Rapid reduction of GO by hydrogen spill-over mechanism by in situ generated nanoparticles at room temperature and their catalytic performance towards 4-nitrophenol reduction and ethanol oxidation

Here, we report the clean and facile synthesis of Pt and Pd nanoparticles decorated on reduced graphene oxide (rGO) by the simultaneous reduction of graphene oxide (GO) and the metal ions in Mg/acid medium. As-generated Pt and Pd nanoparticles serve as a heterogeneous catalyst for the further reduction of the rGO by the hydrogen spill-over process. The C/O ratio is much higher as compared to the rGO obtained by the reduction of GO by only Mg/acid. Overall, the process is rapid, facile and green that does not require any toxic chemical agent or any rigorous chemical reactions. We perform the catalytic reduction of 4-nitophenol (4-NP) to 4-aminophenol (4-AP) at room temperature by Pd@rGO and Pt@rGO. The reduction is complete within 35 s for Pd@rGO and 60 s for Pt@rGO when 50 mu g of hybrid catalyst is used for 0.5 ml of 1 mM of 4-NP. In case of ethanol oxidation, the current density for Pd@rGO is comparable to commercial Pt/C but is doubled for Pt@rGO. Overall, both structures show highly stable catalytic activity compared to commercial Pt/C. (C) 2014 Elsevier B.V. All rights reserved.

Uninterrupted galvanic reaction for scalable and rapid synthesis of metallic and bimetallic sponges/dendrites as efficient catalysts for 4-nitrophenol reduction

Here, we demonstrate an uninterrupted galvanic replacement reaction (GRR) for the synthesis of metallic (Ag, Cu and Sn) and bimetallic (Cu M, M=Ag, Au, Pt and Pd) sponges/dendrites by sacrificing the low reduction potential metals (Mg in our case) in acidic medium. The acidic medium prevents the oxide formation on Mg surface and facilitates the uninterrupted reaction. The morphology of dendritic/spongy structures is controlled by the volume of acid used for this reaction. The growth mechanism of the spongy/dendritic microstructures is explained by diffusion-limited aggregate model (DLA), which is also largely affected by the volume of acid. The significance of this method is that the yield can be easily predicted, which is a major challenge for the commercialization of the products. Furthermore, the synthesis is complete in 1-2 minutes at room temperature. We show that the sponges/dendrites efficiently act as catalysts to reduce 4-nitrophenol (4-NP) to 4-aminophenol (4-AP) using NaBH4-a widely studied conversion process.

Novel triethylamine mediated thermal reactions of 3-aryl-2-cyanoprop-2-enoic acid derivatives-demethylation, reduction and vinylogation

3-Aryl-2-propenoic acid derivatives undergo interesting reactions with hot triethylamine. Substrates like 6 having a methoxyl with a nitro in the ortho and cyanoacrylic derivatives in the para positions give O-demethylated products, for example, entacapone 7. On the other hand compounds like 16 having the NO2 in the para and cyanoacrylic in the ortho position undergo reduction and vinylogation. The latter phenomenon is observed in the absence of the NO2 group also. (C) 2015 Elsevier Ltd. All rights reserved.

Phonon scattering limited performance of monolayer MoS2 and WSe2 n-MOSFET

In this paper we show the effect of electron-phonon scattering on the performance of monolayer (1L) MoS2 and WSe2 channel based n-MOSFETs. Electronic properties of the channel materials are evaluated using the local density approximation (LDA) in density functional theory (DFT). For phonon dispersion we employ the small displacement / frozen phonon calculations in DFT. Thereafter using the non-equilibrium Green's function (NEGF) formalism, we study the effect of electron-phonon scattering and the contribution of various phonon modes on the performance of such devices. It is found that the performance of the WSe2 device is less impacted by phonon scattering, showing a ballisticity of 83% for 1L-WSe2 FET for channel length of 10 nm. Though 1L-MoS2 FET of similar dimension shows a lesser ballisticity of 75%. Also in the presence of scattering there exist a a 21-36% increase in the intrinsic delay time (tau) and a 10-18% reduction in peak transconductance (g(m)) for WSe2 and MoS2 devices respectively. (C) 2015 Author(s).

