Hydrogen Spillover Enhanced Hydroxyl Formation and Catalytic Activity Toward CO Oxidation at the Metal/Oxide Interface

H₂‐promoted catalytic activity of oxide‐supported metal catalysts in low‐temperature CO oxidation is of great interest but its origin remains unknown. Employing an FeO(111)/Pt(111) inverse model catalyst, we herewith report direct experimental evidence for the spillover of H(a) adatoms on the Pt surface formed by H₂ dissociation to the Pt?FeO interface to form hydroxyl groups that facilely oxidize CO(a) on the neighboring Pt surface to produce CO₂. Hydroxyl groups and coadsorbed water play a crucial role in the occurrence of hydrogen spillover. These results unambiguously identify the occurrence of hydrogen spillover from the metal surface to the noble metal/metal oxide interface and the resultant enhanced catalytic activity of the metal/oxide interface in low‐temperature CO oxidation, which provides a molecular‐level understanding of both H₂‐promoted catalytic activity of metal/oxide ensembles in low‐temperature CO oxidation and hydrogen spillover.     

Two-fluid modeling of Geldart A particles in gas–solid micro-fluidized beds

The fluidization behavior of Geldart A particles in a gas–solid micro-fluidized bed was investigated by Eulerian–Eulerian numerical simulation. The commonly used Gidaspow drag model was tested first. The simulation showed that the predicted minimum bubbling velocities were significantly lower than the experimental data even when an extremely fine grid size (of approximately one particle diameter) was used. The modified Gibilaro drag model was therefore tested next. The predicted minimum bubbling velocity and bed voidage were in reasonable agreement with the experimental data available in literature. The experimentally observed regime transition phenomena from bubbling to slugging were also reproduced successfully in the simulations. Parametric studies indicated that the solid-wall boundary conditions had a significant impact on the predicted gas and solid flow behavior.     

Radial basis function (RBF)‐based parametric models for closed and open curves within the method of regularized stokeslets

The method of regularized Stokeslets (MRS) is a numerical approach using regularized fundamental solutions to compute the flow due to an object in a viscous fluid where inertial effects can be neglected. The elastic object is represented as a Lagrangian structure, exerting point forces on the fluid. The forces on the structure are often determined by a bending or tension model, previously calculated using finite difference approximations. In this paper, we study spherical basis function (SBF), radial basis function (RBF), and Lagrange–Chebyshev parametric models to represent and calculate forces on elastic structures that can be represented by an open curve, motivated by the study of cilia and flagella. The evaluation error for static open curves for the different interpolants, as well as errors for calculating normals and second derivatives using different types of clustered parametric nodes, is given for the case of an open planar curve. We determine that SBF and RBF interpolants built on clustered nodes are competitive with Lagrange–Chebyshev interpolants for modeling twice‐differentiable open planar curves. We propose using SBF and RBF parametric models within the MRS for evaluating and updating the elastic structure. Results for open and closed elastic structures immersed in a 2D fluid are presented, showing the efficacy of the RBF–Stokeslets method. Copyright © 2015 John Wiley & Sons, Ltd.     

Three‐dimensional structure of cyclic antibiotic teicoplanin aglycone using NMR distance and dihedral angle restraints in a DMSO solvation model

The three‐dimensional solution conformation of teicoplanin aglycone was determined using NMR spectroscopy. A combination of NOE and dihedral angle restraints in a DMSO solvation model was used to calculate an ensemble of structures having a root mean square deviation of 0.17 Å. The structures were generated using systematic searches of conformational space for optimal satisfaction of distance and dihedral angle restraints. Comparison of the NMR‐derived structure of teicoplanin aglycone with the X‐ray structure of a teicoplanin aglycone analog revealed a common backbone conformation with deviation of two aromatic side chain substituents. Experimentally determined backbone ¹³C chemical shifts showed good agreement with those computed at the density functional level of theory, providing a cross validation of the backbone conformation. The flexible portion of the molecule was consistent with the region that changes conformation to accommodate protein binding. The results showed that a hydrogen‐bonded DMSO molecule in combination with NMR‐derived restraints together enabled calculation of structures that satisfied experimental data. Copyright © 2015 John Wiley & Sons, Ltd.     

Mechanism of [3+2] Cycloaddition of Alkynes to the [Mo3S4(acac)3(py)3][PF6] Cluster

