01

    Relationships were investigated among North American and Japanese isolates of Laetiporus using phylogenetic analysis of ITS sequences and single-spore isolate incompatibility. Single-spore isolate pairings revealed no significant compatibility between North American and Japanese isolates. ITS analysis revealed 12 clades within the core ...

  14. Reaction mechanisms in the radiolysis of peptides, polypeptides and proteins II reactions at side-chain loci in model systems

    International Nuclear Information System (INIS)

    Garrison, W.M.

    1983-11-01

    The major emphasis in radiation biology at the molecular level has been on the nucleic acid component of the nucleic acid-protein complex because of its primary genetic importance. But there is increasing evidence that radiation damage to the protein component also has important biological implications. Damage to capsid protein now appears to be a major factor in the radiation inactivation of phage and other viruses. And, there is increasing evidence that radiation-chemical change in the protein component of chromation leads to changes in the stability of the repressor-operator complexes involved in gene expression. Knowledge of the radiation chemistry of protein is also of importance in other fields such as the application of radiation sterilization to foods and drugs. Recent findings that a class of compounds, the α,α'-diaminodicarboxylic acids, not normally present in food proteins, are formed in protein radiolysis is of particular significance since certain of their peptide derivatives have been showing to exhibit immunological activity. The purpose of this review is to bring together and to correlate our present knowledge of products and mechanisms in the radiolysis of peptides, polypeptides and proteins both aqueous and solid-state. In part 1 we presented a discussion of the radiation-induced reactions of the peptide main-chain in model peptide and polypeptide systems. Here in part 2 the emphasis is on the competing radiation chemistry at side-chain loci of peptide derivatives of aliphatic, aromatic-unsaturated and sulfur-containing amino acids in similar systems. Information obtained with the various experimental techniques of product analysis, competition kinetics, spin-trapping, pulse radiolysis, and ESR spectroscopy are included

  15. OPE3 : A model system for single-molecule transport

    NARCIS (Netherlands)

    Frisenda, R.

    2016-01-01

    In this dissertation, charge-transport through individual organic molecules is investigated. The single molecules are contacted with two-terminal mechanically controllable break junction gold electrodes and their electrical and mechanical behavior studied at room and low temperature.

  16. Modeling and Development of Superconducting Nanowire Single Photon Detectors

    Data.gov (United States)

    National Aeronautics and Space Administration — This proposal outlines a research project as the central component of a Ph.D. program focused on the device physics of superconducting nanowire single photon...

  17. Experimental study and numerical modelling of geochemical reactions occurring during uranium in situ recovery (ISR) mining

    International Nuclear Information System (INIS)

    Ben Simon, R.

    2011-09-01

    The in situ Recovery (ISR) method consists of ore mining by in situ chemical leaching with acid or alkaline solutions. ISR takes place underground and is therefore limited to the analysis of the pumped solutions, hence ISR mine management is still empirical. Numerical modelling has been considered to achieve more efficient management of this process. Three different phenomena have to be taken into account for numerical simulations of uranium ISR mining: (1) geochemical reactions; (2) the kinetics of these reactions, and (3) hydrodynamic transport with respect to the reaction kinetics. Leaching tests have been conducted on ore samples from an uranium mine in Tortkuduk (Kazakhstan) where ISR is conducted by acid leaching. Two types of leaching experiments were performed: (1) tests in batch reactors; and (2) extraction in flow through columns. The assumptions deduced from the leaching tests were tested and validated by modelling the laboratory experiments with the numerical codes CHESS and HYTEC, both developed at the Geosciences research center of Mines ParisTech. A well-constrained 1D hydrogeochemical transport model of the ISR process at laboratory-scale was proposed. It enables to translate the chemical release sequence that is observed during experiments into a geochemical reaction sequence. It was possible to highlight the controlling factors of uranium dissolution, and the precipitation of secondary mineral phase in the deposit, as well as the determination of the relative importance of these factors. (author)

  18. SOA formation from partitioning and heterogeneous reactions: model study in the presence of inorganic species.

    Science.gov (United States)

    Jang, Myoseon; Czoschke, Nadine M; Northcross, Amanda L; Cao, Gang; Shaof, David

    2006-05-01

    A predictive model for secondary organic aerosol (SOA) formation by both partitioning and heterogeneous reactions was developed for SOA created from ozonolysis of alpha-pinene in the presence of preexisting inorganic seed aerosols. SOA was created in a 2 m3 polytetrafluoroethylene film indoor chamber under darkness. Extensive sets of SOA experiments were conducted varying humidity, inorganic seed compositions comprising of ammonium sulfate and sulfuric acid, and amounts of inorganic seed mass. SOA mass was decoupled into partitioning (OM(P)) and heterogeneous aerosol production (OM(H)). The reaction rate constant for OM(H) production was subdivided into three categories (fast, medium, and slow) to consider different reactivity of organic products for the particle phase heterogeneous reactions. The influence of particle acidity on reaction rates was treated in a previous semiempirical model. Model OM(H) was developed with medium and strong acidic seed aerosols, and then extrapolated to OM(H) in weak acidic conditions, which are more relevant to atmospheric aerosols. To demonstrate the effects of preexisting glyoxal derivatives (e.g., glyoxal hydrate and dimer) on OM(H), SOA was created with a seed mixture comprising of aqueous glyoxal and inorganic species. Our results show that heterogeneous SOA formation was also influenced by preexisting reactive glyoxal derivatives.

  19. A Stefan model for mass transfer in a rotating disk reaction vessel

    KAUST Repository

    BOHUN, C. S.

    2015-05-04

    Copyright © Cambridge University Press 2015. In this paper, we focus on the process of mass transfer in the rotating disk apparatus formulated as a Stefan problem with consideration given to both the hydrodynamics of the process and the specific chemical reactions occurring in the bulk. The wide range in the reaction rates of the underlying chemistry allows for a natural decoupling of the problem into a simplified set of weakly coupled convective-reaction-diffusion equations for the slowly reacting chemical species and a set of algebraic relations for the species that react rapidly. An analysis of the chemical equilibrium conditions identifies an expansion parameter and a reduced model that remains valid for arbitrarily large times. Numerical solutions of the model are compared to an asymptotic analysis revealing three distinct time scales and chemical diffusion boundary layer that lies completely inside the hydrodynamic layer. Formulated as a Stefan problem, the model generalizes the work of Levich (Levich and Spalding (1962) Physicochemical hydrodynamics, vol. 689, Prentice-Hall Englewood Cliffs, NJ) and will help better understand the natural limitations of the rotating disk reaction vessel when consideration is made for the reacting chemical species.

  20. Quasiclassical trajectory study of the Cl +CH4 reaction dynamics on a quadratic configuration interaction with single and double excitation interpolated potential energy surface

    Science.gov (United States)

    Castillo, J. F.; Aoiz, F. J.; Bañares, L.