SEPARATION DIMENSION OF BOUNDED DEGREE GRAPHS

The separation dimension of a graph G is the smallest natural number k for which the vertices of G can be embedded in R-k such that any pair of disjoint edges in G can be separated by a hyperplane normal to one of the axes. Equivalently, it is the smallest possible cardinality of a family F of total orders of the vertices of G such that for any two disjoint edges of G, there exists at least one total order in F in which all the vertices in one edge precede those in the other. In general, the maximum separation dimension of a graph on n vertices is Theta(log n). In this article, we focus on bounded degree graphs and show that the separation dimension of a graph with maximum degree d is at most 2(9) (log*d)d. We also demonstrate that the above bound is nearly tight by showing that, for every d, almost all d-regular graphs have separation dimension at least d/2]

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.

Robust design of multiple trailing edge flaps for helicopter vibration reduction: A multi-objective bat algorithm approach

The objective of this study is to determine an optimal trailing edge flap configuration and flap location to achieve minimum hub vibration levels and flap actuation power simultaneously. An aeroelastic analysis of a soft in-plane four-bladed rotor is performed in conjunction with optimal control. A second-order polynomial response surface based on an orthogonal array (OA) with 3-level design describes both the objectives adequately. Two new orthogonal arrays called MGB2P-OA and MGB4P-OA are proposed to generate nonlinear response surfaces with all interaction terms for two and four parameters, respectively. A multi-objective bat algorithm (MOBA) approach is used to obtain the optimal design point for the mutually conflicting objectives. MOBA is a recently developed nature-inspired metaheuristic optimization algorithm that is based on the echolocation behaviour of bats. It is found that MOBA inspired Pareto optimal trailing edge flap design reduces vibration levels by 73% and flap actuation power by 27% in comparison with the baseline design.

A zero charge-pump mismatch current tracking loop for reference spur reduction in PLLs

The charge-pump (CP) mismatch current is a dominant source of static phase error and reference spur in the nano-meter CMOS PLL implementations due to its worsened channel length modulation effect. This paper presents a charge-pump (CP) mismatch current reduction technique utilizing an adaptive body bias tuning of CP transistors and a zero CP mismatch current tracking PLL architecture for reference spur suppression. A chip prototype of the proposed circuit was implemented in 0.13 mu m CMOS technology. The frequency synthesizer consumes 8.2 mA current from a 13 V supply voltage and achieves a phase noise of -96.01 dBc/Hz @ 1 MHz offset from a 2.4 GHz RF carrier. The charge-pump measurements using the proposed calibration technique exhibited a mismatch current of less than 0.3 mu A (0.55%) over the VCO control voltage range of 0.3-1.0 V. The closed loop measurements show a minimized static phase error of within +/- 70 ps and a similar or equal to 9 dB reduction in reference spur level across the PLL output frequency range 2.4-2.5 GHz. The presented CP calibration technique compensates for the DC current mismatch and the mismatch due to channel length modulation effect and therefore improves the performance of CP-PLLs in nano-meter CMOS implementations. (C) 2015 Elsevier Ltd. All rights reserved.

Achieving Highly Efficient, Selective, and Stable CO2 Reduction on Nitrogen-Doped Carbon Nanotubes

The challenge in the electrosynthesis of fuels from CO2 is to achieve durable and active performance with cost-effective catalysts. Here, we report that carbon nanotubes (CNTs), doped with nitrogen to form resident electron-rich defects, can act as highly efficient and, more importantly, stable catalysts for the conversion of CO2 to CO. The unprecedented overpotential (-0.18 V) and selectivity (80%) observed on nitrogen-doped CNTs (NCNTs) are attributed to their unique features to facilitate the reaction, including (i) high electrical conductivity, (ii) preferable catalytic sites (pyridinic N defects), and (iii) low free energy for CO2 activation and high barrier for hydrogen evolution. Indeed, DFT calculations show a low free energy barrier for the potential-limiting step to form key intermediate COOH as well as strong binding energy of adsorbed CON and weak binding energy for the adsorbed CO. The highest selective site toward CO production is pyridinic N, and the NCNT-based electrodes exhibit no degradation over 10 h of continuous operation, suggesting the structural stability of the electrode.

