Self-assembly and potassium ion triggered disruption of peptide-based soft structures

This report describes formation of soft vesicular structures by a tetrapeptide and its disruption triggered by potassium ions.     

Dependence of the fragility of a glass former on the softness of interparticle interactions

We study the influence of the softness of the interparticle interactions on the fragility of a glass former by considering three model binary mixture glass formers. The interaction potential between particles is a modified Lennard-Jones type potential, with the repulsive part of the potential varying with an inverse power q of the interparticle distance, and the attractive part varying with an inverse power p. We consider the combinations (12,11) (model I), (12,6) (model II), and (8,5) (model III) for (q,p) such that the interaction potential becomes softer from model I to III. We evaluate the kinetic fragilities from the temperature variation of diffusion coefficients and relaxation times, and a thermodynamic fragility from the temperature variation of the configurational entropy. We find that the kinetic fragility increases with increasing softness of the potential, consistent with previous results for these model systems, but at variance with the thermodynamic fragility, which decreases with increasing softness of the interactions, as well as expectations from earlier results. We rationalize our results by considering the full form of the Adam-Gibbs relation, which requires, in addition to the temperature dependence of the configurational entropy, knowledge of the high temperature activation energies in order to determine fragility. We show that consideration of the scaling of the high temperature activation energy with the liquid density, analyzed in recent studies, provides a partial rationalization of the observed behavior.     

Interaction of alcohols with 2-fluoro- and 4-fluorophenylacetylenes: infrared-optical double resonance spectroscopic and computational investigation

Alcohol complexes of 4-fluorophenylacetylene and 2-fluorophenylacetylene were investigated using IR-UV double resonance spectroscopy. Methanol forms a cyclic complex with both the fluorophenylacetylenes incorporating C-H···O and O-H···π hydrogen bonds, the structure of which is similar to that of the corresponding water complex but different from that of a phenylacetylene-methanol complex. The anti conformer of ethanol also binds in a similar fashion to both the fluorophenylacetylenes. Additionally, the gauche conformer of ethanol binds to 2-fluorophenylacetylene in a distinctly different structural motif that incorporates C-H···F and O-H···π hydrogen bonds. The OH group of trifluoroethanol interacts primarily with the π electron density of the C≡C bond. The π electron density of the C≡C bond is the principal point of interaction between the alcohols and both the fluorophenylacetylenes. The present results are indicative of the fact that fluorine substitution on the phenyl ring is sufficient to eliminate the subtle hydrogen bonding behavior of phenylacetylene.     

A discrete time model for software reliability with application to a flight control software

This work is motivated by a particular software reliability problem in a unit of flight control software developed by the Indian Space Research Organization (ISRO), in which the testing of the software is carried out in multiple batches, each consisting of several runs. As the errors are found during the runs within a batch, they are noted, but not debugged immediately; they are debugged only at the end of that particular batch of runs. In this work, we introduce a discrete time model suitable for this type of periodic debugging schedule and describe maximum likelihood estimation for the model parameters. This model is used to estimate the reliability of the software. We also develop a method to determine the additional number of error‐free test runs required for the estimated reliability to achieve a specific target with some high probability. We analyze the test data on the flight control software of ISRO. Copyright © 2011 John Wiley & Sons, Ltd.     

Thermal transport and strong mass renormalization in NiCl2-4SC(NH2)2

Several quantum paramagnets exhibit magnetic-field-induced quantum phase transitions to an antiferromagnetic state that exists for H c1 ≤ H ≤ H c2. For some of these compounds, there is a significant asymmetry between the low- and high-field transitions. We present specific heat and thermal conductivity measurements in NiCl2-4SC(NH2)2, together with calculations which show that the asymmetry is caused by a strong mass renormalization due to quantum fluctuations for H ≤ H c1 that are absent for H ≥ H c2. We argue that the enigmatic lack of asymmetry in thermal conductivity is due to a concomitant renormalization of the impurity scattering.     

Molecular simulation study of triangle-well fluids confined in slit pores

Grand canonical Monte Carlo simulations are used to study the behaviour of triangle-well (TW) fluids with variable well widths confined inside slit pores. The effect of individual factors influencing the properties of confined fluids such as fluid–fluid interactions, pore size and pore wall–fluid interactions are obtained using simulations as it is difficult to experimentally determine the same. An interesting observation of this study is that inside the narrow pore of slit height h* = 5 at the high-pressure condition of P* = 0.8, for the TW fluid with long-range attraction or for the fluid at a low temperature for even a short-range attraction, the density profiles show layering such that there is a sticking tendency of the particles at centre, while there is a depletion of particles near the wall (as the layers at the centre have higher density peak heights than near the walls).     

Low-Prandtl-number Rayleigh-Bénard convection with stress-free boundaries

Results of direct numerical simulations on Rayleigh-Bénard convection in low-Prandtl-number convection with stress-free horizontal boundaries are presented. Simulations are done in a three dimensional rectangular simulation box of dimensions L _x × L _y × 1. Instabilities and the corresponding fluid patterns near onset of convection are investigated by varying the horizontal aspect ratio η = L _y /L _x in a range 1 ≤ η ≤ 4. Fluid patterns are complex and unsteady at the instability onset for η ≥ 2. They consist of wavy rolls, rhombic patterns and oblique wavy rolls. The patterns near onset are time periodic for η < 2. We observe periodic wavy rolls for η = 4 / 3. Homoclinic bifurcations are observed for η = 1 for 0 ≤ Pr ≤ 0.03. We observe spontaneous breaking of a single limit cycle in two and again spontaneous merging of two limit cycles into one in a simulation box with η = 1, as the reduced Rayleigh number r = Ra/R a _c is raised at a fixed value of Pr. The effect of Prandtl number on the homoclinic bifurcations is also investigated. We also present a low-dimensional model, which captures the instability sequence quite accurately for η = 1.     

Simultaneous recovery of plutonium and americium from assorted analytical waste solutions using extraction chromatography

A rapid extraction chromatography based methodology was developed for simultaneous recovery of plutonium and americium from various kinds of analytical waste obtained during chemical quality control of plutonium based nuclear materials using sulphonic acid based actinide? resin. Efforts were made to understand the effect of initial feed acidity, gamma radiation and the concentrations of Am³⁺ and Pu⁴⁺ on their k _d. values. Processing of assorted analytical waste solutions through this method revealed that more than 95 % of Am³⁺ and 90 % of Pu⁴⁺ were adsorbed on the resin while iso- propanol can be successfully employed for the quantitative recovery of both the actinides from the loaded resin phase.     

Studies on the radiolytic stability of newly developed solvent systems containing four calix-crown-6 ligands for radio-cesium recovery

Radiolytic stability of solvent systems containing four commercially available calix-crown-6 ligands termed as calix[4]arene-bis-crown-6 (CC), calix[4]arene-benzo-bis-crown-6 (CBC), calix[4]arene-naphtho-bis-crown-6 (CNC), and bis-(octyloxy)calix[4]arene-mono-crown-6 (CMC) dissolved in phenyl trifluoromethyl sulphone (PTMS) was studied which followed the order: CBC > CC > CNC ~ CMC. The radiolytic stability was evaluated by the absolute distribution ratio (D _Cs) vales at a given concentration of nitric acid as well as the nature of the extracted species. The radiolytic degradation products were identified by GC–MS analysis. The present study indicates that CBC in PTMS can be used as a solvent for radio-cesium recovery with good recycling possibilities.