Assessing the critical concentration of NH2 terminal groups on the surface of MWNTs towards chain scission of PC in PC/SAN blends: effect on dispersion, electrical conductivity and EMI shielding

The localization and dispersion quality of as received NH2 terminated multiwall carbon nanotubes (MWNT-I) and ethylene diamine (EDA) functionalized MWNTs in melt mixed blends of polycarbonate ( PC) and poly(styrene-co-acrylonitrile) (SAN) were assessed in this study using rheo-electrical and electromagnetic interference (EMI) shielding measurements. In order to improve the dispersion quality and also to selectively localize MWNTs in the PC phase of the blends, EDA was grafted onto MWNTs by two different strategies like diazonium reaction of the para-substituted benzene ring of MWNTs with EDA ( referred to as MWNT-II) and acylation of carboxyl functionalized MWNTs with thionyl chloride ( referred to as MWNT-III). By this approach we could systematically vary the concentration of NH2 functional groups on the surface of MWNTs at a fixed concentration (1 wt%) in PC/SAN blends. XPS was carried to evaluate the % concentration of N in different MWNTs and was observed to be highest for MWNT-III manifesting in a large surface coverage of EDA on the surface of MWNTs. Viscoelastic properties and melt electrical conductivities were measured to assess the dispersion quality of MWNTs using a rheo-electrical set-up both in the quiescent as well as under steady shear conditions. Rheological properties revealed chain scission of PC in the presence of MWNT-III which is due to specific interactions between EDA and PC leading to smaller PC grafts on the surface of MWNTs. The observed viscoelastic properties in the blends were further correlated with the phase morphologies under quiescent and annealed conditions. Electromagnetic interference (EMI) shielding effectiveness in X and K-u-band frequencies were measured to explore these composites for EMI shielding applications. Interestingly, MWNT-II showed the highest electrical conductivity and EMI shielding in the blends.

Topological blocking in quantum quench dynamics

We study the nonequilibrium dynamics of quenching through a quantum critical point in topological systems, focusing on one of their defining features: ground-state degeneracies and associated topological sectors. We present the notion of ``topological blocking,'' experienced by the dynamics due to a mismatch in degeneracies between two phases, and we argue that the dynamic evolution of the quench depends strongly on the topological sector being probed. We demonstrate this interplay between quench and topology in models stemming from two extensively studied systems, the transverse Ising chain and the Kitaev honeycomb model. Through nonlocal maps of each of these systems, we effectively study spinless fermionic p-wave paired topological superconductors. Confining the systems to ring and toroidal geometries, respectively, enables us to cleanly address degeneracies, subtle issues of fermion occupation and parity, and mismatches between topological sectors. We show that various features of the quench, which are related to Kibble-Zurek physics, are sensitive to the topological sector being probed, in particular, the overlap between the time-evolved initial ground state and an appropriate low-energy state of the final Hamiltonian. While most of our study is confined to translationally invariant systems, where momentum is a convenient quantum number, we briefly consider the effect of disorder and illustrate how this can influence the quench in a qualitatively different way depending on the topological sector considered.

A Stochastic Chemical Dynamic Approach to Correlate Autoimmunity and Optimal Vitamin-D Range

Motivated by several recent experimental observations that vitamin-D could interact with antigen presenting cells (APCs) and T-lymphocyte cells (T-cells) to promote and to regulate different stages of immune response, we developed a coarse grained but general kinetic model in an attempt to capture the role of vitamin-D in immunomodulatory responses. Our kinetic model, developed using the ideas of chemical network theory, leads to a system of nine coupled equations that we solve both by direct and by stochastic (Gillespie) methods. Both the analyses consistently provide detail information on the dependence of immune response to the variation of critical rate parameters. We find that although vitamin-D plays a negligible role in the initial immune response, it exerts a profound influence in the long term, especially in helping the system to achieve a new, stable steady state. The study explores the role of vitamin-D in preserving an observed bistability in the phase diagram (spanned by system parameters) of immune regulation, thus allowing the response to tolerate a wide range of pathogenic stimulation which could help in resisting autoimmune diseases. We also study how vitamin-D affects the time dependent population of dendritic cells that connect between innate and adaptive immune responses. Variations in dose dependent response of anti-inflammatory and pro-inflammatory T-cell populations to vitamin-D correlate well with recent experimental results. Our kinetic model allows for an estimation of the range of optimum level of vitamin-D required for smooth functioning of the immune system and for control of both hyper-regulation and inflammation. Most importantly, the present study reveals that an overdose or toxic level of vitamin-D or any steroid analogue could give rise to too large a tolerant response, leading to an inefficacy in adaptive immune function.