    2006-09-01

    An ab initio interpolated potential energy surface (PES) for the Cl +CH4 reactive system has been constructed using the interpolation method of Collins and co-workers [J. Chem. Phys. 102, 5647 (1995); 108, 8302 (1998); 111, 816 (1999); Theor. Chem. Acc. 108, 313 (2002)]. The ab initio calculations have been performed using quadratic configuration interaction with single and double excitation theory to build the PES. A simple scaling all correlation technique has been used to obtain a PES which yields a barrier height and reaction energy in good agreement with high level ab initio calculations and experimental measurements. Using these interpolated PESs, a detailed quasiclassical trajectory study of integral and differential cross sections, product rovibrational populations, and internal energy distributions has been carried out for the Cl +CH4 and Cl +CD4 reactions, and the theoretical results have been compared with the available experimental data. It has been shown that the calculated total reaction cross sections versus collision energy for the Cl +CH4 and Cl +CD4 reactions is very sensitive to the barrier height. Besides, due to the zero-point energy (ZPE) leakage of the CH4 molecule to the reaction coordinate in the quasiclassical trajectory (QCT) calculations, the reaction threshold falls below the barrier height of the PES. The ZPE leakage leads to CH3 and HCl coproducts with internal energy below its corresponding ZPEs. We have shown that a Gaussian binning (GB) analysis of the trajectories yields excitation functions in somehow better agreement with the experimental determinations. The HCl(v'=0) and DCl(v'=0) rotational distributions are as well very sensitive to the ZPE problem. The GB correction narrows and shifts the rotational distributions to lower values of the rotational quantum numbers. However, the present QCT rotational distributions are still hotter than the experimental distributions. In both reactions the angular distributions shift from

  1. Investigation of nucleon-induced reactions in the Fermi energy domain within the microscopic DYWAN model

    Energy Technology Data Exchange (ETDEWEB)

    Sebille, F.; Bonilla, C. [SUBATECH, Universite de Nantes, CNRS/IN2P3, 44 - Nantes (France); Blideanu, V.; Lecolley, J.F. [Laboratoire de Physique Corpusculaire, ENSICAEN, Universite de Caen, IN2P3-CNRS, 14 - Caen (France)

    2004-06-01

    A microscopic investigation of nucleon-induced reactions is addressed within the DYWAN model, which is based on the projection methods of out of equilibrium statistical physics and on the mathematical theory of wavelets. Due to a strongly compressed representation of the fermionic wave-functions, the numerical simulations of the nucleon transport in target are therefore able to preserve the quantum nature of the colliding system, as well as a least biased many-body information needed to keep track of the cluster formation. A special attention is devoted to the fingerprints of the phase space topology induced by the fluctuations of the self-consistent mean-field. Comparisons be ween theoretical results and experimental data point out that ETDHF type approaches are well suited to describe reaction mechanisms in the Fermi energy domain. The observed sensitivity to physical effects shows that the nucleon-induced reactions provide a valuable probe of the nuclear interaction in this range of energy. (authors)

  2. An under-met and over-met expectations model of employee reactions to merit raises.

    Science.gov (United States)

    Schaubroeck, John; Shaw, Jason D; Duffy, Michelle K; Mitra, Atul

    2008-03-01

    The authors developed a model of how raise expectations influence the relationship between merit pay raises and employee reactions and tested it using a sample of hospital employees. Pay-for-performance (PFP) perceptions were consistently related to personal reactions (e.g., pay raise happiness, pay-level satisfaction, and turnover intentions). Merit pay raises were strongly related to reactions only among employees with high raise expectations and high PFP perceptions. The interactive effects of under-met/over-met expectations and PFP perceptions were mediated by the extent to which participants saw the raise as generous and they were happy with the raises they received. The authors discuss the implications of these findings for expectation-fulfillment theories, merit pay research, and the administration of incentives. Copyright 2008 APA

  3. A reaction-diffusion model of CO2 influx into an oocyte

    Science.gov (United States)

    Somersalo, Erkki; Occhipinti, Rossana; Boron, Walter F.; Calvetti, Daniela

    2012-01-01

    We have developed and implemented a novel mathematical model for simulating transients in surface pH (pHS) and intracellular pH (pHi) caused by the influx of carbon dioxide (CO2) into a Xenopus oocyte. These transients are important tools for studying gas channels. We assume that the oocyte is a sphere surrounded by a thin layer of unstirred fluid, the extracellular unconvected fluid (EUF), which is in turn surrounded by the well-stirred bulk extracellular fluid (BECF) that represents an infinite reservoir for all solutes. Here, we assume that the oocyte plasma membrane is permeable only to CO2. In both the EUF and intracellular space, solute concentrations can change because of diffusion and reactions. The reactions are the slow equilibration of the CO2 hydration-dehydration reactions and competing equilibria among carbonic acid (H2CO3)/bicarbonate ( HCO3-) and a multitude of non-CO2/HCO3- buffers. Mathematically, the model is described by a coupled system of reaction-diffusion equations that—assuming spherical radial symmetry—we solved using the method of lines with appropriate stiff solvers. In agreement with experimental data (Musa-Aziz et al, PNAS 2009, 106:5406–5411), the model predicts that exposing the cell to extracellular 1.5% CO2/10 mM HCO3- (pH 7.50) causes pHi to fall and pHS to rise rapidly to a peak and then decay. Moreover, the model provides insights into the competition between diffusion and reaction processes when we change the width of the EUF, membrane permeability to CO2, native extra-and intracellular carbonic anhydrase-like activities, the non-CO2/HCO3- (intrinsic) intracellular buffering power, or mobility of intrinsic intracellular buffers. PMID:22728674

  4. Modeling Bimolecular Reactions and Transport in Porous Media Via Particle Tracking

    Energy Technology Data Exchange (ETDEWEB)

    Dong Ding; David Benson; Amir Paster; Diogo Bolster

    2012-01-01

    We use a particle-tracking method to simulate several one-dimensional bimolecular reactive transport experiments. In this numerical method, the reactants are represented by particles: advection and dispersion dominate the flow, and molecular diffusion dictates, in large part, the reactions. The particle/particle reactions are determined by a combination of two probabilities dictated by the physics of transport and energetics of reaction. The first is that reactant particles occupy the same volume over a short time interval. The second is the conditional probability that two collocated particles favorably transform into a reaction. The first probability is a direct physical representation of the degree of mixing in an advancing displacement front, and as such lacks empirical parameters except for the user-defined number of particles. This number can be determined analytically from concentration autocovariance, if this type of data is available. The simulations compare favorably to two physical experiments. In one, the concentration of product, 1,2-naphthoquinoe-4-aminobenzene (NQAB) from reaction between 1,2-naphthoquinone-4-sulfonic acid (NQS) and aniline (AN), was measured at the outflow of a column filled with glass beads at different times. In the other, the concentration distribution of reactants (CuSO_4 and EDTA^{4-}) and products (CuEDTA^{4-}) were quantified by snapshots of transmitted light through a column packed with cryloite sand. The thermodynamic rate coefficient in the latter experiment was 10^7 times greater than the former experiment, making it essentially instantaneous. When compared to the solution of the advection-dispersion-reaction equation (ADRE) with the well-mixed reaction coefficient, the experiments and the particle-tracking simulations showed on the order of 20% to 40% less overall product, which is attributed to poor mixing. The poor mixing also leads to higher product concentrations on the edges of the mixing zones, which the particle

  5. Analysis of Milk Production Traits in Early Lactation Using a Reaction Norm Model with Unknown Covariates

    DEFF Research Database (Denmark)

    Mahdi Shariati, Mohammad; Su, Guosheng; Madsen, Per

    2007-01-01

    The reaction norm model is becoming a popular approach to study genotype x environment interaction (GxE), especially when there is a continuum of environmental effects. These effects are typically unknown, and an approximation that is used in the literature is to replace them by the phenotypic...... means of each environment. It has been shown that this method results in poor inferences and that a more satisfactory alternative is to infer environmental effects jointly with the other parameters of the model. Such a reaction norm model with unknown covariates and heterogeneous residual variances...... across herds was fitted to milk, protein, and fat yield of first-lactation Danish Holstein cows to investigate the presence of GxE. Data included 188,502 first test-day records from 299 herds and 3,775 herd-years in a time period ranging from 1991 to 2003. Variance components and breeding values were...

