High order accurate,one-sided finite-difference approximations to concentration gradients at the boundaries,for the simulation of electrochemical reaction-diffusion problems in one-dimensional space geometry

Accurate calculation of concentration gradients at the boundaries is crucial in electrochemical kinetic simulations, owing to the frequent occurrence of gradient-dependent boundary conditions, and the importance of the gradient-dependent electric current. By using the information about higher spatial derivatives of the concentrations, contained in the time-dependent, kinetic reaction-diffusion partial differential equation(s) in one-dimensional space geometry, under appropriate assumptions it is possible to increase the accuracy orders of the conventional, one-sided n-point finite-difference formulae for the concentration gradients at the boundaries, without increasing n. In this way a new class of high order accurate gradient approximations is derived, and tested in simulations of potential-step chronoamperometric and current-step chronopotentiometric transients for the Reinert-Berg system. The new formulae possess advantages over the conventional gradient approximations. For example, they allow one to obtain a third order accuracy by using two space points only, or fourth order accuracy by using three points, and yet they yield smaller errors than the conventional four-point, or five-point formulae, respectively. Needing fewer points, for approximating the gradients with a given accuracy, simplifies also the solution of the linear algebraic equations arising from the application of implicit time integration schemes.     

Quantum-chemical estimates of geometric parameters of free radicals

Experimental geometries of the HCO^· and H₂CO^·+ -electron radicals were compared with those obtained from calculations with the total energy optimization carried out in the framework of widely used ab initio and semiempirical computational procedures. For each structural form of the radicals, the magnetic resonance parameters calculated in the MNDO approximation were correlated with experimental values determined by ESR spectroscopy. Comparative analysis of the results obtained indicates the possibility of systematic correction of the optimized geometric parameters of free radicals using the results of ESR measurements. A simple computational procedure for automatic geometry correction in the MNDO approximation is developed and evaluated.     

Behavioral and computational aspects of language and its acquisition

One of the greatest challenges facing the cognitive sciences is to explain what it means to know a language, and how the knowledge of language is acquired. The dominant approach to this challenge within linguistics has been to seek an efficient characterization of the wealth of documented structural properties of language in terms of a compact generative grammar—ideally, the minimal necessary set of innate, universal, exception-less, highly abstract rules that jointly generate all and only the observed phenomena and are common to all human languages. We review developmental, behavioral, and computational evidence that seems to favor an alternative view of language, according to which linguistic structures are generated by a large, open set of constructions of varying degrees of abstraction and complexity, which embody both form and meaning and are acquired through socially situated experience in a given language community, by probabilistic learning algorithms that resemble those at work in other cognitive modalities.     

Prediction of Γ-L and L-X crossovers in Ga<Subscript>x</Subscript>Al<Subscript>1-x</Subscript>Sb alloys by empirical pseudopotential method

Using empirical pseudopotential method Γ-L crossover is found for the Ga_0.74Al_0.26Sb. The conduction band minimum is observed to switch at the (0.87, 0, 0) point for Ga_0.51Al_0.49Sb which shifts to the X point for Ga_0.21Al_0.79Sb and remains at X leading finally to indirect band gap in AlSb. Band structure calculations for a large number of alloys are performed and bowing parameters b_X and b_L are proposed for the E_X and E_L respectively. Our findings may serve as directive to select the materials in a range of composition to examine the bowing parameters and thereby effective mass experimentally for the Ga_xAl_1-xSb alloys.     

Quasi-equilibrium lattice Boltzmann method

A general lattice Boltzmann method for simulation of fluids with tailored transport coefficients is presented. It is based on the recently introduced quasi-equilibrium kinetic models, and a general lattice Boltzmann implementation is developed. Lattice Boltzmann models for isothermal binary mixtures with a given Schmidt number, and for a weakly compressible flow with a given Prandtl number are derived and validated.     