Critical cysteines in Akt1 regulate its activity and proteasomal degradation: implications for neurodegenerative diseases

Impaired Akt1 signaling is observed in neurodegenerative diseases, including Parkinson's disease (PD). In PD models oxidative modification of Akt1 leads to its dephosphorylation and consequent loss of its kinase activity. To explore the underlying mechanism we exposed Neuro2A cells to cadmium, a pan inhibitor of protein thiol disulfide oxidoreductases, including glutaredoxin 1 (Grx1), or downregulated Grx1, which led to dephosphorylation of Akt1, loss of its kinase activity, and also decreased Akt1 protein levels. Mutation of cysteines to serines at 296 and 310 in Akt1 did not affect its basal kinase activity but abolished cadmium- and Grx1 downregulation-induced reduction in Akt1 kinase activity, indicating their critical role in redox modulation of Akt1 function and turnover. Cadmium-induced decrease in phosphorylated Akt1 correlated with increased association of wild-type (WT) Akt1 with PP2A, which was absent in the C296-310S Akt1 mutant and was also abolished by N-acetylcysteine treatment. Further, increased proteasomal degradation of Akt1 by cadmium was not seen in the C296-310S Akt1 mutant, indicating that oxidation of cysteine residues facilitates degradation of WT Akt1. Moreover, preventing oxidative modification of Akt1 cysteines 296 and 310 by mutating them to serines increased the cell survival effects of Akt1. Thus, in neurodegenerative states such as PD, maintaining the thiol status of cysteines 296 and 310 in Akt1 would be critical for Akt1 kinase activity and for preventing its degradation by proteasomes. Preventing downregulation of Akt signaling not only has long-range consequences for cell survival but could also affect the multiple roles that Ala plays, including in the Akt-mTOR signaling cascade. (C) 2014 Elsevier Inc. All rights reserved.

New insights into the development of microstructure and deformation texture in nickel-60 wt.% cobalt alloy

The present study investigates the critical role of deformation twinning and Bs-type shear bands in the evolution of deformation texture in a low stacking fault energy Ni-60Co alloy up to very large rolling strain (epsilon(t) approximate to 4). The alloy develops a strong brass-type rolling texture, and its formation is initiated at the early stages of deformation. Extensive twinning is observed at the intermediate stages of deformation, which causes significant texture reorientation towards alpha-fiber. A pseudo-in-situ electron back-scattered diffraction technique adopted to capture orientation changes within individual grains during the early stages suggests that twinning should be subsequently aided by crystallographic slip to attain alpha-fiber (< 1 1 0 >parallel to ND) orientations. Beyond 40% reduction, deformation is dominated by Bs-type shear bands, and the banding coincides with the evolution of < 1 1 1 >parallel to ND components. The volume fraction of shear bands is significant at higher strains, and crystallites within the bands preferentially show < 1 1 0 >parallel to ND components. The absence of the Cu {1 1 2}< 1 1 1 > component in the initial texture, and subsequently during rolling, indicates that, for the evolution of a brass-type texture, the presence of the Cu component is not a necessary condition. The final rolling texture is a synergistic effect of deformation twinning and shear banding. (C) 2014 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

SOME UNSTABLE CRITICAL METRICS FOR THE L-n/2-NORM OF THE CURVATURE TENSOR

We consider the Riemannian functional defined on the space of Riemannian metrics with unit volume on a closed smooth manifold M given by R-n/2(g) := integral(M) vertical bar R(g)vertical bar(n//2) dv(g) where R(g), dv(g) denote the Riemannian curvature and volume form corresponding to g. We show that there are locally symmetric spaces which are unstable critical points for this functional.

A critical examination of the paradox of strength and ductility in ultrafine-grained metals

The paradox of strength and ductility is now well established and denotes the difficulty of simultaneously achieving both high strength and high ductility. This paradox was critically examined using a cast Al-7% Si alloy processed by high-pressure torsion (HPT) for up to 10 turns at a temperature of either 298 or 445 K. This processing reduces the grain size to a minimum of similar to 0.4 mu m and also decreases the average size of the Si particles. The results show that samples processed to high numbers of HPT turns exhibit both high strength and high ductility when tested at relatively low strain rates and the strain rate sensitivity under these conditions is similar to 0.14 which suggests that flow occurs by some limited grain boundary sliding and crystallographic slip. The results are also displayed on the traditional diagram for strength and ductility and they demonstrate the potential for achieving high strength and high ductility by increasing the number of turns in HPT.

Molecular effects of encapsulation of glucose oxidase dimer by graphene

Knowing the nature of the enzyme-graphene interface is critical for a design of graphene-based biosensors. Extensive contacts between graphene and enzyme could be obtained by employing a suitable encapsulation which does not impede its enzymatic reaction. We have performed molecular dynamics simulations to obtain an insight on many forms of contact between glucose oxidase dimer and the single-layer graphene nano-sheets. The unconnected graphene sheets tended to form a flat stack regardless of their initial positions around the enzyme, whereas the same graphene sheets linked together formed a flower-like shape engendering different forms of wrapping of the enzyme. During the encapsulation no core hydrophobic residues of the enzyme were exposed. Since the polar and charged amino acids populated the enzyme's surface we also estimated, using DFT calculations, the interaction energies of individual polar and charged amino acid residues with graphene. It was found that the negatively charged residues can bind to graphene unexpectedly strongly; however, the main effect of encapsulation comes from the overlap of adjacent edges of graphene sheets.

