Inherent structures of phase-separating binary mixtures: Nucleation, spinodal decomposition, and pattern formation

An energy landscape view of phase separation and nonideality in binary mixtures is developed by exploring their potential energy landscape (PEL) as functions of temperature and composition. We employ molecular dynamics simulations to study a model that promotes structure breaking in the solute-solvent parent binary liquid, at low temperatures. The PEL of the system captures the potential energy distribution of the inherent structures (IS) of the system and is obtained by removing the kinetic energy (including that of intermolecular vibrations). The broader distribution of the inherent structure energy for structure breaking liquid than that of the structure making liquid demonstrates the larger role of entropy in stabilizing the parent liquid of the structure breaking type of binary mixtures. At high temperature, although the parent structure of the structure breaking binary mixture is homogenous, the corresponding inherent structure is found to be always phase separated, with a density pattern that exhibits marked correlation with the energy of its inherent structure. Over a broad range of intermediate inherent structure energy, bicontinuous phase separation prevails with interpenetrating stripes as signatures of spinodal decomposition. At low inherent structure energy, the structure is largely phase separated with one interface where as at high inherent structure energy we find nucleation type growth. Interestingly, at low temperature, the average inherent structure energy (< EIS >) exhibits a drop with temperature which signals the onset of crystallization in one of the phases while the other remains in the liquid state. The nonideal composition dependence of viscosity is anticorrelated with average inherent structure energy.

Brownian dynamics simulation of dense binary colloidal mixtures. I. Structural evolution and dynamics

We have carried out Brownian dynamics simulations of binary mixtures of charged colloidal suspensions of two different diameter particles with varying volume fractions phi and charged impurity concentrations n(i). For a given phi, the effective temperature is lowered in many steps by reducing n(i) to see how structure and dynamics evolve. The structural quantities studied are the partial and total pair distribution functions g(tau), the static structure factors, the time average g(<(tau)over bar>), and the Wendt-Abraham parameter. The dynamic quantity is the temporal evolution of the total meansquared displacement (MSD). All these parameters show that by lowering the effective temperature at phi = 0.2, liquid freezes into a body-centered-cubic crystal whereas at phi = 0.3, a glassy state is formed. The MSD at intermediate times shows significant subdiffusive behavior whose time span increases with a reduction in the effective temperature. The mean-squared displacements for the supercooled liquid with phi = 0.3 show staircase behavior indicating a strongly cooperative jump motion of the particles.

Brownian dynamics simulation of dense binary colloidal mixtures. II. Translational and bond-orientational order

We report the Brownian dynamics simulation results on the translational and bond-angle-orientational correlations for charged colloidal binary suspensions as the interparticle interactions are increased to form a crystalline (for a volume fraction phi = 0.2) or a glassy (phi = 0.3) state. The translational order is quantified in terms of the two- and four-point density autocorrelation functions whose comparisons show that there is no growing correlation length near the glass transition. The nearest-neighbor orientational order is determined in terms of the quadratic rotational invariant Q(l) and the bond-orientational correlation functions g(l)(t). The l dependence of Q(l) indicates that icosahedral (l = 6) order predominates at the cost of the cubic order (l = 4) near the glass as well as the crystal transition. The density and orientational correlation functions for a supercooled liquid freezing towards a glass fit well to the streched-exponential form exp[-(t/tau)(beta)]. The average relaxation times extracted from the fitted stretched-exponential functions as a function of effective temperatures T* obey the Arrhenius law for liquids freezing to a crystal whereas these obey the Vogel-Tamman-Fulcher law exp[AT(0)*/(T* - T-0*)] for supercooled Liquids tending towards a glassy state. The value of the parameter A suggests that the colloidal suspensions are ''fragile'' glass formers like the organic and molecular liquids.

