Guanidine catalyzed aerobic reduction: a selective aerobic hydrogenation of olefins using aqueous hydrazine

An efficient aerobic reduction of olefins, internal as well as terminal, is developed using guanidine as an organocatalyst. A remarkable chemoselectivity in reduction has been demonstrated in the presence of a variety of functional groups and protective groups and a selective reduction of a terminal olefin in the presence of an internal olefin is revealed.

Reduction of aromatic nitro compounds to amines using zinc and aqueous chelating ethers: Mild and efficient method for zinc activation

A mild, environmentally friendly method for reduction of aromatic nitro group to amine is reported, using zinc powder in aqueous solutions of chelating ethers. The donor ether acts as a ligand and also serves as a co-solvent. Water is the proton source. This procedure is also a new method for the activation of zinc for electron transfer reduction of aromatic nitro compounds. The reduction is accomplished in a neutral medium and other reducing groups remained unaffected. The ethers used are dioxolane, 1,4-dioxane, ethoxymethoxyethane, dimethoxymethane, 1,2-dimethoxyethane, and diglyme.

Criticality guided energy aware speculation for speculative multithreaded processors

Unending quest for performance improvement coupled with the advancements in integrated circuit technology have led to the development of new architectural paradigm. Speculative multithreaded architecture (SpMT) philosophy relies on aggressive speculative execution for improved performance. However, aggressive speculative execution comes with a mixed flavor of improving performance, when successful, and adversely affecting the energy consumption (and performance) because of useless computation in the event of mis-speculation. Dynamic instruction criticality information can be usefully applied to control and guide such an aggressive speculative execution. In this paper, we present a model of micro-execution for SpMT architecture that we have developed to determine the dynamic instruction criticality. We have also developed two novel techniques utilizing the criticality information namely delaying the non-critical loads and the criticality based thread-prediction for reducing useless computations and energy consumption. Experimental results showing break-up of critical instructions and effectiveness of proposed techniques in reducing energy consumption are presented in the context of multiscalar processor that implements SpMT architecture. Our experiments show 17.7% and 11.6% reduction in dynamic energy for criticality based thread prediction and criticality based delayed load scheme respectively while the improvement in dynamic energy delay product is 13.9% and 5.5%, respectively. (c) 2012 Published by Elsevier B.V.

Adaptation of small capacity natural gas engine for producer gas operation

This article addresses the adaptation of a low-power natural gas engine for using producer gas as a fuel. The 5.9 L natural gas engine with a compression ratio of 10.5:1, rated at 55 kW shaft power, delivered 30 kW using producer gas as fuel in the naturally aspirated mode. Optimal ignition timing for peak power was found to be 20 degrees before top dead centre. Air-to-fuel ratio (A/F) was found to be 1.2 +/- 0.1 over a range of loads. Critical evaluation of the energy flows in the engine resulted in identifying losses and optimizing the engine cooling. The specific fuel consumption was found to be 1.2 +/- 0.1 kg of biomass per kilowatt hour. A reduction of 40 per cent in brake mean effective pressure was observed compared with natural gas operation. Governor response to load variations has been studied with respect to frequency recovery time. The study also attempts to adopt a turbocharger for higher power output. Preliminary results suggest a possibility of about 30 per cent increase in the output.

Compiler-assisted energy optimization for clustered VLIW processors

Clustered architecture processors are preferred for embedded systems because centralized register file architectures scale poorly in terms of clock rate, chip area, and power consumption. Although clustering helps by improving the clock speed, reducing the energy consumption of the logic, and making the design simpler, it introduces extra overheads by way of inter-cluster communication. This communication happens over long global wires having high load capacitance which leads to delay in execution and significantly high energy consumption. Inter-cluster communication also introduces many short idle cycles, thereby significantly increasing the overall leakage energy consumption in the functional units. The trend towards miniaturization of devices (and associated reduction in threshold voltage) makes energy consumption in interconnects and functional units even worse, and limits the usability of clustered architectures in smaller technologies. However, technological advancements now permit the design of interconnects and functional units with varying performance and power modes. In this paper, we propose scheduling algorithms that aggregate the scheduling slack of instructions and communication slack of data values to exploit the low-power modes of functional units and interconnects. Finally, we present a synergistic combination of these algorithms that simultaneously saves energy in functional units and interconnects to improves the usability of clustered architectures by achieving better overall energy-performance trade-offs. Even with conservative estimates of the contribution of the functional units and interconnects to the overall processor energy consumption, the proposed combined scheme obtains on average 8% and 10% improvement in overall energy-delay product with 3.5% and 2% performance degradation for a 2-clustered and a 4-clustered machine, respectively. We present a detailed experimental evaluation of the proposed schemes. Our test bed uses the Trimaran compiler infrastructure. (C) 2012 Elsevier Inc. All rights reserved.

