Planar triazinium cations from vanadyl-mediated ring cyclizations: the thiazole species for efficient nuclear staining and photocytotoxicity

Planar triazinium cationic species from vanadyl-assisted cyclization of 1-(2-thiazolylazo)-2-naphthol (H-TAN, 1), 1-(2-pyridylazo)-2-naphthol (H-PAN, 2), 2-(2'-thiazolylazo)-p-cresol (H-TAC, 3) and 6-(2'-thiazolylazo)- resorcinol (H-TAR, 5) were prepared and characterized. A dioxovanadium(V) species VO2(TAR)] (4) was also isolated. Compounds 1, 2 and 4 were structurally characterized. Both 1 and 2 have planar structures. Complex 4 has (VO3N2)-O-V coordination geometry. The cyclised triazinium compound forms a radical species within -0.06 to -0.29 V vs. SCE in DMF-0.1 M tetrabutylammonium perchlorate with a second response due to formation of an anionic species. A confocal microscopic study showed higher nuclear uptake for 1 having a fused thiazole moiety than 2 with a fused pyridine ring. The compounds showed a partial intercalative mode of binding to calf thymus DNA. Compound 1 showed plasmid DNA photo-cleavage activity under argon and photocytotoxicity in HeLa and MCF-7 cells with IC50 values of 15.1 and 3.4 mu M respectively in visible light of 400-700 nm, while being essentially non-toxic in the dark with IC50 values of 90.4 and 21.9 mu M. ATDDFT study was done to rationalize the experimental data.

Mixing enhancement in a compact trapped vortex combustor

Previous studies on a single-cavity, compact trapped vortex combustor concept showed good flame stability for a wide range of flow conditions. However, achieving good mixing between cavity products and mainstream flow was still a major challenge. In the present study, a passive mixing enhancement strategy of using inclined struts along with a flow guide vane is presented and experimentally tested at atmospheric pressure conditions. Results show excellent mixing and consequently low values of the combustor exit pattern factor in the range of 0.1 and small flame lengths (57 times the main-duct depth). The pressure drop is small in the range of 0.35%, and NOx levels of the order of 12ppm are achieved. The flame stability is excellent, and combustion efficiency is reasonable in the range of 96%. The effectiveness of the proposed strategy is explained on the basis of in-situ OH chemiluminescence images and prior numerical simulations of the resulting complex flow field. The flow guide vane is observed to lead to a counterclockwise cavity vortex, which is conducive to the rise of cavity combustion products along the inclined struts and subsequent mixing with the mainstream flow.

Performance analysis of adaptive physical layer network coding for wireless two-way relaying

The performance analysis of adaptive physical layer network-coded two-way relaying scenario is presented which employs two phases: Multiple access (MA) phase and Broadcast (BC) phase. The deep channel fade conditions which occur at the relay referred as the singular fade states fall in the following two classes: (i) removable and (ii) non-removable singular fade states. With every singular fade state, we associate an error probability that the relay transmits a wrong network-coded symbol during the BC phase. It is shown that adaptive network coding provides a coding gain over fixed network coding, by making the error probabilities associated with the removable singular fade states contributing to the average Symbol Error Rate (SER) fall as SNR-2 instead of SNR-1. A high SNR upper-bound on the average end-to-end SER for the adaptive network coding scheme is derived, for a Rician fading scenario, which is found to be tight through simulations. Specifically, it is shown that for the adaptive network coding scheme, the probability that the relay node transmits a wrong network-coded symbol is upper-bounded by twice the average SER of a point-to-point fading channel, at high SNR. Also, it is shown that in a Rician fading scenario, it suffices to remove the effect of only those singular fade states which contribute dominantly to the average SER.

Thermoelectric performance of a single-layer graphene sheet for energy harvesting

We investigate the thermoelectric (TE) figure-of-merit of a single-layer graphene (SLG) sheet by a physics-based analytical technique. We first develop analytical models of electrical and thermal resistances and the Seebeck coefficient of SLG by considering electron interactions with the in-plane and flexural phonons. Using those models, we show that both the figure-of-merit and the TE efficiency can be substantially increased with the addition of isotope doping as it significantly reduces the phonon-dominated thermal conductivity. In addition, we report that the TE open circuit output voltage and output power depends weakly on the SLG sheet dimensions and sheet concentration in the strongly diffusive regime. Proposed models agree well with the available experimental data and demonstrate the immense potential of graphene for waste-heat recovery application.

