Unprecedented formation of a 14-membered dihydropyran macrocycle via sequential olefin cross metathesis-intramolecular hetero Diels-Alder reaction

Formation of a 2,3-dihydro-4H-pyran containing 14-membered macrocycle by sequential olefin cross metathesis and a highly regiospecific hetero Diels-Alder reaction was observed in the reaction of a hydroxydienone derived from tartaric acid with Grubbs' second generation catalyst. It was found that the free alcohol in the hydroxyenone led to the macrocycle formation, while protection of the hydroxy group formed the ring closing metathesis product. (C) 2013 Elsevier Ltd. All rights reserved.

Universal flame propagation behavior in packed bed of biomass

This article aims at seeking the universal behavior of propagation rate variation with air superficial velocity (V-s) in a packed bed of a range of biomass particles in reverse downdraft mode while also resolving the differing and conflicting explanations in the literature. Toward this, measurements are made of exit gas composition, gas phase and condensed phase surface temperature (T-g and T-s), and reaction zone thickness for a number of biomass with a range of properties. Based on these data, two regimes are identified: gasificationvolatile oxidation accompanied by char reduction reactions up to 16 +/- 1cm/s of V-s and above this, and char oxidationsimultaneous char oxidation and gas phase combustion. In the gasification regime, the measured T-s is less than T-g; a surface heat balance incorporating a diffusion controlled model for flaming combustion gives and matches with the experimental results to within 5%. In the char oxidation regime, T-g and T-s are nearly equal and match with the equilibrium temperature at that equivalence ratio. Drawing from a recent study of the authors, the ash layer over the oxidizing char particle is shown to play a critical role in regulating the radiation heat transfer to fresh biomass in this regime and is shown to be crucial in explaining the observed propagation behavior. A simple model based on radiation-convection balance that tracks the temperature-time evolution of a fresh biomass particle is shown to support the universal behavior of the experimental data on reaction front propagation rate from earlier literature and the present work for biomass with ash content up to 10% and moisture fraction up to 10%. Upstream radiant heat transfer from the ash-laden hot char modulated by the air flow is shown to be the dominant feature of this model.

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.

Naphthalene Carbohydrazone Based Dizinc(II) Chemosensor for a Pyrophosphate Ion and Its DNA Assessment Application in Polymerase Chain Reaction Products

A new naphthalene carbohydrazone based dizinc(II) complex has been synthesized and investigated to act as a highly selective fluorescence and visual sensor for a pyrophosphate ion with a quite low detection limit of 155 ppb; this has also been used to detect the pyrophosphate ion released from polymerase-chain-reaction.

Optimisation of an asymmetric polymerase chain reaction assay for the amplification of single-stranded DNA from Wuchereria bancrofti for electrochemical detection

Single-stranded DNA (ssDNA) is a prerequisite for electrochemical sensor-based detection of parasite DNA and other diagnostic applications. To achieve this detection, an asymmetric polymerase chain reaction method was optimised. This method facilitates amplification of ssDNA from the human lymphatic filarial parasite Wuchereria bancrofti. This procedure produced ssDNA fragments of 188 bp in a single step when primer pairs (forward and reverse) were used at a 100:1 molar ratio in the presence of double-stranded template DNA. The ssDNA thus produced was suitable for immobilisation as probe onto the surface of an Indium tin oxide electrode and hybridisation in a system for sequence-specific electrochemical detection of W. bancrofti. The hybridisation of the ssDNA probe and target ssDNA led to considerable decreases in both the anodic and the cathodic currents of the system's redox couple compared with the unhybridised DNA and could be detected via cyclic voltammetry. This method is reproducible and avoids many of the difficulties encountered by conventional methods of filarial parasite DNA detection; thus, it has potential in xenomonitoring.

Synthesis, Characterization, and Properties of Few-Layer MoO3

Nanosheets of MoO3 that consist of only a few layers have been prepared by using four methods, including the oxidation of MoS2 nanosheets, intercalation with LiBr, and ultrasonication. These nanosheets have been characterized by atomic force microscopy and other techniques. Besides showing a blue-shift of the optical absorption band compared to the bulk sample, few-layer MoO3 exhibits enhanced photocatalytic activity. In combination with a borocarbonitride, few-layer MoO3 shows good performance characteristics as a supercapacitor electrode.