A study, involving kinetic measurements on the stopped‐flow and conventional UV/Vis timescales, ESI‐MS, NMR spectroscopy and DFT calculations, has been carried out to understand the mechanism of the reaction of [Mo₃S₄(acac)₃(py)₃][PF₆] ([ 1 ]PF₆; acac=acetylacetonate, py=pyridine) with two RC?CR alkynes (R=CH₂OH (btd), COOH (adc)) in CH₃CN. Both reactions show polyphasic kinetics, but experimental and computational data indicate that alkyne activation occurs in a single kinetic step through a concerted mechanism similar to that of organic [3+2] cycloaddition reactions, in this case through the interaction with one Mo(μ‐S)₂ moiety of [ 1 ]⁺. The rate of this step is three orders of magnitude faster for adc than that for btd, and the products initially formed evolve in subsequent steps into compounds that result from substitution of py ligands or from reorganization to give species with different structures. Activation strain analysis of the [3+2] cycloaddition step reveals that the deformation of the two reactants has a small contribution to the difference in the computed activation barriers, which is mainly associated with the change in the extent of their interaction at the transition‐state structures. Subsequent frontier molecular orbital analysis shows that the carboxylic acid substituents on adc stabilize its HOMO and LUMO orbitals with respect to those on btd due to better electron‐withdrawing properties. As a result, the frontier molecular orbitals of the cluster and alkyne become closer in energy; this allows a stronger interaction.     

On the nature of phase separation of polymer solutions at high extension rates

Experiments with stretching moderately concentrated polymer solutions have been carried out. Model experiments were carried out for poly(acrylonitrile) solutions in dimethyl siloxane. Just the choice of concentrated solutions allowed for a clear demonstration of a demixing effect with the formation of two separate phases—an oriented polymer fiber and solvent drops sitting on its surface. An original experimental device for following all subsequent stages in the demixing process was built. It combined two light beams, one transverse to the fiber and a second directed along (inside) the fiber, the latter played the role of an optical line. This gives a unique opportunity to observe processes occurring inside a fiber. The process of demixing starts from the volume phase separation across the whole cross section of a fiber at some critical deformation and the propagation of the front of demixing along the fiber. Then a solvent cylindrical skin appears which transforms into a system of separate droplets. New experimental data are discussed based on a comparison of the current different points of view on the phenomenon of deformation‐induced phase separation: thermodynamic shift of the equilibrium phase transition temperature, growth of stress‐induced concentration fluctuations in two‐component fluids, and mechanically pressing a solvent out from a polymer network. The general belief is that a rather specific (so‐called “beads‐on‐a‐string”) structure of a filament is realized in stretching dilute solutions: beads of a polymer solution connected by oriented polymer bridges forming a single object. The situation in stretching moderately concentrated solutions appears quite different: real phase separation was observed. So, the alternative phenomenon to the formation of the “beads‐on‐a‐string” structure has been experimentally proven. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2015 , 53, 559–565     

Sobolev Stability of Plane Wave Solutions to the Nonlinear Schrödinger Equation

This article explores the questions of long time orbital stability in high order Sobolev norms of plane wave solutions to the NLSE in the defocusing case.     

Optimal strategy of vaccination and treatment in an SIRS model with Markovian switching

Medical treatment and vaccination decisions are often sequential and uncertain. Markov decision process is an appropriate means to model and handle such stochastic dynamic decisions. This paper studies the near‐optimality of a stochastic SIRS epidemic model that incorporates vaccination and saturated treatment with regime switching. The stochastic model takes white noises and color noise into account. We first prove some priori estimates of the susceptible, infected, and recovered populations. Moreover, we establish some sufficient and necessary conditions of the near‐optimality by Pontryagin stochastic maximum principle. Our results show that the two kinds of environmental noises have great impacts on the infectious diseases. Finally, we illustrate our conclusions through numerical simulations.     

On generalized Nash equilibrium problems with linear coupling constraints and mixed-integer variables

ABSTRACT

We define and discuss different enumerative methods to compute solutions of generalized Nash equilibrium problems with linear coupling constraints and mixed-integer variables. We propose both branch-and-bound methods based on merit functions for the mixed-integer game, and branch-and-prune methods that exploit the concept of dominance to make effective cuts. We show that under mild assumptions the equilibrium set of the game is finite and we define an enumerative method to compute the whole of it. We show that our branch-and-prune method can be suitably modified in order to make a general equilibrium selection over the solution set of the mixed-integer game. We define an application in economics that can be modelled as a Nash game with linear coupling constraints and mixed-integer variables, and we adapt the branch-and-prune method to efficiently solve it.     

Neural network modeling of hydrological systems: A review of implementation techniques

This paper presents a review of procedural steps and implementation techniques used in the development of artificial intelligence models, generally referred to as artificial neural networks (ANNs), within the water resources domain. It focusses on identifying different areas wherein ANNs have found application thereby elucidating its advantages and disadvantages as well as various challenges encountered in its use. Results from this review provide useful insights into how the performance of ANNs can be improved and potential areas of application that are yet to be explored in hydrological modeling. Recommendations for Resource Managers

• Development of integrated and hybrid artificial intelligent tools is critical to achieving improved forecasts in hydrological modeling studies.

• Further research into comprehending the internal mechanisms of neural networks is required to obtain a practical meaning of each network component deployed to solve real‐world problems.

• More robust optimization techniques and tools like differential evolution, particle swarm optimization and deep neural nets, are yet to be fully explored in the water resources analysis, and should be given more attention to enhance neural networks aptitude for modeling complex and nonlinear hydrological processes.