  6. Nonlinear electromechanical modelling and dynamical behavior analysis of a satellite reaction wheel

    Science.gov (United States)

    Aghalari, Alireza; Shahravi, Morteza

    2017-12-01

    The present research addresses the satellite reaction wheel (RW) nonlinear electromechanical coupling dynamics including dynamic eccentricity of brushless dc (BLDC) motor and gyroscopic effects, as well as dry friction of shaft-bearing joints (relative small slip) and bearing friction. In contrast to other studies, the rotational velocity of the flywheel is considered to be controllable, so it is possible to study the reaction wheel dynamical behavior in acceleration stages. The RW is modeled as a three-phases BLDC motor as well as flywheel with unbalances on a rigid shaft and flexible bearings. Improved Lagrangian dynamics for electromechanical systems is used to obtain the mathematical model of the system. The developed model can properly describe electromechanical nonlinear coupled dynamical behavior of the satellite RW. Numerical simulations show the effectiveness of the presented approach.

  7. Modeling spallation reactions in tungsten and uranium targets with the Geant4 toolkit*

    Directory of Open Access Journals (Sweden)

    Greiner Walter

    2012-02-01

    Full Text Available We study primary and secondary reactions induced by 600 MeV proton beams in monolithic cylindrical targets made of natural tungsten and uranium by using Monte Carlo simulations with the Geant4 toolkit [1–3]. Bertini intranuclear cascade model, Binary cascade model and IntraNuclear Cascade Liège (INCL with ABLA model [4] were used as calculational options to describe nuclear reactions. Fission cross sections, neutron multiplicity and mass distributions of fragments for 238U fission induced by 25.6 and 62.9 MeV protons are calculated and compared to recent experimental data [5]. Time distributions of neutron leakage from the targets and heat depositions are calculated.

  8. A review of single-sample-based models and other approaches for radiocarbon dating of dissolved inorganic carbon in groundwater

    Science.gov (United States)

    Han, L. F; Plummer, Niel

    2016-01-01

    Numerous methods have been proposed to estimate the pre-nuclear-detonation 14C content of dissolved inorganic carbon (DIC) recharged to groundwater that has been corrected/adjusted for geochemical processes in the absence of radioactive decay (14C0) - a quantity that is essential for estimation of radiocarbon age of DIC in groundwater. The models/approaches most commonly used are grouped as follows: (1) single-sample-based models, (2) a statistical approach based on the observed (curved) relationship between 14C and δ13C data for the aquifer, and (3) the geochemical mass-balance approach that constructs adjustment models accounting for all the geochemical reactions known to occur along a groundwater flow path. This review discusses first the geochemical processes behind each of the single-sample-based models, followed by discussions of the statistical approach and the geochemical mass-balance approach. Finally, the applications, advantages and limitations of the three groups of models/approaches are discussed.The single-sample-based models constitute the prevailing use of 14C data in hydrogeology and hydrological studies. This is in part because the models are applied to an individual water sample to estimate the 14C age, therefore the measurement data are easily available. These models have been shown to provide realistic radiocarbon ages in many studies. However, they usually are limited to simple carbonate aquifers and selection of model may have significant effects on 14C0 often resulting in a wide range of estimates of 14C ages.Of the single-sample-based models, four are recommended for the estimation of 14C0 of DIC in groundwater: Pearson's model, (Ingerson and Pearson, 1964; Pearson and White, 1967), Han & Plummer's model (Han and Plummer, 2013), the IAEA model (Gonfiantini, 1972; Salem et al., 1980), and Oeschger's model (Geyh, 2000). These four models include all processes considered in single-sample-based models, and can be used in different ranges of

  9. A coupled reaction and transport model for assessing the injection, migration and fate of waste fluids

    International Nuclear Information System (INIS)

    Liu, X.; Ortoleva, P.

    1996-01-01

    The use of reaction-transport modeling for reservoir assessment and management in the context of deep well waste injection is evaluated. The study is based on CIRF.A (Chemical Interaction of Rock and Fluid), a fully coupled multiphase flow, contaminant transport, and fluid and mineral reaction model. Although SWIFT (Sandia Waste-Isolation Flow and Transport Model) is often the numerical model of choice, it can not account for chemical reactions involving rock, wastes, and formation fluids and their effects on contaminant transport, rock permeability and porosity, and the integrity of the reservoir and confining units. CIRF.A can simulate all these processes. Two field cases of waste injection were simulated by CIRF.A. Both observation data and simulation results show mineral precipitation in one case and rock dissolution in another case. Precipitation and dissolution change rock porosity and permeability, and hence the pattern of fluid migration. The model is shown to be invaluable in analyzing near borehole and reservoir-scale effects during waste injection and predicting the 10,000 year fate of the waste plume. The benefits of using underpressured compartments as waste repositories were also demonstrated by CIRF.A simulations

  10. Transport-reaction model for defect and carrier behavior within displacement cascades in gallium arsenide

    Energy Technology Data Exchange (ETDEWEB)

    Wampler, William R.; Myers, Samuel Maxwell,

    2014-02-01

    A model is presented for recombination of charge carriers at displacement damage in gallium arsenide, which includes clustering of the defects in atomic displacement cascades produced by neutron or ion irradiation. The carrier recombination model is based on an atomistic description of capture and emission of carriers by the defects with time evolution resulting from the migration and reaction of the defects. The physics and equations on which the model is based are presented, along with details of the numerical methods used for their solution. The model uses a continuum description of diffusion, field-drift and reaction of carriers and defects within a representative spherically symmetric cluster. The initial radial defect profiles within the cluster were chosen through pair-correlation-function analysis of the spatial distribution of defects obtained from the binary-collision code MARLOWE, using recoil energies for fission neutrons. Charging of the defects can produce high electric fields within the cluster which may influence transport and reaction of carriers and defects, and which may enhance carrier recombination through band-to-trap tunneling. Properties of the defects are discussed and values for their parameters are given, many of which were obtained from density functional theory. The model provides a basis for predicting the transient response of III-V heterojunction bipolar transistors to pulsed neutron irradiation.

  11. The BDS Triple Frequency Pseudo-range Correlated Stochastic Model of Single Station Modeling Method

    Directory of Open Access Journals (Sweden)

    HUANG Lingyong

    2017-05-01

    Full Text Available In order to provide a reliable pseudo-range stochastic model, a method is studied to estimate the BDS triple-frequency pseudo-range related stochastic model based on three BDS triple-frequency pseudo-range minus carrier (GIF combinations using the data of a single station. In this algorithm, the low order polynomial fitting method is used to fit the GIF combination in order to eliminate the error and other constants except non pseudo noise at first. And then, multiple linear regression analysis method is used to model the stochastic function of three linearly independent GIF combinations. Finally the related stochastic model of the original BDS triple-frequency pseudo-range observations is obtained by linear transformation. The BDS triple-frequency data verification results show that this algorithm can get a single station related stochastic model of BDS triple-frequency pseudo-range observation, and it is advantageous to provide accurate stochastic model for navigation and positioning and integrity monitoring.

