ESR studies of phase transitions in double propionates

Detailed ESR investigations of Mn2+ substituting for Ca2+ in Ca2Sr(C2H5COO)6 (DSP), Ca2Pb(C2H5COO)6 (DLP) and Ca2Ba(C2H5COO)6 (DBP), in single crystals and powders, over the temperature range from 200°C to -180°C have been carried out to study the successive phase transitions in these compounds. (DSP: [Tetragonal] ← 8.5°C → [tetragonal, ferroelectric] [tetragonal] ← -169°C → [monoclinic, ferroelectric]; DLP : [tetragonal] ← 60°C → [tetragonal, ferroelectric] ← -71.5°C → [monoclinic, ferroelectric]; [Cubic] ← -6°C → [orthorhombic] ← -75°C → [?]). Spectra have been analysed in terms of axial spin Hamiltonians and the temperature dependences of the parameters studied. In DSP and DLP across the I ↔ II transition, new physically and chemically inequivalent sites appear indicating the disappearance of the diad axes on which the propionate groups are located, bringing out the connection between the motional states of the propionate groups and the occurence of ferroelectricity. The II ↔ III transition also causes chemically inequivalent sites to develop, indicating that the transitions may not be isomorphous as believed previously. In DBP, the -6°C transition leads to (i) a doubling of both physically and chemically inequivalent sites (ii) a small (150 G at -6°C to 170 G at -8°C), but abrupt change in the magnitude of the zero-field splitting tensor D, and (iii) displacements of the orientations of the D tensors. Results are interpreted in terms of alternate rotations of the oxygen octahedra, showing participation of the carboxyl oxygens in the transition. No drastic changes in the parameters occur across the -75°C transition consistent with its second order nature. Similarities and dissimilarities of the ESR spectra of the three compounds in relation to the phase transitions, are discussed.

Effect of inclination on laminar film condensation

The effect of inclination on laminar film condensation over and under isothermal flat plates is investigated analytically. The complete set of Navier Stokes equations in two dimensions is considered. Analysed as a perturbation problem, the zero-order perturbation represents the boundary layer equations. First and second order perturbations are solved to bring about the leading edge effects. Corresponding velocity and temperature profiles are presented. The results show decrease in heat transfer with larger ∥inclinations∥ from the vertical. Comparison with experimental data of Gerstmann and Griffith indicates a closer agreement of the present results than the analytical results of the same authors.

Regularized numerical integration of multibody dynamics with the generalized alpha method*

This paper discusses the consistent regularization property of the generalized α method when applied as an integrator to an initial value high index and singular differential-algebraic equation model of a multibody system. The regularization comes from within the discretization itself and the discretization remains consistent over the range of values the regularization parameter may take. The regularization involves increase of the smallest singular values of the ill-conditioned Jacobian of the discretization and is different from Baumgarte and similar techniques which tend to be inconsistent for poor choice of regularization parameter. This regularization also helps where pre-conditioning the Jacobian by scaling is of limited effect, for example, when the scleronomic constraints contain multiple closed loops or singular configuration or when high index path constraints are present. The feed-forward control in Kane's equation models is additionally considered in the numerical examples to illustrate the effect of regularization. The discretization presented in this work is adopted to the first order DAE system (unlike the original method which is intended for second order systems) for its A-stability and same order of accuracy for positions and velocities.

Numerical studies on quasilinear and linear elliptic equations

We explore here the acceleration of convergence of iterative methods for the solution of a class of quasilinear and linear algebraic equations. The specific systems are the finite difference form of the Navier-Stokes equations and the energy equation for recirculating flows. The acceleration procedures considered are: the successive over relaxation scheme; several implicit methods; and a second-order procedure. A new implicit method—the alternating direction line iterative method—is proposed in this paper. The method combines the advantages of the line successive over relaxation and alternating direction implicit methods. The various methods are tested for their computational economy and accuracy on a typical recirculating flow situation. The numerical experiments show that the alternating direction line iterative method is the most economical method of solving the Navier-Stokes equations for all Reynolds numbers in the laminar regime. The usual ADI method is shown to be not so attractive for large Reynolds numbers because of the loss of diagonal dominance. This loss can however be restored by a suitable choice of the relaxation parameter, but at the cost of accuracy. The accuracy of the new procedure is comparable to that of the well-tested successive overrelaxation method and to the available results in the literature. The second-order procedure turns out to be the most efficient method for the solution of the linear energy equation.

