A Comparative Study of Electrochemical Kinetic Parameters by the Potential Step Method. Electrode Reactions of CyDTA and EDTA Complexes of Cu(II) at DME

By using the same current-time (I-t) curves, electrochemical kinetic parameters are determined by two methods, (a) using the ratio of current at a given potential to the diffusion-controlled limiting current and (b) curve fitting method, for the reduction of Cu(II)–CyDTA complex. The analysis by the method (a) shows that the rate determining step involves only one electron although the overall reduction of the complex involves two electrons suggesting thereby the stepwise reduction of the complex. The nature of I-t curves suggests the adsorption of intermediate species at the electrode surface. Under these circumstances more reliable kinetic parameters can be obtained by the method (a) compared to that of (b). Similar observations are found in the case of reduction of Cu(II)–EDTA complex.

A One-Step Method for the Growth of Ga2O3-Nanorod-Based White-Light-Emitting Phosphors

A one-step synthesis of Ga2O3 nanorods by heating molten gallium in ambient air at high temperatures is presented. The high-temperature synthesis creates oxygen vacancies and incorporates nitrogen from the environment. The oxygen vacancy in Ga2O3 is responsible for the emission in the blue-green region, while nitrogen in Ga2O3 is responsible for red emission.

Room temperature ferromagnetism in ZnO (core)/graphite (shell) nanowires fabricated by a one-step method

ZnO (core)/graphitic (shell) nanowires were successfully fabricated by a one-step method. Morphology of the as-grown nanowires was studied in detail by scanning electron microscopy, transmission electron microscopy (TEM), and energy dispersive X-ray analysis (EDS). High resolution TEM micrographs and selected area electron diffraction patterns reveal the core/shell morphology of the nanowires that grew along the c-axis of ZnO. EDS study of the nanowires confirms that there are no impurities within the detectable limit. Superconducting quantum interference device magnetometer measurements show room temperature ferromagnetic ordering in these core/shell nanowires. (C) 2010 Elsevier Ltd. All rights reserved.

One step synthesis of monoclinic VO2 (B) bundles of nanorods: Cathode for Li ion battery

One of the metastable phases of vanadium dioxide, VO2(B) bundles of nanorods and microspheres have been synthesized through a simple hydrothermal method by dispersing V2O5 in aqueous quinol. The obtained products were characterized by X-ray diffraction (XRD), Fourier transform infrared (FTIR) spectroscopy, scanning electron microscopy (SEM) and electrochemical discharge-charge test for lithium battery. It was found that the morphologies of the obtained VO2(B) can be tuned by manipulating the relative amount of quinol. The electrochemical test found that the bundles of nanorods exhibit an initial discharge capacity of 171 mAh g(-1) and its almost stabilized capacity was reached to 108 mAh g(-1) after 47 cycles at a current density of 0.1 mA g(-1). The formation mechanism of the VO2(B) bundles of nanorods and microspheres was also discussed. (C) 2012 Elsevier Inc. All rights reserved.

Finite volume evolution Galerkin method for hyperbolic conservation laws with spatially varying flux functions

We present a generalization of the finite volume evolution Galerkin scheme [M. Lukacova-Medvid'ova,J. Saibertov'a, G. Warnecke, Finite volume evolution Galerkin methods for nonlinear hyperbolic systems, J. Comp. Phys. (2002) 183 533-562; M. Luacova-Medvid'ova, K.W. Morton, G. Warnecke, Finite volume evolution Galerkin (FVEG) methods for hyperbolic problems, SIAM J. Sci. Comput. (2004) 26 1-30] for hyperbolic systems with spatially varying flux functions. Our goal is to develop a genuinely multi-dimensional numerical scheme for wave propagation problems in a heterogeneous media. We illustrate our methodology for acoustic waves in a heterogeneous medium but the results can be generalized to more complex systems. The finite volume evolution Galerkin (FVEG) method is a predictor-corrector method combining the finite volume corrector step with the evolutionary predictor step. In order to evolve fluxes along the cell interfaces we use multi-dimensional approximate evolution operator. The latter is constructed using the theory of bicharacteristics under the assumption of spatially dependent wave speeds. To approximate heterogeneous medium a staggered grid approach is used. Several numerical experiments for wave propagation with continuous as well as discontinuous wave speeds confirm the robustness and reliability of the new FVEG scheme.