  12. Probing the Energy Transfer Dynamics of Photosynthetic Reaction Center Complexes Through Hole-Burning and Single-Complex Spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Riley, Kerry Joseph [Iowa State Univ., Ames, IA (United States)

    2007-01-01

    Photosynthesis is the process by which light energy is used to drive reactions that generate sugars to supply energy for cellular processes. It is one of the most important fundamental biological reactions and occurs in both prokaryotic (e.g. bacteria) and eukaryotic (e.g. plants and algae) organisms. Photosynthesis is also remarkably intricate, requiring the coordination of many different steps and reactions in order to successfully transform absorbed solar energy into a biochemical usable form of energy. However, the net reaction for all photosynthetic organisms can be reduced to the following, deceptively general, equation developed by Van Niel[1] H2 - D + Aimplieshv A - H2 + D where H2-D is the electron donor, e.g. H2O, H2S. A is the electron acceptor, e.g. CO2, and A-H2 is the synthesized sugar. Amazingly, this simple net equation is responsible for creating the oxidizing atmosphere of Earth and the recycling of CO2, both of which are necessary for the sustainment of the global ecosystem.

  13. Lower limb muscle pre-motor time measures during a choice reaction task associate with knee abduction loads during dynamic single leg landings.

    Science.gov (United States)

    McLean, Scott G; Borotikar, Bhushan; Lucey, Sarah M

    2010-07-01

    Female neuromuscular control during dynamic landings is considered central to their increased ACL injury risk relative to males. There is limited insight, however, into the neuromuscular parameters governing this risk, which may hinder prevention success. This study targeted a new screenable and potentially trainable neuromuscular risk factor. Specifically, we examined whether lower limb muscle pre-motor times, being the time between stimulus presentation and initiation of the muscle EMG burst, elicited during a simple choice reaction task correlated with knee abduction loads during separate single leg landings. Twenty female NCAA athletes had muscle (n=8) pre-motor time and knee biomechanics data recorded bilaterally during a choice reaction task. Knee biomechanics were also quantified during anticipated and unanticipated single (dominant and non-dominant) leg landings. Mean peak knee abduction loads during landings were submitted to a two-way ANOVA to test for limb and decision effects. Individual regression coefficients were initially computed between-limb-based muscle pre-motor times and peak abduction moments elicited during both the choice reaction and landing tasks. Limb-based linear stepwise regression coefficients were also computed between muscle PMT's demonstrating significant (Pmuscle pre-motor times during a specific choice reaction task are associated with peak knee abduction loads during separate single leg landings. These muscles appear critical in stabilizing the knee against the extreme dynamic load states associated with such tasks. Targeted screening and training of supraspinal processes governing these muscle pre-motor times may ultimately enable external knee loads associated with landings to be more effectively countered by the overarching neuromuscular strategy. Copyright (c) 2010 Elsevier Ltd. All rights reserved.

  14. Simple and efficient site-directed mutagenesis using two single-primer reactions in parallel to generate mutants for protein structure-function studies

    Directory of Open Access Journals (Sweden)

    Edelheit Oded

    2009-06-01

    Full Text Available Abstract Background In protein engineering, site-directed mutagenesis methods are used to generate DNA sequences with mutated codons, insertions or deletions. In a widely used method, mutations are generated by PCR using a pair of oligonucleotide primers designed with mismatching nucleotides at the center of the primers. In this method, primer-primer annealing may prevent cloning of mutant cDNAs. To circumvent this problem we developed an alternative procedure that does not use forward-reverse primer pair in the same reaction. Results In initial studies we used a double-primer PCR mutagenesis protocol, but sequencing of products showed tandem repeats of primer in cloned DNA. We developed an alternative method that starts with two Single-Primer Reactions IN Parallel using high-fidelity Pwo DNA polymerase. Thus, we call the method with the acronym SPRINP. The SPRINP reactions are then combined, denatured at 95°C, and slowly cooled, promoting random annealing of the parental DNA and the newly synthesized strands. The products are digested with DpnI that digests methylated parental strands, and then transformed into E. coli. Using this method we generated >40 mutants in cDNAs coding for human Epithelial Na+ Channel (ENaC subunits. The method has been tested for 1–3 bp codon mutation and insertion of a 27 bp epitope tag into cDNAs. Conclusion The SPRINP mutagenesis protocol yields mutants reliably and with high fidelity. The use of a single primer in each amplification reaction increases the probability of success of primers relative to previous methods employing a forward and reverse primer pair in the same reaction.

  15. Simple and efficient site-directed mutagenesis using two single-primer reactions in parallel to generate mutants for protein structure-function studies.

    Science.gov (United States)

    Edelheit, Oded; Hanukoglu, Aaron; Hanukoglu, Israel

    2009-06-30

    In protein engineering, site-directed mutagenesis methods are used to generate DNA sequences with mutated codons, insertions or deletions. In a widely used method, mutations are generated by PCR using a pair of oligonucleotide primers designed with mismatching nucleotides at the center of the primers. In this method, primer-primer annealing may prevent cloning of mutant cDNAs. To circumvent this problem we developed an alternative procedure that does not use forward-reverse primer pair in the same reaction. In initial studies we used a double-primer PCR mutagenesis protocol, but sequencing of products showed tandem repeats of primer in cloned DNA. We developed an alternative method that starts with two Single-Primer Reactions IN Parallel using high-fidelity Pwo DNA polymerase. Thus, we call the method with the acronym SPRINP. The SPRINP reactions are then combined, denatured at 95 degrees C, and slowly cooled, promoting random annealing of the parental DNA and the newly synthesized strands. The products are digested with DpnI that digests methylated parental strands, and then transformed into E. coli. Using this method we generated >40 mutants in cDNAs coding for human Epithelial Na+ Channel (ENaC) subunits. The method has been tested for 1-3 bp codon mutation and insertion of a 27 bp epitope tag into cDNAs. The SPRINP mutagenesis protocol yields mutants reliably and with high fidelity. The use of a single primer in each amplification reaction increases the probability of success of primers relative to previous methods employing a forward and reverse primer pair in the same reaction.

  16. Position-specific isotope modeling of organic micropollutants transformation through different reaction pathways

    International Nuclear Information System (INIS)

    Jin, Biao; Rolle, Massimo

    2016-01-01

    The degradation of organic micropollutants occurs via different reaction pathways. Compound specific isotope analysis is a valuable tool to identify such degradation pathways in different environmental systems. We propose a mechanism-based modeling approach that provides a quantitative framework to simultaneously evaluate concentration as well as bulk and position-specific multi-element isotope evolution during the transformation of organic micropollutants. The model explicitly simulates position-specific isotopologues for those atoms that experience isotope effects and, thereby, provides a mechanistic description of isotope fractionation occurring at different molecular positions. To demonstrate specific features of the modeling approach, we simulated the degradation of three selected organic micropollutants: dichlorobenzamide (BAM), isoproturon (IPU) and diclofenac (DCF). The model accurately reproduces the multi-element isotope data observed in previous experimental studies. Furthermore, it precisely captures the dual element isotope trends characteristic of different reaction pathways as well as their range of variation consistent with observed bulk isotope fractionation. It was also possible to directly validate the model capability to predict the evolution of position-specific isotope ratios with available experimental data. Therefore, the approach is useful both for a mechanism-based evaluation of experimental results and as a tool to explore transformation pathways in scenarios for which position-specific isotope data are not yet available. - Highlights: • Mechanism-based, position-specific isotope modeling of micropollutants degradation. • Simultaneous description of concentration and primary and secondary isotope effects. • Key features of the model are demonstrated with three illustrative examples. • Model as a tool to explore reaction mechanisms and to design experiments. - We propose a modeling approach incorporating mechanistic information and