Life-history of Neurospora intermedia in a sugar cane field

The life-history of Neurospora in nature has remained largely unknown. The present study attempts to remedy this. The following conclusions are based on observation of Neurospora on fire-scorched sugar cane in agricultural fields, and reconstruction experiments using a colour mutant to inoculate sugar cane burned in the laboratory. The fungus persists in soil as heat-resistant dormant ascospores. These are activated by a chemical(s) released into soil from the burnt substrate. The chief diffusible activator of ascospores is furfural and the germinating ascospores infect the scorched substrate. An invasive mycelium grows progressively upwards inside the juicy sugar cane and produces copious macroconidia externally through fire-induced openings formed in the plant tissue, or by the mechanical rupturing of the plant epidermal tissue by the mass of mycelium. The loose conidia are dispersed by wind and/or foraged by microfauna. It is suggested that the constant production of macroconidia, and their ready dispersal, serve a physiological role: to drain the substrate of minerals and soluble sugars, thereby creating nutritional conditions which stimulate sexual reproduction by the fungus. Sexual reproduction in the sugar-depleted cellulosic substrate occurs after macroconidiation has ceased totally and is favoured by the humid conditions prevailing during the monsoon rains. Profuse microconidiophores and protoperithecia are produced simultaneously in the pockets below the loosened epidermal tissue. Presumably protoperithecia are fertilized by microconidia which are possibly transmitted by nematodes active in the dead plant tissue. Mature perithecia release ascospores in situ which are passively liberated in the soil by the disintegration of the plant material and are, apparently, distributed by rain or irrigation water.

''Phase reversal'' of non-resonant microwave absorption in superconducting YBaCuO/CuO powder mixtures

Non-resonant microwave absorption is studied as a function of temperature and composition in superconducting YBa2Cu3O7/CuO ceramic composite samples. In pure YBa2Cu3O7 only normal field dependence of the absorption is observed, where as in composites an anomalous non-monotonic field dependence is seen. The results are explained using an extended resistively shunted junction model and invoking the occurrence of junctions with phase difference psi(0) such that pi/2 < psi(0) < 3 pi/2. Copyright (C) 1996 Elsevier Science Ltd

Nature of the Oxygen Species at Ni(110) and Ni(100) Surfaces Revealed by Exposure to Oxygen and Oxygen-Ammonia Mixtures: Evidence for the Surface Reactivity of O- Type Species

Adsorption of dioxygen at clean Ni(110) and Ni(100) surfaces gives rise to two prominent features in the O(1s) spectra at 530 and 531 eV due to O2- and O- type species, respectively. Interaction of ammonia with a Ni(100)-O surface where theta(oxygen) < 0.1 ML favors the dissociation of NH3 giving NHn, (n = 1, 2) and N(a) species. This is accompanied by a decrease in the intensity of the 531 eV feature. On the other hand. a Ni(100)-O surface where the oxygen species are mainly of the O2- type is unreactive, Coadsorption studies of NH3-O-2 mixtures show that at Ni(110) surfaces the uptake of both oxygen and ammonia increase with the proportion of oxygen in the NH3-O-2 mixture. The surface concentrations of the O- species and the NHn species also increase with the increase in the O-2/NH3 ratio while the slope of the plot of sigma(N) versus sigma(O-) is around unity. The results demonstrate the high surface reactivity of the O- species and its role in the dissociation of ammonia. Based on these observations, the possibility of the formation of a surface complex between ammonia and oxygen (specifically O-) is suggested. Results from vibrational spectroscopic studies of the coadsorption of NH3-O-2 mixtures are consistent with those from core-level spectroscopic studies.

Temperature dependence of the levitation effect - Implications for separation of multicomponent mixtures

Sufficiently long molecular dynamics simulations have been carried out on spherical monatomic sorbates in NaY zeolite, interacting via simple Lennard-Jones potentials, to investigate the dependence of the levitation effect on the temperature. Simulations carried out in the range 100-300 K suggest that the anomalous peak in the diffusion coefficient (observed when the levitation parameter, gamma, is near unity) decreases in intensity with increase in temperature. The rate of cage-to-cage migrations also exhibits a similar trend. The activation energy obtained from Arrhenius plots is found to exhibit a minimum when the diffusion coefficient is a maximum, corresponding to the gamma approximate to 1 sorbate diameter. In the linear or normal regime, the activation energy increases with increase in sorbate diameter until it shows a sharp decrease in the anomalous regime. Locations and energies of the adsorption sites and their dependence on the sorbate size gives interesting insight into the nature of the underlying potential-energy surface and further explain the observed trend in the activation energy with sorbate size. Cage residence times, tau(c), show little or no change with temperature for the sorbate with diameter corresponding to gamma approximate to 1, whereas there is a significant decrease in tau(c) with increase in temperature for sorbates in the linear regime. The implications of the present study for the separation of mixtures of sorbates are discussed.