Yield stress, thixotropy and shear banding in a dilute aqueous suspension of few layer graphene oxide platelets

We demonstrate a rigidity percolation transition and the onset of yield stress in a dilute aqueous dispersion of graphene oxide platelets (aspect ratio similar to 5000) above a critical volume fraction of 3.75 x 10(-4) with a percolation exponent of 2.4 +/- 0.1. The viscoelastic moduli of the gel at rest measured as a function of time indicate the absence of structural evolution of the 3D percolated network of disks. However a shear-induced aging giving rise to a compact jammed state and shear rejuvenation indicating a homogenous flow is observed when a steady shear stress (sigma) is imposed in creep experiments. We construct a shear diagram (sigma vs. volume fraction phi) and the critical stress above which shear rejuvenation occurs is identified as the yield stress sigma(y) of the gel. The minimum steady state shear rate (gamma) over dot(m) obtained from creep experiments agrees well with the end of the plateau region in a controlled shear rate flow curve, indicating a shear localization below (gamma) over dot(m). A steady state shear banding in the plateau region of the flow curve observed in particle velocimetry measurements in a Couette geometry confirms that the dilute suspensions of GO platelets form a thixotropic yield stress fluid.

Dynamics of the Indian-Ocean oxygen minimum zones

In the Indian Ocean, mid-depth oxygen minimum zones (OMZs) occur in the Arabian Sea and the Bay of Bengal. The lower part of the Arabian-Sea OMZ (ASOMZ; below 400 m) intensifies northward across the basin; in contrast, its upper part (above 400 m) is located in the central/eastern basin, well east of the most productive regions along the western boundary. The Bay-of-Bengal OMZ (BBOMZ), although strong, is weaker than the ASOMZ. To investigate the processes that maintain the Indian-Ocean OMZs, we obtain a suite of solutions to a coupled biological/physical model. Its physical component is a variable-density, 6 1/2-layer model, in which each layer corresponds to a distinct dynamical regime or water-mass type. Its biological component has six compartments: nutrients, phytoplankton, zooplankton, two size classes of detritus, and oxygen. Because the model grid is non-eddy resolving (0.5 degrees), the biological model also includes a parameterization of enhanced mixing based on the eddy kinetic energy derived from satellite observations. To explore further the impact of local processes on OMZs, we also obtain analytic solutions to a one-dimensional, simplified version of the biological model. Our control run is able to simulate basic features of the oxygen, nutrient, and phytoplankton fields throughout the Indian Ocean. The model OMZs result from a balance, or lack thereof, between a sink of oxygen by remineralization and subsurface oxygen sources due primarily to northward spreading of oxygenated water from the Southern Hemisphere, with a contribution from Persian-Gulf water in the northern Arabian Sea. The northward intensification of the lower ASOMZ results mostly from horizontal mixing since advection is weak in its depth range. The eastward shift of the upper ASOMZ is due primarily to enhanced advection and vertical eddy mixing in the western Arabian Sea, which spread oxygenated waters both horizontally and vertically. Advection carries small detritus from the western boundary into the central/eastern Arabian Sea, where it provides an additional source of remineralization that drives the ASOMZ to suboxic levels. The model BBOMZ is weaker than the ASOMZ because the Bay lacks a remote source of detritus from the western boundary. Although detritus has a prominent annual cycle, the model OMZs do not because there is not enough time for significant remineralization to occur.

A multifold reduction in the transition Reynolds number, and ultra-fast mixing, in a micro-channel due to a dynamical instability induced by a soft wall

A dynamical instability is observed in experimental studies on micro-channels of rectangular cross-section with smallest dimension 100 and 160 mu m in which one of the walls is made of soft gel. There is a spontaneous transition from an ordered, laminar flow to a chaotic and highly mixed flow state when the Reynolds number increases beyond a critical value. The critical Reynolds number, which decreases as the elasticity modulus of the soft wall is reduced, is as low as 200 for the softest wall used here (in contrast to 1200 for a rigid-walled channel) The instability onset is observed by the breakup of a dye-stream introduced in the centre of the micro-channel, as well as the onset of wall oscillations due to laser scattering from fluorescent beads embedded in the wall of the channel. The mixing time across a channel of width 1.5 mm, measured by dye-stream and outlet conductance experiments, is smaller by a factor of 10(5) than that for a laminar flow. The increased mixing rate comes at very little cost, because the pressure drop (energy requirement to drive the flow) increases continuously and modestly at transition. The deformed shape is reconstructed numerically, and computational fluid dynamics (CFD) simulations are carried out to obtain the pressure gradient and the velocity fields for different flow rates. The pressure difference across the channel predicted by simulations is in agreement with the experiments (within experimental errors) for flow rates where the dye stream is laminar, but the experimental pressure difference is higher than the simulation prediction after dye-stream breakup. A linear stability analysis is carried out using the parallel-flow approximation, in which the wall is modelled as a neo-Hookean elastic solid, and the simulation results for the mean velocity and pressure gradient from the CFD simulations are used as inputs. The stability analysis accurately predicts the Reynolds number (based on flow rate) at which an instability is observed in the dye stream, and it also predicts that the instability first takes place at the downstream converging section of the channel, and not at the upstream diverging section. The stability analysis also indicates that the destabilization is due to the modification of the flow and the local pressure gradient due to the wall deformation; if we assume a parabolic velocity profile with the pressure gradient given by the plane Poiseuille law, the flow is always found to be stable.