  17. Toward the modeling of combustion reactions through discrete element method (DEM) simulations

    Science.gov (United States)

    Reis, Martina Costa; Alobaid, Falah; Wang, Yongqi

    2018-03-01

    In this work, the process of combustion of coal particles under turbulent regime in a high-temperature reaction chamber is modeled through 3D discrete element method (DEM) simulations. By assuming the occurrence of interfacial transport phenomena between the gas and solid phases, one investigates the influence of the physicochemical properties of particles on the rates of heterogeneous chemical reactions, as well as the influence of eddies present in the gas phase on the mass transport of reactants toward the coal particles surface. Moreover, by considering a simplistic chemical mechanism for the combustion process, thermochemical and kinetic parameters obtained from the simulations are employed to discuss some phenomenological aspects of the combustion process. In particular, the observed changes in the mass and volume of coal particles during the gasification and combustion steps are discussed by emphasizing the changes in the chemical structure of the coal. In addition to illustrate how DEM simulations can be used in the modeling of consecutive and parallel chemical reactions, this work also shows how heterogeneous and homogeneous chemical reactions become a source of mass and energy for the gas phase.

  18. A Semi-Empirical Two Step Carbon Corrosion Reaction Model in PEM Fuel Cells

    Energy Technology Data Exchange (ETDEWEB)

    Young, Alan; Colbow, Vesna; Harvey, David; Rogers, Erin; Wessel, Silvia

    2013-01-01

    The cathode CL of a polymer electrolyte membrane fuel cell (PEMFC) was exposed to high potentials, 1.0 to 1.4 V versus a reversible hydrogen electrode (RHE), that are typically encountered during start up/shut down operation. While both platinum dissolution and carbon corrosion occurred, the carbon corrosion effects were isolated and modeled. The presented model separates the carbon corrosion process into two reaction steps; (1) oxidation of the carbon surface to carbon-oxygen groups, and (2) further corrosion of the oxidized surface to carbon dioxide/monoxide. To oxidize and corrode the cathode catalyst carbon support, the CL was subjected to an accelerated stress test cycled the potential from 0.6 VRHE to an upper potential limit (UPL) ranging from 0.9 to 1.4 VRHE at varying dwell times. The reaction rate constants and specific capacitances of carbon and platinum were fitted by evaluating the double layer capacitance (Cdl) trends. Carbon surface oxidation increased the Cdl due to increased specific capacitance for carbon surfaces with carbon-oxygen groups, while the second corrosion reaction decreased the Cdl due to loss of the overall carbon surface area. The first oxidation step differed between carbon types, while both reaction rate constants were found to have a dependency on UPL, temperature, and gas relative humidity.

  19. Resonances and fusion in heavy ion reactions: new models and developments

    International Nuclear Information System (INIS)

    Cindro, N.

    1982-01-01

    Several aspects of the problem of the resonant behaviour of heavy-ion induced reactions are discussed. First, the problem is set in its relation to fundamental nuclear physics and our understanding of nuclear structure. It is suggested that, if the resonant behaviour of heavy-ion reactions is indeed due to the presence of particular configurations in the composite systems, these configurations must have a very specific nature which prevents their mixing with the adjacent states or else other conditons (e.g. low level density) should be met. Further on, the problem of resonant behaviour observed in back-angle elastic scattering and in forward-angle reaction data is discussed. Collisions between heavy ions leading to the composite systems 36 Ar and 40 Ca are used to discuss the apparent lack of correlation between these two sets of data. A way to understand it, based on the fragmentation of broad resonances, is suggested. In the third part the relation between structure in the fusion cross section excitation functions and that in reaction channel cross sections is discussed. Finally, in the fourth part, the orbiting-cluster model of heavy-ion resonances is briefly described and its predictions discussed. Based on this model a list is given of colliding heavy-ion systems where resonances are expected. (author)

  20. Modeling the BZ reaction in gels with chemo-responsive crosslinks

    Science.gov (United States)

    Yashin, Victor V.; Kuksenok, Olga; Balazs, Anna C.

    2010-03-01

    We model chemo-responsive polymer gels, which expand and contract periodically in response to the ongoing oscillatory Belousov-Zhabotinsky (BZ) reaction. This behavior is due to a ruthenium catalyst, which is grafted to the polymers and affects the polymer-solvent interactions as it undergoes the redox oscillations in the course of the reaction. We consider a permanently crosslinked polymer gel that encompasses Ru(terpy)2 catalytic units having both the terpyridine ligands chemically bonded to the network. It is known that oxidation of the Ru metal-ion from Ru(II) to Ru(III) results in the dissociation of the Ru(terpy)2 complexes since the Ru(III) ions form only mono-complexes with terpyridine. Hence, the grafted Ru(terpy)2 units would effectively create crosslinks that break and re-form in the response to the BZ reaction. We modified the Oregonator model for the BZ reaction and took into account that the re-formation of Ru(terpy)2 complexes is frustrated by the gel network. The time-dependent elastic contribution of the Ru(terpy)2 crosslinks was described by the BKZ-type constitutive equation. We report on the results of simulations in 1D. We show, in particular, that compression of the sample leads to stiffening of the gel due to an increase in the crosslink density.

  1. Elementary reaction modeling of reversible CO/CO2 electrochemical conversion on patterned nickel electrodes

    Science.gov (United States)

    Luo, Yu; Shi, Yixiang; Li, Wenying; Cai, Ningsheng

    2018-03-01

    CO/CO2 are the major gas reactant/product in the fuel electrode of reversible solid oxide cells (RSOC). This study proposes a two-charge-transfer-step mechanism to describe the reaction and transfer processes of CO-CO2 electrochemical conversion on a patterned Ni electrode of RSOC. An elementary reaction model is developed to couple two charge transfer reactions, C(Ni)+O2-(YSZ) ↔ CO(Ni)+(YSZ) +2e- and CO(Ni)+O2-(YSZ) ↔ CO2(Ni)+(YSZ)+2e-, with adsorption/desorption, surface chemical reactions and surface diffusion. This model well validates in both solid oxide electrolysis cell (SOEC) and solid oxide fuel cell (SOFC) modes by the experimental data from a patterned Ni electrode with 10 μm stripe width at different pCO (0-0.25 atm), pCO2 (0-0.35 atm) and operating temperature (600-700 °C). This model indicates SOEC mode is dominated by charge transfer step C(Ni)+O2-(YSZ)↔CO(Ni)+(YSZ) +2e-, while SOFC mode by CO(Ni)+ O2-(YSZ)↔CO2(Ni)+(YSZ)+2e- on the patterned Ni electrode. The sensitivity analysis shows charge transfer step is the major rate-determining step for RSOC, besides, surface diffusion of CO and CO2 as well as CO2 adsorption also plays a significant role in the electrochemical reaction of SOEC while surface diffusion of CO and CO2 desorption could be co-limiting in SOFC.