Dual Drug Delivery Microcapsules via Layer-by-Layer Self-Assembly

The integration of hydrophobic and hydrophilic drugs in the polymer microcapsule offers the possibility of developing a new drug delivery system that combines the best features of these two distinct classes of material. Recently, we have reported the encapsulation of an uncharged water-insoluble drug in the polymer membrane. The hydrophobic drug is deposited using a layer-by-layer (LbL) technique, which is based on the sequential adsorption of oppositely charged polyelectrolytes onto a charged substrate. In this paper, we report the encapsulation of two different drugs, which are invariably different in structure and in their solubility in water. We have characterized these dual drug vehicular capsules by confocal laser scanning microscopy, atomic force microscopy, visible microscopy, and transmission electron microscopy. The growth of a thin film on a flat substrate by LbL was monitored by UV−vis spectra. The desorption kinetics of two drugs from the thin film was modeled by a second-order rate model.

Studies on Aspergillus niger glutamine synthetase: Regulation of enzyme levels by nitrogen sources and identification of active site residues

The specific activity of glutamine synthetase (L-glutamate: ammonia ligase, EC 6.3.1.2) in surface grown Aspergillus niger was increased 3-5 fold when grown on L-glutamate or potassium nitrate, compared to the activity obtained on ammonium chloride. The levels of glutamine synthetase was regulated by the availability of nitrogen source like NH4 + , and further, the enzyme is repressed by increasing concentrations of NH4 +. In contrast to other micro-organisms, the Aspergillus niger enzyme was neither specifically inactivated by NH4+ or L-glutamine nor regulated by covalent modification.Glutamine synthetase from Aspergillus niger was purified to homogenity. The native enzyme is octameric with a molecular weight of 385,000±25,000. The enzyme also catalyses Mn2+ or Mg2+-dependent synthetase and Mn2+-dependent transferase activity.Aspergillus niger glutamine synthetase was completely inactivated by two mol of phenylglyoxal and one mol of N-ethylmaleimide with second order rate constants of 3·8 M–1 min–1 and 760 M–1 min–1 respectively. Ligands like Mg. ATP, Mg. ADP, Mg. AMP, L-glutamate NH4+, Mn2+ protected the enzyme against inactivation. The pattern of inactivation and protection afforded by different ligands against N-ethylamaleimide and phenylglyoxal was remarkably similar. These results suggest that metal ATP complex acts as a substrate and interacts with an arginine ressidue at the active site. Further, the metal ion and the free nucleotide probably interact at other sites on the enzyme affecting the catalytic activity.

Vanadate stimulates oxidation of NADH to generate hydrogen peroxide

Vanadate in the polymeric form of decavanadate, but not other forms, stimulated oxidation of NADH to NAD+ NADPH was also oxidized with comparable rates. This oxidation of NADH was accompanied by uptake of oxygen and generated hydrogen peroxide with the following stoichiometry: NADH + H+ + O2 → NAD+ + H2O2. The reaction followed second-order kinetics. The rate was dependent on the concentration of both NADH and vanadate and increased with decreasing pH. The reaction had an obligatory requirement for phosphate ions. Esr studies in the presence of the spin trap dimethyl pyrroline N oxide indicated the involvement of Superoxide anion as an intermediate. The reaction was sensitive to Superoxide dismutase and other scavengers of superoxide anions.

Modified design procedure for a sparger reactor sequence

In an earlier communication[l] we have indicated a general graphical design procedure for a sequence of sparger reactors in which a second order liquid phase reaction proceeds in a stagewise fashion. The prediction of the reactant concentration in each stage and hence the conversion depended on a search procedure initiated along a straight line representing the mass balance equation at the given stage and drawn from the known feed stage located on the abscissa in a E-IU diagram for the given system.

On energy-momentum tensors as sources of spin-2 fields

The improvement terms in the generalised energy-momentum tensor of Callan, Coleman and Jackiw can be derived from a variational principle if the Lagrangian is generalised to describe coupling between ‘matter’ fields and a spin-2 boson field. The required Lorentz-invariant theory is a linearised version of Kibble-Sciama theory with an additional (generally-covariant) coupling term in the Lagrangian. The improved energy-momentum tensor appears as the source of the spin-2 field, if terms of second order in the coupling constant are neglected.

Non-linear systems with quadratic and cubic damping - an analytical approach

The possible equivalence of second-order non-linear systems having quadratic and cubic damping with third-order linear systems is studied in this paper. It is shown that this equivalence can be established through transformation techniques under certain constraints on the form of the non-linearity of the given system.

On the computation of two-dimensional compressible flow fields by the modified local stability scheme

The modified local stability scheme is applied to several two-dimensional problems—blunt body flow, regular reflection of a shock and lambda shock. The resolution of the flow features obtained by the modified local stability scheme is found to be better than that achieved by the other first order schemes and almost identical to that achieved by the second order schemes incorporating artificial viscosity. The scheme is easy for coding, consumes moderate amount of computer storage and time. The scheme can be advantageously used in place of second order schemes.