A critical review of the definition of FRA resonance frequency of transformers as per IEEE Std C57.149-2012

The explanation of resonance given in IEEE Std C57.149-2012 to define resonance during frequency response analysis (FRA) measurements on transformers implicitly uses the conditions prevalent during resonance in a series R-L-C circuit. This dependence is evident from the two assertions made in the definition, viz., resulting in zero net reactive impedance, and, accompanied by a zero value appearing in the phase angle of the frequency response function. These two conditions are satisfied (at resonance) only in a series R-L-C circuit and certainly not in a transformer, as has been assumed in the Standard. This can be proved by considering a ladder-network model. Circuit analysis of this ladder network reveals the origin of this fallacy and proves that, at resonance, neither is the ladder network purely resistive and nor is the phase angle (between input voltage and input current) always zero. Also, during FRA measurements, it is often seen that phase angle does not traverse the conventional cyclic path from +90 degrees to -90 degrees (or vice versa) at all resonant frequencies. This peculiar feature can also be explained using pole-zero maps. Simple derivations, simulations and experimental results on an actual winding are presented. In summary, authors believe that this study dispels existing misconceptions about definition of FRA resonance and provides material for its correction in IEEE Std C57.149-2012. (C) 2014 Elsevier B.V. All rights reserved.

A trade-off between maxima in efficiency and specific work output of super- and trans-critical CO2 Brayton cycles

Several operational aspects for thermal power plants in general are non-intuitive and involve simultaneous optimization of a number of operational parameters. In the case of solar operated power plants, it is even more difficult due to varying heat source temperatures induced by variability in insolation levels. This paper introduces a quantitative methodology for load regulation of a CO2 based Brayton cycle power plant using the `thermal efficiency and specific work output' coordinate system. The analysis shows that a transcritical CO2 cycle offers more flexibility under part load performance than the supercritical cycle in case of non-solar power plants. However, for concentrated solar power, where efficiency is important, supercritical CO2 cycle fares better than transcritical CO2 cycle. A number of empirical equations relating heat source temperature, high side pressure with efficiency and specific work output are proposed which could assist in generating control algorithms. (C) 2015 Elsevier B.V. All rights reserved.

Lactoylglutathione lyase, a critical enzyme in methylglyoxal detoxification, contributes to survival of Salmonella in the nutrient rich environment

Glyoxalase I which is synonymously known as lactoylglutathione lyase is a critical enzyme in methylglyoxal (MG) detoxification. We assessed the STM3117 encoded lactoylglutathione lyase (Lgl) of Salmonella Typhimurium, which is known to function as a virulence factor, due in part to its ability to detoxify methylglyoxal. We found that STM3117 encoded Lgl isomerises the hemithioacetal adduct of MG and glutathione (GSH) into S-lactoylglutathione. Lgl was observed to be an outer membrane bound protein with maximum expression at the exponential growth phase. The deletion mutant of S. Typhimurium (lgl) exhibited a notable growth inhibition coupled with oxidative DNA damage and membrane disruptions, in accordance with the growth arrest phenomenon associated with typical glyoxalase I deletion. However, growth in glucose minimal medium did not result in any inhibition. Endogenous expression of recombinant Lgl in serovar Typhi led to an increased resistance and growth in presence of external MG. Being a metalloprotein, Lgl was found to get activated maximally by Co2+ ion followed by Ni2+, while Zn2+ did not activate the enzyme and this could be attributed to the geometry of the particular protein-metal complex attained in the catalytically active state. Our results offer an insight on the pivotal role of the virulence associated and horizontally acquired STM3117 gene in non-typhoidal serovars with direct correlation of its activity in lending survival advantage to Salmonella spp.

Influence of initial degree of saturation on swell pressures of compacted Barmer bentonite specimens

Densely compacted bentonite or bentonite-sand mixture has been identified as suitable buffer in deep geological repositories as its exceptionally high swelling capacity enables tight contact between the waste canister and surrounding rock. The degree of saturation of the compacted bentonite buffer can increase upon ingress of groundwater from the surrounding rock mass or decrease from evaporation due to high temperature (50-210 degrees C) derived from the waste canister. Available studies indicate that the influence of initial moisture content or degree of saturation on the swell pressure or swell potential of compacted bentonites is unclear. Some studies suggest that initial degree of saturation has an influence, while others suggest that it does not have bearing on the swell pressure of compacted bentonites. This paper examines the influence of initial degree of saturation in montmorillonite voids (termed,S-r,S-MF) on swell pressure of compacted Barmer bentonite-sand mixtures (dry density range: 1.4-2 Mg/m(3)) from micro-structural considerations. The experimental results bring out that, constant dry density specimens that developed similar number of hydration layers upon wetting developed comparable swell pressures and were unaffected by variations in initial S-r,S-MF values. Comparatively, constant dry density specimens that developed dis-similar number of hydration layers upon wetting established different swell pressures and were responsive to variations in initial S-r,S-MF. (C) 2015 Elsevier Ltd. All rights reserved.