  2. Comparative analysis on surface property in anodic oxidation polishing of reaction-sintered silicon carbide and single-crystal 4H silicon carbide

    Science.gov (United States)

    Shen, Xinmin; Tu, Qunzhang; Deng, Hui; Jiang, Guoliang; He, Xiaohui; Liu, Bin; Yamamura, Kazuya

    2016-04-01

    For effective machining of difficult-to-machine materials, such as reaction-sintered silicon carbide (RS-SiC) and single-crystal 4H silicon carbide (4H-SiC), a novel polishing technique named anodic oxidation polishing was proposed, which combined with the anodic oxidation of substrate and slurry polishing of oxide. By scanning electron microscopy/energy-dispersive X-ray spectroscopy (SEM-EDX) observation and atomic force microscopy analysis, both the anodic oxidation behaviors of RS-SiC and 4H-SiC were investigated. Through comparison of the surfaces before and after hydrofluoric acid etching of the oxidized samples by the scanning white light interferometry (SWLI) measurement, the relationships between oxidation depth and oxidation time were obtained, and the calculated oxidation rate for RS-SiC was 5.3 nm/s and that for 4H-SiC was 5.8 nm/s based on the linear Deal-Grove model. Through anodic oxidation polishing of RS-SiC substrate and 4H-SiC substrate, respectively, the surface roughness rms obtained by SWLI was improved to 2.103 nm for RS-SiC and to 0.892 nm for 4H-SiC. Experimental results indicate that anodic oxidation polishing is an effective method for the machining of RS-SiC and 4H-SiC samples, which would improve the process level of SiC substrates and promote the application of SiC products in the fields of optics, ceramics, semiconductors, electronics, and so on.

  3. Experimental tests of recent nuclear models with the (n,γ) reaction

    International Nuclear Information System (INIS)

    Casten, R.F.

    1978-01-01

    The nonselectivity of the (n,γ) reaction provides a powerful tool for the study of those nuclear models of broad applicability whose characteristic excitations span a wide range of degrees of freedom. Several recent examples of this are discussed with particular emphasis on the recent discovery of the 0(6) limit of the interacting boson model and of a new interpretation of the Pt--0s transition region which consequently emerges. Other topics considered include recent extensions of the Nilsson model to new regions of nucleus, excitation energy and complexity of states. 43 references

  4. Mathematical Modeling and Dynamic Simulation of Metabolic Reaction Systems Using Metabolome Time Series Data.

    Science.gov (United States)

    Sriyudthsak, Kansuporn; Shiraishi, Fumihide; Hirai, Masami Yokota

    2016-01-01

    The high-throughput acquisition of metabolome data is greatly anticipated for the complete understanding of cellular metabolism in living organisms. A variety of analytical technologies have been developed to acquire large-scale metabolic profiles under different biological or environmental conditions. Time series data are useful for predicting the most likely metabolic pathways because they provide important information regarding the accumulation of metabolites, which implies causal relationships in the metabolic reaction network. Considerable effort has been undertaken to utilize these data for constructing a mathematical model merging system properties and quantitatively characterizing a whole metabolic system in toto. However, there are technical difficulties between benchmarking the provision and utilization of data. Although, hundreds of metabolites can be measured, which provide information on the metabolic reaction system, simultaneous measurement of thousands of metabolites is still challenging. In addition, it is nontrivial to logically predict the dynamic behaviors of unmeasurable metabolite concentrations without sufficient information on the metabolic reaction network. Yet, consolidating the advantages of advancements in both metabolomics and mathematical modeling remain to be accomplished. This review outlines the conceptual basis of and recent advances in technologies in both the research fields. It also highlights the potential for constructing a large-scale mathematical model by estimating model parameters from time series metabolome data in order to comprehensively understand metabolism at the systems level.

  5. The effect of learning models and emotional intelligence toward students learning outcomes on reaction rate

    Science.gov (United States)

    Sutiani, Ani; Silitonga, Mei Y.

    2017-08-01

    This research focused on the effect of learning models and emotional intelligence in students' chemistry learning outcomes on reaction rate teaching topic. In order to achieve the objectives of the research, with 2x2 factorial research design was used. There were two factors tested, namely: the learning models (factor A), and emotional intelligence (factor B) factors. Then, two learning models were used; problem-based learning/PBL (A1), and project-based learning/PjBL (A2). While, the emotional intelligence was divided into higher and lower types. The number of population was six classes containing 243 grade X students of SMAN 10 Medan, Indonesia. There were 15 students of each class were chosen as the sample of the research by applying purposive sampling technique. The data were analyzed by applying two-ways analysis of variance (2X2) at the level of significant α = 0.05. Based on hypothesis testing, there was the interaction between learning models and emotional intelligence in students' chemistry learning outcomes. Then, the finding of the research showed that students' learning outcomes in reaction rate taught by using PBL with higher emotional intelligence is higher than those who were taught by using PjBL. There was no significant effect between students with lower emotional intelligence taught by using both PBL and PjBL in reaction rate topic. Based on the finding, the students with lower emotional intelligence were quite hard to get in touch with other students in group discussion.

  6. Single-Tube Reaction Using Perfluorocarbons: A Prerequisite Step Leading to the Whole-Slide In Situ Technique on Histopathological Slides.

    Directory of Open Access Journals (Sweden)

    Yi-Chang Chen

    Full Text Available Developing a robust, novel method for performing multiple reactions in a single tube is not only time- and cost-saving but also critical for future high-throughput whole-slide in situ techniques on diseased tissues. In this study, we introduce the use of perfluorocarbons and compound-coated magnetic particles to create pseudochambers in a single tube, allowing different reactions to be performed in different phases. Perfluorocarbons also serve as cell lysis buffer and polymerase chain reaction (PCR buffer owing to their highly penetrating, repellent and emulsifiable properties. Using this method, nucleic acids can be isolated and purified from various sample types and sizes, followed by PCR, real-time PCR, or multiplex PCR in the same tube. No incubation or enzyme digesting time is needed and the risk of cross-contamination is reduced. Tests can be performed in microemulsions (water-in-oil droplets containing sequence-specific captures and probes for further high-throughput detection. We present a simple, quick, and robust procedure as a prerequisite step to future high-throughput in situ techniques.

  7. Preparation of single-crystal spherical γ-Mo2N by temperature-programmed reaction between β-MoO3 and NH3

    Science.gov (United States)

    Wang, Lu; Zhang, Guo-Hua; Chou, Kuo-Chih

    2017-10-01

    In the present wok, single-crystalline spherical γ-Mo2N powders was successfully prepared by the temperature-programmed reaction of single-crystal spherical β-MoO3 with NH3 in the temperature ranges of 1013-1073 K. Herein, the Mo source used was monoclinic system, β-MoO3, a metastable phase of MoO3. It is found that the characterizations of the as-prepared γ-Mo2N powders are strongly depended on the selection of the MoO3 precursor. In other words, the as-prepared γ-Mo2N powders inherited the shape, size and structure of the used β-MoO3 precursors upon reaction with NH3. In order to make a comparison, β-MoO3 was also reduced by the mixed gases of N2 and H2 with the flow rate ratio of 1:3 at the identical conditions. It was found that pure β-Mo2N polycrystalline can be obtained when the temperature was 1013 K; while further increasing the reaction temperature, metal Mo powder will be turned up.