Visualization of coherent structures in turbulent subsonic jet using planar laser induced fluorescence of acetone

In this paper, we present the molecular density distribution measurement in turbulent nitrogen jet (Re approximate to 3 x 10(3)), using acetone as molecular tracer. The tracer was seeded in the nitrogen jet by purging through the liquid acetone at ambient temperature. Planar laser sheet of 266 nm wavelength from frequency quadrupled, Q-switched, Nd:YAG laser was used as an excitation source. Emitted fluorescence images of jet flow field were recorded on CMOS camera. The dependence of planar laser induced fluorescence (PLIF) intensity on acetone vapor density was used to convert PLIF image of nitrogen jet into the density image on pixel-by-pixel basis. Instantaneous quantitative density image of nitrogen jet, seeded with acetone, was obtained. The arrowhead-shaped coherent turbulent structures were observed in the present work. It was found that coherent structures were non-overlapping with separate boundaries. Breaking of coherent structures into turbulence was clearly observed above four times jet width.

Modeling of temperature and field-dependent electron mobility in a single-layer graphene sheet

In this paper, we address a physics-based analytical model of electric-field-dependent electron mobility (mu) in a single-layer graphene sheet using the formulation of Landauer and Mc Kelvey's carrier flux approach under finite temperature and quasi-ballistic regime. The energy-dependent, near-elastic scattering rate of in-plane and out-of-plane (flexural) phonons with the electrons are considered to estimate mu over a wide range of temperature. We also demonstrate the variation of mu with carrier concentration as well as the longitudinal electric field. We find that at high electric field (>10(6) Vm(-1)), the mobility falls sharply, exhibiting the scattering between the electrons and flexural phonons. We also note here that under quasi-ballistic transport, the mobility tends to a constant value at low temperature, rather than in between T-2 and T-1 in strongly diffusive regime. Our analytical results agree well with the available experimental data, while the methodologies are put forward to estimate the other carrier-transmission-dependent transport properties.

Physical Layer Network Coding for the K-User Multiple Access Relay Channel

We propose a Physical layer Network Coding (PNC) scheme for the K-user wireless Multiple Access Relay Channel, in which K source nodes want to transmit messages to a destination node D with the help of a relay node R. The proposed scheme involves (i) Phase 1 during which the source nodes alone transmit and (ii) Phase 2 during which the source nodes and the relay node transmit. At the end of Phase 1, the relay node decodes the messages of the source nodes and during Phase 2 transmits a many-to-one function of the decoded messages. To counter the error propagation from the relay node, we propose a novel decoder which takes into account the possibility of error events at R. It is shown that if certain parameters are chosen properly and if the network coding map used at R forms a Latin Hypercube, the proposed decoder offers the maximum diversity order of two. Also, it is shown that for a proper choice of the parameters, the proposed decoder admits fast decoding, with the same decoding complexity order as that of the reference scheme based on Complex Field Network Coding (CFNC). Simulation results indicate that the proposed PNC scheme offers a large gain over the CFNC scheme.

Albumin-mediated incorporation of water-insoluble therapeutics in layer-by-layer assembled thin films and microcapsules

The present study demonstrates a method to deliver hydrophobic drugs by incorporation into thin films and microcapsules fabricated via a layer-by-layer assembly approach. The hydrophobic molecule binding properties of albumin have been exploited for solubilization of a water-insoluble molecule, pyrene (model drug), by preparation of non-covalent conjugates with bovine serum albumin (BSA). Conjugation with BSA renders a highly negative zeta potential to the previously uncharged pyrene which favors the assembly formation by electrostatic interaction with a positively charged polyelectrolyte, chitosan (at acidic pH). The growth of the assembly was followed by monitoring pyrene absorbance with successive layer deposition. The thin film assembly was demonstrated to be capable of releasing its hydrophobic cargo under physiological conditions. We demonstrated the applicability of this approach by encapsulating a water-insoluble drug, curcumin. These assemblies were further loaded with the anti-cancer drug Doxorubicin. Biocompatible calcium carbonate microparticles were used for capsule preparation. The porous nature of the microparticles allows for the pre-encapsulation of therapeutic macromolecules like protein. The fabrication of protein encapsulated stable microcapsules with hydrophobic molecules incorporated into the shell of the microcapsules has been demonstrated. The microcapsules were further capable of loading hydrophilic molecules like Rhodamine B. Thus, using the approach described, a multi-agent carrier for hydrophobic and hydrophilic drugs as well as therapeutic macromolecules can be envisioned.