Local time-stepping procedures for the space-time conservation element and solution element method

A local time-stepping procedure for the space-time conservation element and solution element (CESE) method has been developed. This new procedure allows for variation of time-step size in both space and time, and can also be extended to become multi-dimensional solvers with structured/unstructured spatial grids. Moreover, it differs substantially in concept and methodology from the existing approaches. By taking full advantage of key concepts of the CESE method, in a simple and efficient manner it can enforce flux conservation across an interface separating grid zones of different time-step sizes. In particular, no correction pass is needed. Numerical experiments show that, for a variety of flow problems involving moving shock and flame discontinuities, accurate and robust numerical simulations can be achieved even with a reduction in time-step size on the order of 10 or higher for grids across a single interface.     

Resolution of computational aeroacoustics problems on unstructured grids with a higher-order finite volume scheme

Computational fluid dynamics (CFD) has become increasingly used in the industry for the simulation of flows. Nevertheless, the complex configurations of real engineering problems make the application of very accurate methods that only work on structured grids difficult. From this point of view, the development of higher-order methods for unstructured grids is desirable. The finite volume method can be used with unstructured grids, but unfortunately it is difficult to achieve an order of accuracy higher than two, and the common approach is a simple extension of the one-dimensional case. The increase of the order of accuracy in finite volume methods on general unstructured grids has been limited due to the difficulty in the evaluation of field derivatives. This problem is overcome with the application of the Moving Least Squares (MLS) technique on a finite volume framework. In this work we present the application of this method (FV-MLS) to the solution of aeroacoustic problems.     

The development of an integrated platform to identify breast cancer glycoproteome changes in human serum

Protein glycosylation represents one of the major post-translational modifications and can have significant effects on protein function. Moreover, changes in the carbohydrate structure are increasingly being recognized as an important modification associated with cancer etiology. In this report, we describe the development of a proteomics approach to identify breast cancer related changes in either concentration and/or the carbohydrate structures of glycoprotein(s) present in blood samples. Diseased and healthy serum samples were processed by an optimized sample preparation protocol using multiple lectin affinity chromatography (M-LAC) that partitions serum proteins based on glycan characteristics. Subsequently, three separate procedures, 1D SDS-PAGE, isoelectric focusing and an antibody microarray, were applied to identify potential candidate markers for future study. The combination of these three platforms is illustrated in this report with the analysis of control and cancer glycoproteomic fractions. Firstly, a molecular weight based separation of glycoproteins by 1D SDS-PAGE was performed, followed by protein, glycoprotein staining, lectin blotting and LC–MS analysis. To refine or confirm the list of interesting glycoproteins, isoelectric focusing (targeting sialic acid changes) and an antibody microarray (used to detect neutral glycan shifts) were selected as the orthogonal methods. As a result, several glycoproteins including alpha-1B-glycoprotein, complement C3, alpha-1-antitrypsin and transferrin were identified as potential candidates for further study.     

On hydraulic permeability of random packs of monodisperse spheres: Direct flow simulations versus correlations

Hydraulic permeability is studied in porous media consisting of randomly distributed monodisperse spheres by means of computational fluid dynamics (CFD) simulations. The packing of spheres is generated by inserting a certain number of nonoverlapping spherical particles inside a cubic box at both low and high packing fractions using proper algorithms. Fluid flow simulations are performed within the interparticulate porous space by solving Navier-Stokes equations in a low-Reynolds laminar flow regime. The hydraulic permeability is calculated from the Darcy equation once the mean values of velocity and pressure gradient are calculated across the particle packing. The simulation results for the pressure drop across the packing are verified by the Ergun equation for the lower range of porosities (<0.75), and the Stokes equation for higher porosities (∼1). Using the results of simulations, the effects of porosity and particle diameters on the hydraulic permeability are investigated. Simulations precisely specified the range of applicability of empirical or semi-empirical correlations for hydraulic permeability, namely the Carman-Kozeny, Rumpf-Gupte, and Howells-Hinch formulas. The number of spheres in the model is gradually decreased from 2000 to 20 to discover the finite-size effect of pores on the hydraulic permeability of spherical packing, which has not been clearly addressed in the literature. In addition, the scale dependence of hydraulic permeability is studied via simulations of the packing of spheres shrunk to lower scales. The results of this work not only reveal the validity range of the aforementioned correlations, but also show the finite-size effect of pores and the scale-independence of direct CFD simulations for hydraulic permeability.