Stability of fluctuating and transient aggregates of amphiphilic solutes in aqueous binary mixtures: Studies of dimethylsulfoxide, ethanol, and tert-butyl alcohol

In aqueous binary mixtures, amphiphilic solutes such as dimethylsulfoxide (DMSO), ethanol, tertbutyl alcohol (TBA), etc., are known to form aggregates (or large clusters) at small to intermediate solute concentrations. These aggregates are transient in nature. Although the system remains homogeneous on macroscopic length and time scales, the microheterogeneous aggregation may profoundly affect the properties of the mixture in several distinct ways, particularly if the survival times of the aggregates are longer than density relaxation times of the binary liquid. Here we propose a theoretical scheme to quantify the lifetime and thus the stability of these microheterogeneous clusters, and apply the scheme to calculate the same for water-ethanol, water-DMSO, and water-TBA mixtures. We show that the lifetime of these clusters can range from less than a picosecond (ps) for ethanol clusters to few tens of ps for DMSO and TBA clusters. This helps explaining the absence of a strong composition dependent anomaly in water-ethanol mixtures but the presence of the same in water-DMSO and water-TBA mixtures. (C) 2013 AIP Publishing LLC.

Effect of analyte concentration on the laser-induced plasma temperature and electron density in liquid matrix

In the present work, we report spectroscopic studies of laser-induced plasmas produced by focusing the second harmonic (532nm) of a Nd:YAG laser onto the laminar flow of a liquid containing chromium. The plasma temperature is determined from the coupled Saha-Boltzmann plot and the electron density is evaluated from the Stark broadening of an ionic line of chromium Cr(II)] at 267.7nm. Our results reveal a decrease in plasma temperature with an increase in Cr concentration up to a certain concentration level; after that, it becomes approximately constant, while the electron density increases with an increase in analyte (Cr) concentration in liquid matrix.

Solvent Sensitivity of Protein Unfolding: Dynamical Study of Chicken Villin Headpiece Subdomain in Water Ethanol Binary Mixture

We carry out a series of long atomistic molecular dynamics simulations to study the unfolding of a small protein, chicken villin headpiece (HP-36), in water-ethanol (EtOH) binary mixture. The prime objective of this work is to explore the sensitivity of protein unfolding dynamics toward increasing concentration of the cosolvent and unravel essential features of intermediates formed in search of a dynamical pathway toward unfolding. In water ethanol binary mixtures, HP-36 is found to unfold partially, under ambient conditions, that otherwise requires temperature as high as similar to 600 K to denature in pure aqueous solvent. However, an interesting course of pathway is observed to be followed in the process, guided by the formation of unique intermediates. The first step of unfolding is essentially the separation of the cluster formed by three hydrophobic (phenylalanine) residues, namely, Phe-7, Phe-11, and Phe-18, which constitute the hydrophobic core, thereby initiating melting of helix-2 of the protein. The initial steps are similar to temperature-induced unfolding as well as chemical unfolding using DMSO as cosolvent. Subsequent unfolding steps follow a unique path. As water-ethanol shows composition-dependent anomalies, so do the details of unfolding dynamics. With an increase in cosolvent concentration, different partially unfolded intermediates are found to be formed. This is reflected in a remarkable nonmonotonic composition dependence of several order parameters, including fraction of native contacts and protein-solvent interaction energy. The emergence of such partially unfolded states can be attributed to the preferential solvation of the hydrophobic residues by the ethyl groups of ethanol. We further quantify the local dynamics of unfolding by using a Marcus-type theory.

Anomalous phase transitions in soft colloid-polymer binary mixtures

We have shown earlier [1] that these PGNPs resemble star polymers or spherical brushes in terms of their morphology in the melt. However, these particles show dynamics in melt which is quite different from other soft colloidal particles. Since most of the work on soft colloidal particles have been performed in solutions we have now explored the phase behavior of the PGNPs in good solvent using microscopic structural and dynamical measurements on binary mixtures of homopolymers and soft colloids consisting of polymer grafted nanoparticles. We observe anomalous structural and dynamical phase transitions of these binary mixtures, including appearance of spontaneous orientational alignment and logarithmic structural relaxations, as a function of added homopolymers of different molecular weights. Our experiments points to the possibility of exploiting the phase space in density and homopolymer size, of such hybrid systems, to create new materials with unique properties.