Novel procedure for the estimation of swelling pressures of compacted bentonites based on diffuse double layer theory

Bentonite clays are proven to be attractive as buffer and backfill material in high-level nuclear waste repositories around the world. A quick estimation of swelling pressures of the compacted bentonites for different clay-water-electrolyte interactions is essential in the design of buffer and backfill materials. The theoretical studies on the swelling behavior of bentonites are based on diffuse double layer (DDL) theory. To establish theoretical relationship between void ratio and swelling pressure (e versus P), evaluation of elliptic integral and inverse analysis are unavoidable. In this paper, a novel procedure is presented to establish theoretical relationship of e versus P based on the Gouy-Chapman method. The proposed procedure establishes a unique relationship between electric potentials of interacting and non-interacting diffuse clay-water-electrolyte systems. A procedure is, thus, proposed to deduce the relation between swelling pressures and void ratio from the established relation between electric potentials. This approach is simple and alleviates the need for elliptic integral evaluation and also the inverse analysis. Further, application of the proposed approach to estimate swelling pressures of four compacted bentonites, for example, MX 80, Febex, Montigel and Kunigel V1, at different dry densities, shows that the method is very simple and predicts solutions with very good accuracy. Moreover, the proposed procedure provides continuous distributions of e versus P and thus it is computationally efficient when compared with the existing techniques.

Plasmons in spatially separated rolled-up electron-hole double-layer systems

Using the two-component random phase approximation, we report the collective mode spectrum of a quasi-one-dimensional spatially separated electron-hole double-layer system characterized by rolled-up type-II band aligned quantum wells. We find two intra-subband collective excitations, which can be classified into optic and acoustic plasmon branches, and several inter-subband plasmon modes. At the long wavelength limit and up to a given wave vector, our model predicts and admits an undamped acoustic branch, which always lies in the gap between the intra-subband electron and hole continua, and an undamped optic branch residing within the gap between the inter-subband electron and hole continua, for all values of the electron-hole charge separations. This theoretical investigation suggests that the low-energy and Landau-undamped plasmon modes might exist based on quasi-one-dimensional, two-component spatially separated electron-hole plasmas, and their possibility could be experimentally examined. (C) 2013 AIP Publishing LLC.

Effect of high-temperature shock-wave compression on few-layer MoS2, WS2 and MoSe2

Exposure of few-layer MoS2, WS2 and MoSe2 to high-temperature shock waves causes morphological changes and a significant decrease in the interlayer separation between the (002) planes, the decrease being greatest in MoSe2. Raman spectra show softening of both the A(1g) and the E-2g(1) modes initially, followed by a slightly stiffening. Using first-principles density functional theoretical analysis of the response of few-layer MoS2 to shock waves, we propose that a combination of shear and uniaxial compressive deformation leads to flattening of MoS2 sheets which is responsible for the changes in the vibrational spectra. (C) 2013 Elsevier B.V. All rights reserved.

EFFECT OF OFF-STOICHIOMETRY AND TERNARY ADDITIONS ON PLANAR FAULT ENERGIES IN Ni3Al

First principles calculations were done to evaluate the lattice parameter, cohesive energy and stacking fault energies of ordered gamma' (Ll(2)) precipitates in superalloys as a function of composition. It was found that addition of Ti and Ta lead to an increase in lattice parameter and decrease in cohesive energy, while Ni antisites had the opposite effect. Ta and Ti addition to stoichiometric Ni3Al resulted in an initial increase in the energies of APB((111)), CSF(111), APB((001)) and SISF(111). However, at higher concentrations, the fault energies decreased. Addition of Ni antisites decreased the energy of all four faults monotonically. A model based on nearest neighbor bonding was used for Ni-3(Al, Ta), Ni-3(Al, Ti) and Ni-3(Al, Ni) pseudo-binary systems and extended to pseudo- ternary Ni-3(Al, Ta, Ni) and Ni-3(Al, Ti, Ni) systems. Recipes were developed for predicting lattice parameters, cohesive energies and fault energies in pseudo- ternary systems on the basis of coefficients derived from simpler pseudobinary systems. The model predictions were found to be in good agreement with first principles calculations for lattice parameters, cohesive energies, and energies of APB((111)) and CSF(111).