VAM Applied to Dimensional Reduction of Nonlinear Multifunctional Film-fabric Laminates

This work aims at asymptotically accurate dimensional reduction of non-linear multi-functional film-fabric laminates having specific application in design of envelopes for High Altitude Airships (HAA). The film-fabric laminate for airship envelope consists of a woven fabric core coated with thin films on each face. These films provide UV protection and Helium leakage prevention, while the core provides required structural strength. This problem is both geometrically and materially non-linear. To incorporate the geometric non-linearity, generalized warping functions are used and finite deformations are allowed. The material non-linearity is handled by using hyper-elastic material models for each layer. The development begins with three-dimensional (3-D) nonlinear elasticity and mathematically splits the analysis into a one-dimensional through-the-thickness analysis and a two-dimensional (2-D) plate analysis. The through-the-thickness analysis provides the 2-D constitutive law which is then given as an input to the 2-D reference surface analysis. The dimensional reduction is carried out using Variational Asymptotic Method (VAM) for moderate strains and very small thickness-to-wavelength ratio. It features the identification and utilization of additional small parameters such as ratio of thicknesses and stiffness coefficients of core and films. Closed form analytical expressions for warping functions and 2-D constitutive law of the film-fabric laminate are obtained.

Effect of the nature of a transition metal dopant in BaTiO3 perovskite on the catalytic reduction of nitrobenzene

In the present study, we have synthesized Fe, Co and Ni doped BaTiO3 catalyst by a wet chemical synthesis method using oxalic acid as a chelating agent. The concentration of the metal dopant varies from 0 to 5 mol% in the catalysts. The physical and chemical properties of doped BaTiO3 catalysts were studied using various analytical methods such as X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR), BET surface area and Transmission electron microscopy (TEM). The acidic strength of the catalysts was measured using a n-butylamine potentiometric titration method. The bulk BaTiO3 catalyst exhibits a tetragonal phase with the P4mm space group. A structural transition from tetrahedral to cubic phase was observed for Fe, Co and Ni doped BaTiO3 catalysts with an increase in doped metal concentration from 1 to 5 mol%. The particle sizes of the catalysts were calculated from TEM images and are in the range of 30-80 nm. All the catalysts were tested for the catalytic reduction of nitrobenzene to azoxybenzene. The BaTiO3 catalyst was found to be highly active and less selective compared to the doped catalysts which are active and highly selective towards azoxybenzene. The increase in selectivity towards azoxybenzene is due to an increase in acidic strength and reduction ability of the doped metal. It was also observed that the nature of the metal dopant and their content at the B-site has an impact on the catalytic reduction of nitrobenzene. The Co doped BaTiO3 catalyst showed better activity with only 0.5 mol% doping than Fe and Ni doped BaTiO3 catalysts with maximum nitrobenzene conversion of 91% with 78% selectivity to azoxybenzene. An optimum Fe loading of 2.5 mol% in BaTiO3 is required to achieve 100% conversion with 93% selectivity whereas Ni with 5 mol% showed a conversion of 93% and a azoxybenzene selectivity of 84%.

Modified Greedy Pursuits for Improving Sparse Recovery

Compressive Sensing (CS) theory combines the signal sampling and compression for sparse signals resulting in reduction in sampling rate. In recent years, many recovery algorithms have been proposed to reconstruct the signal efficiently. Subspace Pursuit and Compressive Sampling Matching Pursuit are some of the popular greedy methods. Also, Fusion of Algorithms for Compressed Sensing is a recently proposed method where several CS reconstruction algorithms participate and the final estimate of the underlying sparse signal is determined by fusing the estimates obtained from the participating algorithms. All these methods involve solving a least squares problem which may be ill-conditioned, especially in the low dimension measurement regime. In this paper, we propose a step prior to least squares to ensure the well-conditioning of the least squares problem. Using Monte Carlo simulations, we show that in low dimension measurement scenario, this modification improves the reconstruction capability of the algorithm in clean as well as noisy measurement cases.