Half-sandwich (eta(6)-arene)ruthenium(II) chiral Schiff base complexes: Analysis of the diastereomeric mixtures in solution by 2D-NMR spectroscopy

2D NMR spectroscopy has been used to determine the metal configuration in solution of three complexes, viz. [(eta(6)-p-cymene)Ru(L*)Cl] (1) and [(eta(6)-p-cymene)Ru(L*)(L')] (ClO4) (L' = H2O, 2; PPh3, 3), where L* is the anion of (S)-(1-phenylethyl)salicylaldimine. The complexes exist in two diastereomeric forms in solution. Both the (R-Ru,S-C)- and (S-Ru,S-C)-diastereomers display the presence of attractive, CH/pi interaction involving the phenyl group attached to the chiral carbon and the cymene ring hydrogens. This interaction restricts the rotation of the C*-N single bond and, as a result, two structural types with either the hydrogen atom attached to the chiral carbon (C*) or the methyl group attached to C* in close proximity of the cymene ring protons get stabilized. Using 2D NMR spectroscopy as a tool, the spatial interaction involving these protons are studied in order to obtain the metal configuration(s) of the diastereomeric complexes in solution. This technique has enabled us to determine the metal configuration as (R-Ru,S-C) for the major isomers of 1-3 in solution.

Thermal Lipid Order−Disorder Transitions in Mixtures of Cationic Cholesteryl Lipid Analogues and Dipalmitoyl Phosphatidylcholine Membranes

Two types of cationic cholesteryl amphiphiles, one where the headgroup is attached to the steroid by an ester linkage and the second by an ether linkage, were synthesized. A third type of cholesteryl lipid bearing an oligoethylene glycol segment was also prepared. Each of these synthetic lipids generated vesicle-like aggregates with closed inner aqueous compartments from their aqueous suspensions. We examined their interaction with L-α-dipalmitoyl phosphatidylcholine (DPPC) membranes using fluorescence anisotropy, transmission electron microscopy (TEM), and differential scanning calorimetry (DSC). When included in membranes, the synthetic cholesteryl lipids were found to quench the chain motion of the acyl chains of DPPC. This suggests that these cationic cholesteryl derivatives act as filler molecules despite modification at the headgroup level from the molecular structure of natural cholesterol. Careful analyses of DSC and fluorescence anisotropy data suggest that the nature of perturbation induced by each of these cationic cholesterol derivatives is dependent on the details of their molecular structure and provides significant information on the nature of interaction of these derivatives with phospholipid molecules. In general, amphiphiles that support structured water at the interfacial region tend to rigidify the fluid phase more than others. Importantly, these cholesteryl amphiphiles behave less like cholesterol in that their incorporation in DPPC not only abolishes the phase transition but also depresses the phase transition temperature.

Three-dimensional double-diffusive convection and macrosegregation during non-equilibrium solidification of binary mixtures

A three-dimensional transient mathematical model (following a fixed-grid enthalpy-based continuum formulation) is used to study the interaction of double-diffusive natural convection and non-equilibrium solidification of a binary mixture in a cubic enclosure cooled from a side. Investigations are carried out for two separate test systems, one corresponding to a typical model "metal-alloy analogue" system and other corresponding to a real metal-alloy system. Due to stronger effects of solutal buoyancy in actual metal-alloy systems than in corresponding analogues, the convective transport mechanisms for the two cases are quite different. However, in both cases, similar elements of three-dimensionality are observed in the curvature and spacing of the projected streamlines. As a result of three-dimensional convective flow patterns, a significant solute macrosegregation is observed across the transverse sections of the cavity, which cannot be captured by two-dimensional simulations. (C) 2003 Elsevier Science Ltd. All rights reserved.

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.

The selection of a sugar for transport and storage of carbon in plants

Sugars perform two vital functions in plants: as compatible solutes protecting the cell against osmotic stress and as mobile source of immediate and long-term energy requirement for growth and development. The two sugars that occur commonly in nature are sucrose and trehalose. Sucrose comprises one glucose and one fructose molecule; trehalose comprises two glucose molecules. Trehalose occurs in significant amounts in insects and fungi which greatly outnumber the plants. Surprisingly, in plants trehalose has been found in barely detectable amounts, if at all, raising the question `why did nature select sucrose instead of trehalose as the mobile energy source and as storage sugar for the plants'? Modelling revealed that when attached to the ribbon-shaped beta-1,4 glucan a trehalose molecule is shaped like a hook. This suggests that the beta-1,4 glucan chains with attached trehalose will fail to align to form inter-chain hydrogen bonds and coalesce into a cellulose microfibril, as a result of which in trehalose-accumulating plant cells, the cell wall will tend to become leaky. Thus in plants an evolutionary selection was made in favour of sucrose as the mobile energy source. Genetic engineering of plant cells for combating abiotic stresses through microbial trehalose-producing genes is fraught with risk of damage to plant cell walls.