Multivariate Granger causality: an estimation framework based on factorization of the spectral density matrix

Granger causality is increasingly being applied to multi-electrode neurophysiological and functional imaging data to characterize directional interactions between neurons and brain regions. For a multivariate dataset, one might be interested in different subsets of the recorded neurons or brain regions. According to the current estimation framework, for each subset, one conducts a separate autoregressive model fitting process, introducing the potential for unwanted variability and uncertainty. In this paper, we propose a multivariate framework for estimating Granger causality. It is based on spectral density matrix factorization and offers the advantage that the estimation of such a matrix needs to be done only once for the entire multivariate dataset. For any subset of recorded data, Granger causality can be calculated through factorizing the appropriate submatrix of the overall spectral density matrix.

Polymer-Derived In-Situ Metal Matrix Composites Created by Direct Injection of a Liquid Polymer into Molten Magnesium

We show that a liquid organic precursor can be injected directly into molten magnesium to produce nanoscale ceramic dispersions within the melt. The castings made in this way possess good resistance to tensile deformation at 673 K (400 degrees C), confirming the non-coarsening nature of these dispersions. Direct liquid injection into molten metals is a significant step toward inserting different chemistries of liquid precursors to generate a variety of polymer-derived metal matrix composites. (C) The Minerals, Metals & Materials Society and ASM International 2013

Goldstone modes and bifurcations in phase-separated binary condensates at finite temperature

We show that the third Goldstone mode, which emerges in binary condensates at phase separation, persists to higher interspecies interaction for density profiles where one component is surrounded on both sides by the other component. This is not the case with symmetry-broken density profiles where one species is entirely to the left and the other is entirely to the right. We, then, use Hartree-Fock-Bogoliubov theory with Popov approximation to examine the mode evolution at T not equal 0 and demonstrate the existence of mode bifurcation near the critical temperature. The Kohn mode, however, exhibits deviation from the natural frequency at finite temperatures after the phase separation. This is due to the exclusion of the noncondensate atoms in the dynamics.

Calibration Curve with Improved Limit of Detection for Cadmium in Soil: An Approach to Minimize the Matrix Effect in Laser-Induced Breakdown Spectroscopic Analysis

The present article describes a working or combined calibration curve in laser-induced breakdown spectroscopic analysis, which is the cumulative result of the calibration curves obtained from neutral and singly ionized atomic emission spectral lines. This working calibration curve reduces the effect of change in matrix between different zone soils and certified soil samples because it includes both the species' (neutral and singly ionized) concentration of the element of interest. The limit of detection using a working calibration curve is found better as compared to its constituent calibration curves (i.e., individual calibration curves). The quantitative results obtained using the working calibration curve is in better agreement with the result of inductively coupled plasma-atomic emission spectroscopy as compared to the result obtained using its constituent calibration curves.

In-situ Stabilization of Tin Nanoparticles in Porous Carbon Matrix derived from Metal Organic Framework: High Capacity and High Rate Capability Anodes for Lithium-ion Batteries

It is a formidable challenge to arrange tin nanoparticles in a porous matrix for the achievement of high specific capacity and current rate capability anode for lithium-ion batteries. This article discusses a simple and novel synthesis of arranging tin nanoparticles with carbon in a porous configuration for application as anode in lithium-ion batteries. Direct carbonization of synthesized three-dimensional Sn-based MOF: K2Sn2(1,4-bdc)(3)](H2O) (1) (bdc = benzenedicarboxylate) resulted in stabilization of tin nanoparticles in a porous carbon matrix (abbreviated as Sn@C). Sn@C exhibited remarkably high electrochemical lithium stability (tested over 100 charge and discharge cycles) and high specific capacities over a wide range of operating currents (0.2-5 Ag-1). The novel synthesis strategy to obtain Sn@C from a single precursor as discussed herein provides an optimal combination of particle size and dispersion for buffering severe volume changes due to Li-Sn alloying reaction and provides fast pathways for lithium and electron transport.

Vortex reconnections between coreless vortices in binary condensates

Vortex reconnections plays an important role in the turbulent flows associated with the superfluids. To understand the dynamics, we examine the reconnections of vortex rings in the superfluids of dilute atomic gases confined in trapping potentials using Gross-Petaevskii equation. Further more we study the reconnection dynamics of coreless vortex rings, where one of the species can act as a tracer.

Effect of adsorbate loading on selectivity during adsorption of C/C and C/C n-alkane binary mixtures in silicalite

Adsorption experiments of mixtures of long chain alkanes into silicalite under liquid phase conditions show selectivity inversion and azeotrope formation. These effects are due to the subtle interplay between the size of the adsorbed molecules and pore topology of the adsorbent. In this study, the selective uptake of lighter component during liquid phase adsorption of C/C and C/C n-alkane binary mixtures in the zeolite silicalite is understood through configurational bias grand-canonical Monte Carlo molecular simulation technique and a coarse-grained siting analysis. The simulations are conducted under conditions of low and intermediate levels of loading. The siting pattern of the adsorbates inside the zeolite pores explain the selectivity as seen in experiments.