  8. Single item inventory models : A time- and event- averages approach

    NARCIS (Netherlands)

    E.M. Bazsa-Oldenkamp; P. den Iseger

    2003-01-01

    textabstractThis paper extends a fundamental result about single-item inventory systems. This approach allows more general performance measures, demand processes and order policies, and leads to easier analysis and implementation, than prior research. We obtain closed form expressions for the

  9. Scaling analysis in modeling transport and reaction processes a systematic approach to model building and the art of approximation

    CERN Document Server

    Krantz, William B

    2007-01-01

    This book is unique as the first effort to expound on the subject of systematic scaling analysis. Not written for a specific discipline, the book targets any reader interested in transport phenomena and reaction processes. The book is logically divided into chapters on the use of systematic scaling analysis in fluid dynamics, heat transfer, mass transfer, and reaction processes. An integrating chapter is included that considers more complex problems involving combined transport phenomena. Each chapter includes several problems that are explained in considerable detail. These are followed by several worked examples for which the general outline for the scaling is given. Each chapter also includes many practice problems. This book is based on recognizing the value of systematic scaling analysis as a pedagogical method for teaching transport and reaction processes and as a research tool for developing and solving models and in designing experiments. Thus, the book can serve as both a textbook and a reference boo...

  10. Effect of Dangguibohyul-Tang, a Mixed Extract of Astragalus membranaceus and Angelica sinensis, on Allergic and Inflammatory Skin Reaction Compared with Single Extracts of Astragalus membranaceus or Angelica sinensis

    Directory of Open Access Journals (Sweden)

    You Yeon Choi

    2016-01-01

    Full Text Available Dangguibohyul-tang (DBT, herbal formula composed of Astragalus membranaceus (AM and Angelica sinensis (AS at a ratio of 5 : 1, has been used for the treatment of various skin diseases in traditional medicine. We investigated the effect of DBT on allergic and inflammatory skin reaction in atopic dermatitis-like model compared to the single extract of AM or AS. DBT treatment showed the remission of clinical symptoms, including decreased skin thickness and scratching behavior, the total serum IgE level, and the number of mast cells compared to DNCB group as well as the single extract of AM- or AS-treated group. Levels of cytokines (IL-4, IL-6, IFN-γ, TNF-α, and IL-1β and inflammatory mediators (NF-κB, phospho-IκBα, and phospho-MAPKs were significantly decreased in AM, AS, and DBT groups. These results demonstrated that AM, AS, and DBT may have the therapeutic property on atopic dermatitis by inhibition of allergic and inflammatory mediators and DBT formula; a mixed extract of AM and AS based on the herb pairs theory especially might be more effective on antiallergic reaction as compared with the single extract of AM or AS.

  11. Mass transfer model for two-layer TBP oxidation reactions: Revision 1

    International Nuclear Information System (INIS)

    Laurinat, J.E.

    1994-01-01

    To prove that two-layer, TBP-nitric acid mixtures can be safely stored in the Canyon evaporators, it must be demonstrated that a runaway reaction between TBP and nitric acid will not occur. Previous bench-scale experiments showed that, at typical evaporator temperatures, this reaction is endothermic and therefore cannot run away, due to the loss of heat from evaporation of water in the organic layer. However, the reaction would be exothermic and could run away if the small amount of water in the organic layer evaporates before the nitric acid in this layer is consumed by the reaction. Provided that there is enough water in the aqueous layer, this would occur if the organic layer is sufficiently thick so that the rate of loss of water by evaporation exceeds the rate of replenishment due to mixing with the aqueous layer. Bubbles containing reaction products enhance the rate of transfer of water from the aqueous layer to the organic layer. These bubbles are generated by the oxidation of TBP and its reaction products in the organic layer and by the oxidation of butanol in the aqueous layer. Butanol is formed by the hydrolysis of TBP in the organic layer. For aqueous-layer bubbling to occur, butanol must transfer into the aqueous layer. Consequently, the rate of oxidation and bubble generation in the aqueous layer strongly depends on the rate of transfer of butanol from the organic to the aqueous layer. This report presents measurements of mass transfer rates for the mixing of water and butanol in two-layer, TBP-aqueous mixtures, where the top layer is primarily TBP and the bottom layer is comprised of water or aqueous salt solution. Mass transfer coefficients are derived for use in the modeling of two-layer TBP-nitric acid oxidation experiments

  12. The improvement of the heat transfer model for sodium-water reaction jet code

    International Nuclear Information System (INIS)

    Hashiguchi, Yoshirou; Yamamoto, Hajime; Kamoshida, Norio; Murata, Shuuichi

    2001-02-01

    For confirming the reasonable DBL (Design Base Leak) on steam generator (SG), it is necessary to evaluate phenomena of sodium-water reaction (SWR) in an actual steam generator realistically. The improvement of a heat transfer model on sodium-water reaction (SWR) jet code (LEAP-JET ver.1.40) and application analysis to the water injection tests for confirmation of propriety for the code were performed. On the improvement of the code, the heat transfer model between a inside fluid and a tube wall was introduced instead of the prior model which was heat capacity model including both heat capacity of the tube wall and inside fluid. And it was considered that the fluid of inside the heat exchange tube was able to treat as water or sodium and typical heat transfer equations used in SG design were also introduced in the new heat transfer model. Further additional work was carried out in order to improve the stability of the calculation for long calculation time. The test calculation using the improved code (LEAP-JET ver.1.50) were carried out with conditions of the SWAT-IR·Run-HT-2 test. It was confirmed that the SWR jet behavior on the result and the influence to the result of the heat transfer model were reasonable. And also on the improved code (LEAP-JET ver.1.50), user's manual was revised with additional I/O manual and explanation of the heat transfer model and new variable name. (author)

  13. Study of nickel nuclei by (p,d) and (p,t) reactions. Shell model interpretation

    International Nuclear Information System (INIS)

    Kong-A-Siou, D.-H.

    1975-01-01

    The experimental techniques employed at the Nuclear Science Institute (Grenoble) and at Michigan State University are described. The development of the transition amplitude calculation of the one-or two-nucleon transfer reactions is described first, after which the principle of shell model calculations is outlined. The choices of configuration space and two-body interactions are discussed. The DWBA method of analysis is studied in more detail. The effects of different approximations and the influence of the parameters are examined. Special attention is paid to the j-dependence of the form of the angular distributions, on effect not explained in the standard DWBA framework. The results are analysed and a large section is devoted to a comparative study of the experimental results obtained and those from other nuclear reactions. The spectroscopic data obtained are compared with the results of shell model calculations [fr

  14. Two-phase model of hydrogen transport to optimize nanoparticle catalyst loading for hydrogen evolution reaction

    DEFF Research Database (Denmark)

    Kemppainen, Erno; Halme, Janne; Hansen, Ole

    2016-01-01

    With electrocatalysts it is important to be able to distinguish between the effects of mass transport and reaction kinetics on the performance of the catalyst. When the hydrogen evolution reaction (HER) is considered, an additional and often neglected detail of mass transport in liquid...... is the evolution and transport of gaseous H2, since HER leads to the continuous formation of H2 bubbles near the electrode. We present a numerical model that includes the transport of both gaseous and dissolved H2, as well as mass exchange between them, and combine it with a kinetic model of HER at platinum (Pt......) nanoparticle electrodes. We study the effect of the diffusion layer thickness and H2 dissolution rate constant on the importance of gaseous transport, and the effect of equilibrium hydrogen coverage and Pt loading on the kinetic and mass transport overpotentials. Gaseous transport becomes significant when...