Mesh-free approximations via the error reproducing kernel method and applications to nonlinear systems developing shocks

Error estimates for the error reproducing kernel method (ERKM) are provided. The ERKM is a mesh-free functional approximation scheme [A. Shaw, D. Roy, A NURBS-based error reproducing kernel method with applications in solid mechanics, Computational Mechanics (2006), to appear (available online)], wherein a targeted function and its derivatives are first approximated via non-uniform rational B-splines (NURBS) basis function. Errors in the NURBS approximation are then reproduced via a family of non-NURBS basis functions, constructed using a polynomial reproduction condition, and added to the NURBS approximation of the function obtained in the first step. In addition to the derivation of error estimates, convergence studies are undertaken for a couple of test boundary value problems with known exact solutions. The ERKM is next applied to a one-dimensional Burgers equation where, time evolution leads to a breakdown of the continuous solution and the appearance of a shock. Many available mesh-free schemes appear to be unable to capture this shock without numerical instability. However, given that any desired order of continuity is achievable through NURBS approximations, the ERKM can even accurately approximate functions with discontinuous derivatives. Moreover, due to the variation diminishing property of NURBS, it has advantages in representing sharp changes in gradients. This paper is focused on demonstrating this ability of ERKM via some numerical examples. Comparisons of some of the results with those via the standard form of the reproducing kernel particle method (RKPM) demonstrate the relative numerical advantages and accuracy of the ERKM.

The Alpha-Method Direct Transcription In Path Constrained Dynamic Optimization

Numerically discretized dynamic optimization problems having active inequality and equality path constraints that along with the dynamics induce locally high index differential algebraic equations often cause the optimizer to fail in convergence or to produce degraded control solutions. In many applications, regularization of the numerically discretized problem in direct transcription schemes by perturbing the high index path constraints helps the optimizer to converge to usefulm control solutions. For complex engineering problems with many constraints it is often difficult to find effective nondegenerat perturbations that produce useful solutions in some neighborhood of the correct solution. In this paper we describe a numerical discretization that regularizes the numerically consistent discretized dynamics and does not perturb the path constraints. For all values of the regularization parameter the discretization remains numerically consistent with the dynamics and the path constraints specified in the, original problem. The regularization is quanti. able in terms of time step size in the mesh and the regularization parameter. For full regularized systems the scheme converges linearly in time step size.The method is illustrated with examples.

Critical Evaluation of Determining Swelling Pressure by Swell-Load Method and Constant Volume Method

For any construction activity in expansive soils, determination of swelling pressure/heave is an essential step. Though many attempts have been made to develop laboratory procedures by using the laboratory one-dimensional oedometer to determine swelling pressure of expansive soils, they are reported to yield varying results. The main reason for these variations could be heterogeneous moisture distribution of the sample over its thickness. To overcome this variation the experimental procedure should be such that the soil gets fully saturated. Attempts were made to introduce vertical sand drains in addition to the top and bottom drains. In this study five and nine vertical sand drains were introduced to experimentally find out the variations in the swell and swelling pressure. The variations in the moisture content at middle, top, and bottom of the sample in the oedometer test are also reported. It is found that swell-load method is better as compared to zero-swell method. Further, five number of vertical sand drains are found to be sufficient to obtain uniform moisture content distribution.