Physical layer network coding for two-way relaying with QAM and latin squares

In the design of modulation schemes for the physical layer network-coded two way relaying scenario with two phases (Multiple access (MA) Phase and Broadcast (BC) Phase), it was observed by Koike-Akino et al. that adaptively changing the network coding map used at the relay according to the channel conditions greatly reduces the impact of multiple access interference and all these network coding maps should satisfy a requirement called the exclusive law. In [11] the case in which the end nodes use M-PSK signal sets is extensively studied using Latin Squares. This paper deals with the case in which the end nodes use square M-QAM signal sets. In a fading scenario, for certain channel conditions, termed singular fade states, the MA phase performance is greatly reduced. We show that the square QAM signal sets lead to lesser number of singular fade states compared to PSK signal sets. Because of this, the complexity at the relay is enormously reduced. Moreover lesser number of overhead bits are required in the BC phase. We find the number of singular fade states for PAM and QAM signal sets used at the end nodes. The fade state γejθ = 1 is a singular fade state for M-QAM for all values of M and it is shown that certain block circulant Latin Squares remove this singular fade state. Simulation results are presented to show that QAM signal set perform better than PSK.

In-situ impedance spectroscopy of layer-by-layer self-assembly of polyelectrolytes

In-situ impedance spectroscopy of layer-by-layer self-assembly of weak polyelectrolytes is presented. Interdigitated capacitors with active area of 1×1 mm2 and electrode spacing of 5 μm are fabricated and used for this purpose. Measurement results indicate that the impedance decreases with increase in number of polyelectrolyte layers. About 2.5% of relative change in magnitude of impedance at 104.7 KHz is seen for four bi-layers of Poly(Allylamine Hydrochloride) (PAH)/Poly(Acrylic acid) (PAA). An electrical equivalent for polyelectrolyte binding is obtained.

Enhancing Surface Coverage and Growth in Layer-by-Layer Assembly of Protein Nanoparticles

Thin films of bovine serum albumin (BSA) nanoparticles are fabricated via layer-by-layer assembly. The surface of BSA nanoparticles have two oppositely acting functional groups on the surface: amine (NH2) and carboxylate (COO-). The protonation and deprotonation of these functional groups at different pH vary the charge density on the particle surface, and entirely different growth can be observed by varying the nature of the complementary polymer and the pH of the particles. The complementary polymers used in this study are poly(dimethyldiallylammonium chloride) (PDDAC) and poly(acrylic acid) (PAA). The assembly of BSA nanoparticles based on electrostatic interaction with PDDAC suffers from the poor loading of the nanoparticles. The assembly with PAA aided by a hydrogen bonding interaction shows tremendous improvement in the growth of the assembly over PDDAC. Moreover, the pH of the BSA nanoparticles was observed to affect the loading of nanoparticles in the LbL assembly with PAA significantly.

Influence of binder solvent on carbon-layer structure in electrical-double-layer capacitors

Porous activated-carbons with a large surface-area have been the most common materials for electrical-double-layer capacitors (EDLCs). These carbons having a wide pore distribution ranges from micropores to macropores in conjunction with a random pore connection that facilitates the high specific-capacitance values. Pore distribution plays a central role in controlling the capacitance value of EDLCs, since electrolyte distribution inside the active material mainly depends on the pore distribution. This has a direct influence on the distribution of resistance and capacitance values within the electrode. As a result, preparation of electrodes remains a vital issue in realising high-performance EDLCs. Generally, carbon materials along with some binders are dispersed into a solvent and coated onto the current collectors. This study examines the role of binder solvents used for the carbon-ink preparation on the microstructure of the electrodes and the consequent performance of the EDLCs. It is observed that the physical properties of the binder solvent namely its dielectric constant, viscosity and boiling point have important role in determining the pore-size distribution as well as the microstructure of electrodes which influence their specific capacitance values.