  15. Modeling of a Reaction-Distillation-Recycle System to Produce Dimethyl Ether through Methanol Dehydration

    Science.gov (United States)

    Muharam, Y.; Zulkarnain, L. M.; Wirya, A. S.

    2018-03-01

    The increase in the dimethyl ether yield through methanol dehydration due to a recycle integration to a reaction-distillation system was studied in this research. A one-dimensional phenomenological model of a methanol dehydration reactor and a shortcut model of distillation columns were used to achieve the aim. Simulation results show that 10.7 moles/s of dimethyl ether is produced in a reaction-distillation system with the reactor length being 4 m, the reactor inlet pressure being 18 atm, the reactor inlet temperature being 533 K, the reactor inlet velocity being 0.408 m/s, and the distillation pressure being 8 atm. The methanol conversion is 90% and the dimethyl ether yield is 48%. The integration of the recycle stream to the system increases the dimethyl ether yield by 8%.

  16. Modified Step Variational Iteration Method for Solving Fractional Biochemical Reaction Model

    Directory of Open Access Journals (Sweden)

    R. Yulita Molliq

    2011-01-01

    Full Text Available A new method called the modification of step variational iteration method (MoSVIM is introduced and used to solve the fractional biochemical reaction model. The MoSVIM uses general Lagrange multipliers for construction of the correction functional for the problems, and it runs by step approach, which is to divide the interval into subintervals with time step, and the solutions are obtained at each subinterval as well adopting a nonzero auxiliary parameter ℏ to control the convergence region of series' solutions. The MoSVIM yields an analytical solution of a rapidly convergent infinite power series with easily computable terms and produces a good approximate solution on enlarged intervals for solving the fractional biochemical reaction model. The accuracy of the results obtained is in a excellent agreement with the Adam Bashforth Moulton method (ABMM.

  17. Digital Microfluidics Assisted Sealing of Individual Magnetic Particles in Femtoliter-Sized Reaction Wells for Single-Molecule Detection.

    Science.gov (United States)

    Decrop, Deborah; Ruiz, Elena Pérez; Kumar, Phalguni Tewari; Tripodi, Lisa; Kokalj, Tadej; Lammertyn, Jeroen

    2017-01-01

    Digital microfluidics has emerged in the last years as a promising liquid handling technology for a variety of applications. Here, we describe in detail how to build up an electrowetting-on-dielectric-based digital microfluidic chip with unique advantages for performing single-molecule detection. We illustrate how superparamagnetic particles can be printed with very high loading efficiency (over 98 %) and single-particle resolution in the microwell array patterned in the Teflon-AF ® surface of the grounding plate of the chip. Finally, the potential of the device for its application to single-molecule detection is demonstrated by the ultrasensitive detection of the biotinylated enzyme β-Galactosidase captured on streptavidin-coated particles in the described platform.

  18. Catalytic Hydrotreatment of Fast Pyrolysis Oil: Model Studies on Reaction Pathways for the Carbohydrate Fraction

    OpenAIRE

    Wildschut, J.; Arentz, J.; Rasrendra, C. B.; Venderbosch, R. H.; Heeres, H. J.

    2009-01-01

    Fast pyrolysis oil can be upgraded by a catalytic hydrotreatment (250-400 degrees C, 100-200 bar) using heterogeneous catalysts such as Ru/C to hydrocarbon-like products that can serve as liquid transportation fuels. Insight into the complex reaction pathways of the various component fractions during hydrotreatment is desirable to reduce the formation of by-products such as char and gaseous components. This paper deals with the catalytic hydrotreatment of representative model components for t...

  19. A coupled mechanical and chemical damage model for concrete affected by alkali–silica reaction

    Energy Technology Data Exchange (ETDEWEB)

    Pignatelli, Rossella, E-mail: rossellapignatelli@gmail.com [Department of Civil and Environmental Engineering, Politecnico di Milano, Piazza L. da Vinci 32, 20133 Milano (Italy); Lombardi Ingegneria S.r.l., Via Giotto 36, 20145 Milano (Italy); Comi, Claudia, E-mail: comi@stru.polimi.it [Department of Civil and Environmental Engineering, Politecnico di Milano, Piazza L. da Vinci 32, 20133 Milano (Italy); Monteiro, Paulo J.M., E-mail: monteiro@ce.berkeley.edu [Department of Civil and Environmental Engineering, University of California, Berkeley, CA 94720 (United States)

    2013-11-15

    To model the complex degradation phenomena occurring in concrete affected by alkali–silica reaction (ASR), we formulate a poro-mechanical model with two isotropic internal variables: the chemical and the mechanical damage. The chemical damage, related to the evolution of the reaction, is caused by the pressure generated by the expanding ASR gel on the solid concrete skeleton. The mechanical damage describes the strength and stiffness degradation induced by the external loads. As suggested by experimental results, degradation due to ASR is considered to be localized around reactive sites. The effect of the degree of saturation and of the temperature on the reaction development is also modeled. The chemical damage evolution is calibrated using the value of the gel pressure estimated by applying the electrical diffuse double-layer theory to experimental values of the surface charge density in ASR gel specimens reported in the literature. The chemo-damage model is first validated by simulating expansion tests on reactive specimens and beams; the coupled chemo-mechanical damage model is then employed to simulate compression and flexure tests results also taken from the literature. -- Highlights: •Concrete degradation due to ASR in variable environmental conditions is modeled. •Two isotropic internal variables – chemical and mechanical damage – are introduced. •The value of the swelling pressure is estimated by the diffuse double layer theory. •A simplified scheme is proposed to relate macro- and microscopic properties. •The chemo-mechanical damage model is validated by simulating tests in literature.

  20. Joint ICTP-IAEA advanced workshop on model codes for spallation reactions

    International Nuclear Information System (INIS)

    Filges, D.; Leray, S.; Yariv, Y.; Mengoni, A.; Stanculescu, A.; Mank, G.

    2008-08-01

    The International Atomic Energy Agency (IAEA) and the Abdus Salam International Centre for Theoretical Physics (ICTP) organised an expert meeting at the ICTP from 4 to 8 February 2008 to discuss model codes for spallation reactions. These nuclear reactions play an important role in a wide domain of applications ranging from neutron sources for condensed matter and material studies, transmutation of nuclear waste and rare isotope production to astrophysics, simulation of detector set-ups in nuclear and particle physics experiments, and radiation protection near accelerators or in space. The simulation tools developed for these domains use nuclear model codes to compute the production yields and characteristics of all the particles and nuclei generated in these reactions. These codes are generally Monte-Carlo implementations of Intra-Nuclear Cascade (INC) or Quantum Molecular Dynamics (QMD) models, followed by de-excitation (principally evaporation/fission) models. Experts have discussed in depth the physics contained within the different models in order to understand their strengths and weaknesses. Such codes need to be validated against experimental data in order to determine their accuracy and reliability with respect to all forms of application. Agreement was reached during the course of the workshop to organise an international benchmark of the different models developed by different groups around the world. The specifications of the benchmark, including the set of selected experimental data to be compared to the models, were also defined during the workshop. The benchmark will be organised under the auspices of the IAEA in 2008, and the first results will be discussed at the next Accelerator Applications Conference (AccApp'09) to be held in Vienna in May 2009. (author)