CSSI-PRO: a method for secondary structure type editing, assignment and estimation in proteins using linear combination of backbone chemical shifts

Estimation of secondary structure in polypeptides is important for studying their structure, folding and dynamics. In NMR spectroscopy, such information is generally obtained after sequence specific resonance assignments are completed. We present here a new methodology for assignment of secondary structure type to spin systems in proteins directly from NMR spectra, without prior knowledge of resonance assignments. The methodology, named Combination of Shifts for Secondary Structure Identification in Proteins (CSSI-PRO), involves detection of specific linear combination of backbone H-1(alpha) and C-13' chemical shifts in a two-dimensional (2D) NMR experiment based on G-matrix Fourier transform (GFT) NMR spectroscopy. Such linear combinations of shifts facilitate editing of residues belonging to alpha-helical/beta-strand regions into distinct spectral regions nearly independent of the amino acid type, thereby allowing the estimation of overall secondary structure content of the protein. Comparison of the predicted secondary structure content with those estimated based on their respective 3D structures and/or the method of Chemical Shift Index for 237 proteins gives a correlation of more than 90% and an overall rmsd of 7.0%, which is comparable to other biophysical techniques used for structural characterization of proteins. Taken together, this methodology has a wide range of applications in NMR spectroscopy such as rapid protein structure determination, monitoring conformational changes in protein-folding/ligand-binding studies and automated resonance assignment.

On the Transform Method of Solution of an External Crack Problem

The breakdown of the usual method of Fourier transforms in the problem of an external line crack in a thin infinite elastic plate is discovered and the correct solution of this problem is derived using the concept of a generalised Fourier transform of a type discussed first by Golecki [1] in connection with Flamant's problem.

Analysis-By-Synthesis Based Switched Transform Domain Split Vq Using Gaussian Mixture Model

Using analysis-by-synthesis (AbS) approach, we develop a soft decision based switched vector quantization (VQ) method for high quality and low complexity coding of wideband speech line spectral frequency (LSF) parameters. For each switching region, a low complexity transform domain split VQ (TrSVQ) is designed. The overall rate-distortion (R/D) performance optimality of new switched quantizer is addressed in the Gaussian mixture model (GMM) based parametric framework. In the AbS approach, the reduction of quantization complexity is achieved through the use of nearest neighbor (NN) TrSVQs and splitting the transform domain vector into higher number of subvectors. Compared to the current LSF quantization methods, the new method is shown to provide competitive or better trade-off between R/D performance and complexity.

Approximate analysis of coupled non-linear non-conservative systems subjected to step-function excitation

The paper deals with the approximate analysis of non-linear non-conservative systems oftwo degrees of freedom subjected to step-function excitation. The method of averaging of Krylov and Bogoliubov is used to arrive at the approximate equations for amplitude and phase. An example of a spring-mass-damper system is presented to illustrate the method and a comparison with numerical results brings out the validity of the approach.

Liquid phase oxidation of propionaldehyde: Kinetics of initiation step

A method of determining the rate of the initiation reaction in the liquid phase oxidation of propionaldehyde is described.

A critical analysis of the shear difference method

The shear difference method which is commonly used for the separation of normal stresses using photoelastic techniques depends on the step-by-step integration of one of the differential equations of equilibrium. It is assumed that the isoclinic and the isochromatic parameters measured by the conventional methods pertain to the state of stress at the midpoint of the light path. In practice, a slice thin enough for the above assumption to be true and at the same time thick enough to give differences in the shear-stress values over the thickness is necessary. The paper discusses the errors introduced in the isoclinic and isochromatic values by the conventional methods neglecting the variation of stresses along the light path. It is shown that while the error introduced in the measurement of the isochromatic parameter may not be serious, the error caused in the isoclinic measurement may lead to serious errors. Since the shear-difference method involves step-by-step integration the error introduced will be of a cumulative nature.

Comparison of Prediction Based LSF Quantization Methods using Split VQ

Further improvement in performance, to achieve near transparent quality LSF quantization, is shown to be possible by using a higher order two dimensional (2-D) prediction in the coefficient domain. The prediction is performed in a closed-loop manner so that the LSF reconstruction error is the same as the quantization error of the prediction residual. We show that an optimum 2-D predictor, exploiting both inter-frame and intra-frame correlations, performs better than existing predictive methods. Computationally efficient split vector quantization technique is used to implement the proposed 2-D prediction based method. We show further improvement in performance by using weighted Euclidean distance.