Magnetism and superconductivity in Sb-doped binary and ternary iron chalcogenide single crystals

We report the single crystal growth of antimony doped Fe1+yTe and Fe1+yTe0.5Se0.5 (Fe1+ySbxTe1-x (x=0, 2%, 5%) and Fe1+yTe0.49Se0.49Sb0.02) by a modified horizontal Bridgman method. Growth parameters are optimized to obtain high quality single crystals. The antiferromagnetic (AFM) transition at T-N = 62.2 K which is a first order transition, shifts to lower temperature on doping in Fe1+yTe. Alternately when the chalcogen site of the ternary compound Fe1+yTe0.5Se0.5 is doped with Sb, superconductivity is preserved albeit the superconducting transition temperature (T-C) falls slightly and a concomitant reduction occurs in superconducting volume fraction. (C) 2013 Elsevier B.V. All rights reserved,

Calculation of three-phase methane-ethane binary clathrate hydrate phase equilibrium from Monte Carlo molecular simulations

Methane and ethane are the simplest hydrocarbon molecules that can form clathrate hydrates. Previous studies have reported methods for calculating the three-phase equilibrium using Monte Carlo simulation methods in systems with a single component in the gas phase. Here we extend those methods to a binary gas mixture of methane and ethane. Methane-ethane system is an interesting one in that the pure components form sII clathrate hydrate whereas a binary mixture of the two can form the sII clathrate. The phase equilibria computed from Monte Carlo simulations show a good agreement with experimental data and are also able to predict the sI-sII structural transition in the clathrate hydrate. This is attributed to the quality of the TIP4P/Ice and TRaPPE models used in the simulations. (C) 2014 Elsevier B.V. All rights reserved.

The generalized Onsager model for a binary gas mixture

The Onsager model for the secondary flow field in a high-speed rotating cylinder is extended to incorporate the difference in mass of the two species in a binary gas mixture. The base flow is an isothermal solid-body rotation in which there is a balance between the radial pressure gradient and the centrifugal force density for each species. Explicit expressions for the radial variation of the pressure, mass/mole fractions, and from these the radial variation of the viscosity, thermal conductivity and diffusion coefficient, are derived, and these are used in the computation of the secondary flow. For the secondary flow, the mass, momentum and energy equations in axisymmetric coordinates are expanded in an asymptotic series in a parameter epsilon = (Delta m/m(av)), where Delta m is the difference in the molecular masses of the two species, and the average molecular mass m(av) is defined as m(av) = (rho(w1)m(1) + rho(w2)m(2))/rho(w), where rho(w1) and rho(w2) are the mass densities of the two species at the wall, and rho(w) = rho(w1) + rho(w2). The equation for the master potential and the boundary conditions are derived correct to O(epsilon(2)). The leading-order equation for the master potential contains a self-adjoint sixth-order operator in the radial direction, which is different from the generalized Onsager model (Pradhan & Kumaran, J. Fluid Mech., vol. 686, 2011, pp. 109-159), since the species mass difference is included in the computation of the density, viscosity and thermal conductivity in the base state. This is solved, subject to boundary conditions, to obtain the leading approximation for the secondary flow, followed by a solution of the diffusion equation for the leading correction to the species mole fractions. The O(epsilon) and O(epsilon(2)) equations contain inhomogeneous terms that depend on the lower-order solutions, and these are solved in a hierarchical manner to obtain the O(epsilon) and O(epsilon(2)) corrections to the master potential. A similar hierarchical procedure is used for the Carrier-Maslen model for the end-cap secondary flow. The results of the Onsager hierarchy, up to O(epsilon(2)), are compared with the results of direct simulation Monte Carlo simulations for a binary hard-sphere gas mixture for secondary flow due to a wall temperature gradient, inflow/outflow of gas along the axis, as well as mass and momentum sources in the flow. There is excellent agreement between the solutions for the secondary flow correct to O(epsilon(2)) and the simulations, to within 15 %, even at a Reynolds number as low as 100, and length/diameter ratio as low as 2, for a low stratification parameter A of 0.707, and when the secondary flow velocity is as high as 0.2 times the maximum base flow velocity, and the ratio 2 Delta m/(m(1) + m(2)) is as high as 0.5. Here, the Reynolds number Re = rho(w)Omega R-2/mu, the stratification parameter A = root m Omega R-2(2)/(2k(B)T), R and Omega are the cylinder radius and angular velocity, m is the molecular mass, rho(w) is the wall density, mu is the viscosity and T is the temperature. The leading-order solutions do capture the qualitative trends, but are not in quantitative agreement.