Reduction in DNA topoisomerase I level affects growth, phenotype and nucleoid architecture of Mycobacterium smegmatis

The steady-state negative supercoiling of eubacterial genomes is maintained by the action of DNA topoisomerases. Topoisomerase distribution varies in different species of mycobacteria. While Mycobacterium tuberculosis (Mtb) contains a single type I (Topol) and a single type II (Gyrase) enzyme, Mycobacterium smegmatis (Msm) and other members harbour additional relaxases. Topol is essential for Mtb survival. However, the necessity of Topol or other relaxases in Msm has not been investigated. To recognize the importance of Topol for growth, physiology and gene expression of Msm, we have developed a conditional knock-down strain of Topol in Msm. The Topol-depleted strain exhibited extremely slow growth and drastic changes in phenotypic characteristics. The cessation of growth indicates the essential requirement of the enzyme for the organism in spite of having additional DNA relaxation enzymes in the cell. Notably, the imbalance in Topol level led to the altered expression of topology modulatory proteins, resulting in a diffused nucleoid architecture. Proteomic and transcript analysis of the mutant indicated reduced expression of the genes involved in central metabolic pathways and core DNA transaction processes. RNA polymerase (RNAP) distribution on the transcription units was affected in the Topol-depleted cells, suggesting global alteration in transcription. The study thus highlights the essential requirement of Topol in the maintenance of cellular phenotype, growth characteristics and gene expression in mycobacteria. A decrease in Topol level led to altered RNAP occupancy and impaired transcription elongation, causing severe downstream effects.

Effect of Size Reduction on Magnetic Ordering in Sm1-x Ca (x) MnO3 (x=0.35, 0.65 and 0.92) Manganites: Magnetic and EMR Studies

We have employed the highly sensitive electron magnetic resonance technique complimented by magnetization measurements to study the impact of size reduction on the magnetic ordering in nanosized Sm1-x Ca (x) MnO3 (x = 0.35, 0.65 and 0.92). In the bulk form, x = 0.35 sample shows a charge ordering transition at 235 K followed by a mixed magnetic phase, the sample with x = 0.65 exhibits charge order below 275 K and shows an antiferromagnetic insulator phase below 135 K while that with x = 0.92 has a ferromagnetic-cluster glass ground state. Thus, a comparative study of magnetic ground states of bulk and nanoparticles (diameter similar to 25 nm) enables us to investigate size-induced effects on different types of magnetic ordering. It is seen that in the bulk samples the temperature dependences of the EPR parameters are quite different from each other. This difference diminishes for the nanosamples where all the three samples show qualitatively similar behavior. The magnetization measurements corroborate this conclusion.

Tandem aziridine ring opening-disulfide formation-reduction-Michael addition in one-pot mediated by tetrathiomolybdate

A detailed study of tetrathiomolybdate mediated tandem regio- and stereoselective ring opening of aziridine, disulfide formation, reduction of disulfide bond and Michael reaction in a one-pot operation is reported. This constitutes four reactions that take place in one-pot operation. In the reaction of BnEt3N](4)MoS4 with an aziridine derived from cyclohexene and in the absence of Michael acceptor intermediates sulfonamidodisulfide and sulfonamidothiol were isolated and fully characterized. It has also been shown that it is possible to carry out selective opening of the aziridine ring in the presence of an epoxide. By incorporating a suitable Michael acceptor as part of the substrate, intramolecular 1,4-addition could be performed, to achieve the synthesis of sulfur containing acyclic, cyclic amino acid ester derivatives and thia-bicyclo3.3.1]nonane derivatives in good yields. (C) 2015 Elsevier Ltd. All rights reserved.