Thermodynamic analysis of enzyme catalysed reactions: new insights into the Michaelis-Menten equation

A simple thermodynamic analysis of the well-known Michaelis-Menten equation (MME) of enzyme catalysis is proposed that employs the chemical potential mu to follow the Gibbs free energy changes attending the formation of the enzyme-substrate complex and its turnover to the product. The main conclusion from the above analysis is that low values of the Michaelis constant KM and high values of the turnover number k(cat) are advantageous: this supports a simple algebraic analysis of the MME, although at variance with current thinking. Available data apparently support the above findings. It is argued that transition state stabilisation - rather than substrate distortion or proximity - is the key to enzyme catalysis.

Grain Floatation During Equiaxed Solidification of an Al-Cu Alloy in a Side-Cooled Cavity: Part II-Numerical Studies

In this article, a single-phase, one-domain macroscopic model is developed for studying binary alloy solidification with moving equiaxed solid phase, along with the associated transport phenomena. In this model, issues such as thermosolutal convection, motion of solid phase relative to liquid and viscosity variations of the solid-liquid mixture with solid fraction in the mobile zone are taken into account. Using the model, the associated transport phenomena during solidification of Al-Cu alloys in a rectangular cavity are predicted. The results for temperature variation, segregation patterns, and eutectic fraction distribution are compared with data from in-house experiments. The model predictions compare well with the experimental results. To highlight the influence of solid phase movement on convection and final macrosegregation, the results of the current model are also compared with those obtained from the conventional solidification model with stationary solid phase. By including the independent movement of the solid phase into the fluid transport model, better predictions of macrosegregation, microstructure, and even shrinkage locations were obtained. Mechanical property prediction models based on microstructure will benefit from the improved accuracy of this model.

Characterization of Ni-Pd alloy as anode for methanol oxidative fuel cell

Electrochemical deposition of Ni-Pd alloy films of various compositions from bath solution containing ethylenediamine (EDA) was carried out to use as anode material for methanol oxidative fuel cell in H2SO4 medium. Electronic absorption spectrum of bath solution containing Ni2+ Pd2+ ions and EDA indicated the formation of a four coordinate square planar metal-ligand complex of both the metal ions. X-ray diffraction (XRD) patterns of the deposited alloy films show an increase in Pd-Ni alloy lattice parameter with increase in Pd content, and indicate the substitution of Pd in the lattice. A nano/ultrafine kind of crystal growth was observed in the alloy film deposited at low current density (2.5 mA cm(-2)). X-ray photoelectron spectroscopic (XPS) studies on the successively sputtered films showed the presence of Ni and Pd in pure metallic states and the surface concentration ratio of Ni to Pd is less than bulk indicating the segregation of Pd on the surface. Electro-catalytic oxidation of methanol in H2SO4 medium is found to be promoted on Ni-Pd electrodeposits. The anodic peak current characteristics to oxidation reaction on Ni-Pd was found typically high when compared to pure nickel and the relative increase in surface area by alloying the Ni by Pd was found to be as much as 300 times. (C) 2003 Elsevier Science B.V. All rights reserved.

Turbulent non-equlibrium wakes

We consider here the detailed application of a model Reynolds stress equation (Narasimha 1969) to plane turbulent wakes subjected to pressure gradients. The model, which is a transport equation for the stress exhibiting relaxation and diffusion, is found to be consistent with the observed response of a wake to a nearly impulsive pressure gradient (Narasimha & Prabhu 1971). It implies in particular that a wake can be in equilibrium only if the longitudinal strain rate is appreciably less than the wake shear. We then describe a further series of experiments, undertaken to investigate the range of validity of the model. It is found that, with an appropriate convergence correction when necessary, the model provides excellent predictions of wake development under favourable, adverse and mixed pressure gradients. Furthermore, the behaviour of constant-pressure distorted wakes, as reported by Keffer (1965, 1967), is also explained very well by the model when account is taken of the effective flow convergence produced by the distortion. In all these calculations, only a simple version of the model is used, involving two non-dimensional constants both of which have been estimated from a single relaxation experiment.