Stability of Filaments in Star-Forming Clouds and the Formation of Prestellar Cores in Them

The exact process(es) that generate(s) dense filaments which then form prestellar cores within them is unclear. Here we study the formation of a dense filament using a relatively simple set-up of a pressure-confined, uniform-density cylinder. We examine if its propensity to form a dense filament and further, to the formation of prestellar cores along this filament, bears on the gravitational state of the initial volume of gas. We report a radial collapse leading to the formation of a dense filamentary cloud is likely when the initial volume of gas is at least critically stable (characterised by the approximate equality between the mass line-density for this volume and its maximum value). Though self-gravitating, this volume of gas, however, is not seen to be in free-fall. This post-collapse filament then fragments along its length due to the growth of a Jeans-like instability to form prestellar cores. We suggest dense filaments in typical star-forming clouds classified as gravitationally super-critical under the assumption of: (i) isothermality when in fact, they are not, and (ii) extended radial profiles as against pressure-truncated, that significantly over-estimates their mass line-density, are unlikely to experience gravitational free-fall. The radial density and temperature profile derived for this post-collapse filament is consistent with that deduced for typical filamentary clouds mapped in recent surveys of nearby star-forming regions.

A critical review on in situ reduction of graphene oxide during preparation of conducting polymeric nanocomposites

Graphene oxide (GO), prepared by chemical oxidation of graphite, serves as a building block for developing polymeric nanocomposites. However, their application in electrical conductivity is limited by the fact that the oxygen sites on GO trap electrons and impede charge transport. Conducting nanocomposites can be developed by reducing GO. Various strategies have been adopted to either reduce GO ex situ, before the composite preparation, or in situ during the development of the nanocomposites. The current state of research on in situ reduction of GO during the preparation of conducting polymeric nanocomposites is discussed in this review. The mechanism and the efficiency of reduction is discussed with respect to various strategies employed during the preparation of the nanocomposite, the type of polymer used, and the processing conditions employed, etc. Its overall effect on the electrical conductivity of the nanocomposites is also discussed and the future outlook in this area is presented.

Phase formation and stability of alloy phases in free nanoparticles: some insights

This paper explores phase formation and phase stability in free nanoparticles of binary alloys. A procedure for estimating the size and composition dependent free energies incorporating the contributions from the interfaces has been presented. Both single phase solid solution and two phase morphology containing interphase interfaces have been considered. A free energy scenario has been evaluated for two binary alloy systems Ag-Ni and Ag-Cu to predict the microstructure of the alloy nanoparticles at different size ranges as a function of composition. Both Ag-Cu and Ag-Ni systems exhibit wide bulk immiscibility. Ag-Ni nanoparticles were synthesized using the wet chemical synthesis technique whereas Ag-Cu nanoparticles were synthesized using laser ablation of a Ag-Cu target immersed in distilled water. Microstructural and compositional characterization of Ag-Ni and Ag-Cu nanoparticles on a single nanoparticle level was conducted using transmission electron microscopy. Nanoparticle microstructures observed from the microscopic investigation have been correlated with thermodynamic calculation results. It is shown that the observed two phase microstructure consisting of Ag-Ni solid solution in partial decomposed state coexisting with pure Ag phases in the case of Ag-Ni nanoparticles can be only be rationalized by invoking the tendency for phase separation of an initial solid solution with increase in nanoparticle size. Smaller sized Ag-Ni nanoparticles prefer a single phase solid solution microstructure. Due to an increase in particle size during the synthesis process the initial solid solution decomposes into an ultrafine scale phase separated microstructure. We have shown that it is necessary to invoke critical point phenomenon and wetting transition in systems showing a critical point that leads to phase separated Ag-Ni nanoparticles providing a catalytic substrate for the nucleation of equilibrium Ag over it. In the case of the Ag-Cu system, we report the experimental observation of a core shell structure at small sizes. This can be rationalized in terms of a metastable solid solution. It is argued that the nucleation barrier can prevent the formation of biphasic morphology with an internal interface. In such a situation, demixing of the solid solution can bring the system to a lower energy configuration. This has lead to the observed core-shell morphology in the Ag-Cu system during room temperature synthesis.