Simulation of laminar flow in a three-dimensional lid-driven cavity by lattice Boltzmann method

Purpose - The purpose of this paper is to apply lattice Boltzmann equation method (LBM) with multiple relaxation time (MRT) model, to investigate lid-driven flow in a three-dimensional (3D), rectangular cavity, and compare the results with flow in an equivalent two-dimensional (2D) cavity. Design/methodology/approach - The second-order MRT model is implemented in a 3D LBM code. The flow structure in cavities of different aspect ratios (0.25-4) and Reynolds numbers (0.01-1000) is investigated. The LBM simulation results are compared with those from numerical solution of Navier-Stokes (NS) equations and with available experimental data. Findings - The 3D simulations demonstrate that 2D models may predict the flow structure reasonably well at low Reynolds numbers, but significant differences with experimental data appear at high Reynolds numbers. Such discrepancy between 2D and 3D results are attributed to the effect of boundary layers near the side-walls in transverse direction (in 3D), due to which the vorticity in the core-region is weakened in general. Secondly, owing to the vortex stretching effect present in 3D flow, the vorticity in the transverse plane intensifies whereas that in the lateral plane decays, with increase in Reynolds number. However, on the symmetry-plane, the flow structure variation with respect to cavity aspect ratio is found to be qualitatively consistent with results of 2D simulations. Secondary flow vortices whose axis is in the direction of the lid-motion are observed; these are weak at low. Reynolds numbers, but become quite strong at high Reynolds numbers. Originality/value - The findings will be useful in the study of variety of enclosed fluid flows.

Automata and logics over finitely varying functions

We extend some of the classical connections between automata and logic due to Büchi (1960) [5] and McNaughton and Papert (1971) [12] to languages of finitely varying functions or “signals”. In particular, we introduce a natural class of automata for generating finitely varying functions called View the MathML source’s, and show that it coincides in terms of language definability with a natural monadic second-order logic interpreted over finitely varying functions Rabinovich (2002) [15]. We also identify a “counter-free” subclass of View the MathML source’s which characterise the first-order definable languages of finitely varying functions. Our proofs mainly factor through the classical results for word languages. These results have applications in automata characterisations for continuously interpreted real-time logics like Metric Temporal Logic (MTL) Chevalier et al. (2006, 2007) [6] and [7].

Boundary-layer effects on internal flow choking in dual-thrust solid rocket motors

Theoretical studies have been carried out to examine internal flow choking in the inert simulators of a dual-thrust motor. Using a two-dimensional k-omega turbulence model, detailed parametric studies have been carried out to examine aerodynamic choking and the existence of a fluid throat at the transition region during the startup transient of dual-thrust motors. This code solves standard k-omega turbulence equations with shear flow corrections using a coupled second-order-implicit unsteady formulation. In the numerical study, a fully implicit finite volume scheme of the compressible, Reynolds-averaged, Navier-Stokes equations is employed. It was observed that, at the subsonic inflow conditions, there is a possibility of the occurrence of internal flow choking in dual-thrust motors due to the formation of a fluid throat at the beginning of the transition region induced by area blockage caused by boundary-layer-displacement thickness. It has been observed that a 55% increase in the upstream port area of the dual-thrust motor contributes to a 25% reduction in blockage factor at the transition region, which could negate the internal How choking and supplement with an early choking of the dual-thrust motor nozzle. If the height of the upstream port relative to the motor length is too small, the developing boundary layers from either side of the port can interact, leading to a choked,flow. On the other hand, if the developing boundary layers are far enough apart, then choking does not occur. The blockage factor is greater in magnitude for the choked case than for the unchoked case. More tangible explanations are presented in this paper for the boundary-layer blockage and the internal flow choking in dual-thrust motors, which hitherto has been unexplored.

Charge transport in a Tomonaga-Luttinger liquid: Effects of pumping and bias

We study the current produced in a Tomonaga-Luttinger liquid by an applied bias and by weak, pointlike impurity potentials which are oscillating in time. We use bosonization to perturbatively calculate the current up to second order in the impurity potentials. In the regime of small bias and low pumping frequency, both the dc and ac components of the current have power-law dependences on the bias and pumping frequencies with an exponent 2K-1 for spinless electrons, where K is the interaction parameter. For K < 1/2, the current grows large for special values of the bias. For noninteracting electrons with K=1, our results agree with those obtained using Floquet scattering theory for Dirac fermions. We also discuss the cases of extended impurities and of spin-1/2 electrons.