The role of competition and habitat in structuring small mammal communities in a tropical montane ecosystem in southern India

Small mammals were sampled in two natural habitats (montane stunted evergreen forests and montane grassland) and four anthropogenic habitats (tea, wattle, bluegum and pine plantation) in the Upper Nilgiris in southern India. Of the species trapped, eight were in montane evergreen forests and three were in other habitats. Habitat discrimination was studied in the rodents Rattus rattus and Mus famulus and the shrew Suncus montanus in the montane forest habitat. Multivariate tests on five variables (canopy cover, midstorey density, ground cover, tree density, canopy height) showed that R. rattus uses areas of higher tree density and lower canopy cover. Suncus montanus and M. famulus use habitat with higher tree density and ground cover and lower canopy height. Multivariate tests did not discriminate habitat use between the species. Univariate tests, however, showed that M. famulus uses areas of higher tree density than R. rattus and S. montanus. Rattus rattus was the dominant species in the montane forest, comprising 60.9% of total density, while the rodent Millardia meltada was the dominant species in the grassland. Studies of spatial interaction between these two species in habitats where they coexisted showed neither overlap nor avoidance between the species. Rattus rattus, however, did use areas of lower ground cover than did M. meltada. The analysis of spatial interactions between the species, habitat discrimination and use, and the removal experiments suggest that interspecific competition may not be a strong force in structuring these small mammal communities. There are distinct patterns in the use of different habitats by some species, but microhabitat selection and segregation is weak. Other factors such as intraspecific competition may play a more important role in these communities.

Growth and Characterization Studies of ABi2ta2o9 (A = Ba, Sr and Ca) Ferroelectric Thin Films

Thin films of ferroelectric ABi2Ta2O9 bismuth-layered structure, where A = Ba, Sr and Ca, were prepared by pulsed laser deposition technique on Pt/TiO2/SiO2/Si(100) substrates. The influence of substrate temperature between 500 to 750°C, and oxygen partial pressure 100-300 mTorr, on the structural and electrical properties of the films was investigated. The films deposited above 650°C substrate temperature showed complete Aurivillius layered structure. Films annealed at 750°C for 1h in oxygen atmosphere have exhibited better electrical properties. Atomic force microscopy study of surface topography shows that the films grown at lower temperature has smaller grains and higher surface roughness. This paper discusses the pronounced influence of A-site cation substitution on the structural and ferroelectric properties with the aid of Raman spectroscopy, X-ray diffraction and electrical properties. The degradation of ferroelectric properties with Ba and Ca substitution at A-sites is attributed to the higher structural distortion caused by changing tolerance factor. A systematic proportionate variation of coercive field is attributed to electronegativity difference of A-site cations.

Low Complexity Wideband LSFQuantization Using GMM of Uncorrelated Gaussian Mixtures

We develop a Gaussian mixture model (GMM) based vector quantization (VQ) method for coding wideband speech line spectrum frequency (LSF) parameters at low complexity. The PDF of LSF source vector is modeled using the Gaussian mixture (GM) density with higher number of uncorrelated Gaussian mixtures and an optimum scalar quantizer (SQ) is designed for each Gaussian mixture. The reduction of quantization complexity is achieved using the relevant subset of available optimum SQs. For an input vector, the subset of quantizers is chosen using nearest neighbor criteria. The developed method is compared with the recent VQ methods and shown to provide high quality rate-distortion (R/D) performance at lower complexity. In addition, the developed method also provides the advantages of bitrate scalability and rate-independent complexity.

Low complexity Bit allocation algorithms for AAC encoding

We have developed two reduced complexity bit-allocation algorithms for MP3/AAC based audio encoding, which can be useful at low bit-rates. One algorithm derives optimum bit-allocation using constrained optimization of weighted noise-to-mask ratio and the second algorithm uses decoupled iterations for distortion control and rate control, with convergence criteria. MUSHRA based evaluation indicated that the new algorithm would be comparable to AAC but requiring only about 1/10 th the complexity.

On a Novel Geometric Representation of Rotation

This paper presents a novel method of representing rotation and its application to representing the ranges of motion of coupled joints in the human body, using planar maps. The present work focuses on the viability of this representation for situations that relied on maps on a unit sphere. Maps on a unit sphere have been used in diverse applications such as Gauss map, visibility maps, axis-angle and Euler-angle representations of rotation etc. Computations on a spherical surface are difficult and computationally expensive; all the above applications suffer from problems associated with singularities at the poles. There are methods to represent the ranges of motion of such joints using two-dimensional spherical polygons. The present work proposes to use multiple planar domain “cube” instead of a single spherical domain, to achieve the above objective. The parameterization on the planar domains is easy to obtain and convert to spherical coordinates. Further, there is no localized and extreme distortion of the parameter space and it gives robustness to the computations. The representation has been compared with the spherical representation in terms of computational ease and issues related to singularities. Methods have been proposed to represent joint range of motion and coupled degrees of freedom for various joints in digital human models (such as shoulder, wrist and fingers). A novel method has been proposed to represent twist in addition to the existing swing-swivel representation.

Direct mdct domain psychoacoustic modeling

We extend the recently proposed spectral integration based psychoacoustic model for sinusoidal distortions to the MDCT domain. The estimated masking threshold additionally depends on the sub-band spectral flatness measure of the signal which accounts for the non- sinusoidal distortion introduced by masking. The expressions for masking threshold are derived and the validity of the proposed model is established through perceptual transparency test of audio clips. Test results indicate that we do achieve transparent quality reconstruction with the new model. Performance of the model is compared with MPEG psychoacoustic models with respect to the estimated perceptual entropy (PE). The results show that the proposed model predicts a lower PE than other models.

High-rate analysis of channel-optimized vector quantization

High-rate analysis of channel-optimized vector quantizationThis paper considers the high-rate performance of channel optimized source coding for noisy discrete symmetric channels with random index assignment. Specifically, with mean squared error (MSE) as the performance metric, an upper bound on the asymptotic (i.e., high-rate) distortion is derived by assuming a general structure on the codebook. This structure enables extension of the analysis of the channel optimized source quantizer to one with a singular point density: for channels with small errors, the point density that minimizes the upper bound is continuous, while as the error rate increases, the point density becomes singular. The extent of the singularity is also characterized. The accuracy of the expressions obtained are verified through Monte Carlo simulations.

Lossy distribution source coding with side information

In a typical sensor network scenario a goal is to monitor a spatio-temporal process through a number of inexpensive sensing nodes, the key parameter being the fidelity at which the process has to be estimated at distant locations. We study such a scenario in which multiple encoders transmit their correlated data at finite rates to a distant and common decoder. In particular, we derive inner and outer bounds on the rate region for the random field to be estimated with a given mean distortion.

An Overmodulation Scheme for Vector Controlled Induction Motor Drives

This paper presents an algorithm for control of line side voltage of a voltage source inverter upto six-step mode. This is a modified version of an existing overmodulation algorithm. The modified algorithm maintains proportionality between the reference voltage and the output fundamental voltage, and also reduces the computational effort required for implementation, while resulting in a marginally higher harmonic distortion. An estimation method is proposed for calculation of lower order ripple current. This estimation method is applied to a sensorless vector controlled induction motor drive to improve the performance of the drive during overmodulation.

Novel Switching Sequences for a Space-Vector-Modulated Three-Level Inverter

A three-level inverter produces six active vectors, each of normalized magnitudes 1, 0.866, and 0.5, besides a zero vector. The vectors of relative length 0.5 are termed pivot vectors.The three nearest voltage vectors are usually used to synthesize the reference vector. In most continuous pulsewidth-modulation(PWM) schemes, the switching sequence begins from a pivot vector and ends with the same pivot vector. Thus, the pivot vector is applied twice in a subcycle or half-carrier cycle. This paper proposes and investigates alternative switching sequences, which use the pivot vector only once but employ one of the other two vectors twice within the subcycle. The total harmonic distortion(THD) in the fundamental line current pertaining to these novel sequences is studied theoretically as well as experimentally over the whole range of modulation. Compared with centered space vector PWM, two of the proposed sequences lead to reduced THD at high modulation indices at a given average switching frequency.

Solubilities of Pb+2, Bi+3, Sb+3 and Cu+1 sulphides in (NaCl KCl Na2S) melts

Solubilities of common metal sulfides have been determined in the (NaCl+KCl) eutectic melt with and without Na2S. A novel gas-phase equilibrium technique has been used for PbS, Bi2S3, and So2S3, and an improved liquid phase equilibrium technique for Cu2S, which eliminates the errors due to physical entrapment of the sulfide phase and segregation on quenching, enabling precise measurements to be made. Solubilities in the (NaCl+KCl) eutectic melt were determined as a function of temperature in the rante 700° to 950°C, and were found to be small. The partial molar heats of mixing of the sulfides in the eutectic melt have been calculated from the solubility measurements, to be 13.3, 31.4, 37.1, and 49.0 kcal for PbSs), Sb2S2(l), and Cu2S(s), respectively. Sodium sulfide addition was observed to enhance these solubilities, the effect being largest for Cu2S followed by Sb2S3, Bi2S3, and PbS. This effect is explained qualitatively. It was observed that PbS and Sb2S3 obey Henry's law up to saturation in (NaCl+KCl+Na2S) melts.