Surrogate based design optimisation of composite aerofoil cross-section for helicopter vibration reduction

Design optimisation of a helicopter rotor blade is performed. The objective is to reduce helicopter vibration and constraints are put on frequencies and aeroelastic stability. The ply angles of the D-spar and skin of the composite rotor blade with NACA 0015 aerofoil section are considered as design variables. Polynomial response surfaces and space filling experimental designs are used to generate surrogate models of the objective function with respect to cross-section properties. The stacking sequence corresponding to the optimal cross-section is found using a real-coded genetic algorithm. Ply angle discretisation of 1 degrees, 15 degrees, 30 degrees and 45 degrees are used. The mean value of the objective function is used to find the optimal blade designs and the resulting designs are tested for variance. The optimal designs show a vibration reduction of 26% to 33% from the baseline design. A substantial reduction in vibration and an aeroelastically stable blade is obtained even after accounting for composite material uncertainty.

An approach to chiral amino acids via reductive amination of ketones: hydride reduction of 1-(S)-phenethyl amine derived Schiff bases of C-protected alpha-keto acids

Various 1-acyl-2,4,10-trioxaadamantanes were prepared from the corresponding 1-methoxycarbonyl derivatives, via conversion to the N-acylpiperidine derivatives followed by reaction with a Grignard reagent in refluxing THF. These alpha-keto orthoformates were converted to the corresponding imines with 1-(S)-phenethyl amine (TiCl4/Et3N/toluene/reflux), with the Schiff bases being reduced further with NaBH4 (MeOH/0 degrees C) into the corresponding 1-(S)-phenethyl amines (diastereomeric excess 91:9 by NMR). Hydrogenolysis of the phenethyl group (Pd-C/MeOH) finally led to the 1-(aminoalkyl)trioxaadamantanes, which are chiral C-protected alpha-amino acids, in excellent overall yields. (C) 2012 Elsevier Ltd. All rights reserved.

VAM applied to dimensional reduction of non-linear hyperelastic plates

This work aims at dimensional reduction of non-linear isotropic hyperelastic plates in an asymptotically accurate manner. The problem is both geometrically and materially non-linear. The geometric non-linearity is handled by allowing for finite deformations and generalized warping while the material non-linearity is incorporated through hyperelastic material model. The development, based on the Variational Asymptotic Method (VAM) with moderate strains and very small thickness to shortest wavelength of the deformation along the plate reference surface as small parameters, begins with three-dimensional (3-D) non-linear elasticity and mathematically splits the analysis into a one-dimensional (1-D) through-the-thickness analysis and a two-dimensional (2-D) plate analysis. Major contributions of this paper are derivation of closed-form analytical expressions for warping functions and stiffness coefficients and a set of recovery relations to express approximately the 3-D displacement, strain and stress fields. Consistent with the 2-D non-linear constitutive laws, 2-D plate theory and corresponding finite element program have been developed. Validation of present theory is carried out with a standard test case and the results match well. Distributions of 3-D results are provided for another test case. (c) 2012 Elsevier Ltd. All rights reserved.

Metal and Alloy Nanoparticles by Amine-Borane Reduction of Metal Salts by Solid-Phase Synthesis: Atom Economy and Green Process

A new solid state synthetic route has been developed toward metal and bimetallic alloy nanoparticles from metal salts employing amine-boranes, as the reducing agent. During the reduction, amine-borane plays a dual role: acts as a reducing agent and reduces the metal salts to their elemental form and simultaneously generates a stabilizing agent in situ which controls the growth of the particles and stabilizes them in the nanosize regime. Employing different amine-boranes with differing reducing ability (ammonia borane (AB), dimethylamine borane (DMAB), and triethylamine borane (TMAB)) was found to have a profound effect on the particle size and the size distribution. Usage of AB as the reducing agent provided the smallest possible size with best size distribution. Employment of TMAB also afforded similar results; however, when DMAB was used as the reducing agent it resulted in larger sized nanoparticles that are polydisperse too. In the AB mediated reduction, BNHx polymer generated in situ acts as a capping agent whereas, the complexing amine of the other amine-boranes (DMAB and TMAB) play the same role. Employing the solid state route described herein, monometallic Au, Ag, Cu, Pd, and Ir and bimetallic CuAg and CuAu alloy nanoparticles of <10 nm were successfully prepared. Nucleation and growth processes that control the size and the size distribution of the resulting nanoparticles have been elucidated in these systems.

Accelerating Reduction for Enabling Fast Multiplication over Large Binary Fields

In this paper we present a hardware-software hybrid technique for modular multiplication over large binary fields. The technique involves application of Karatsuba-Ofman algorithm for polynomial multiplication and a novel technique for reduction. The proposed reduction technique is based on the popular repeated multiplication technique and Barrett reduction. We propose a new design of a parallel polynomial multiplier that serves as a hardware accelerator for large field multiplications. We show that the proposed reduction technique, accelerated using the modified polynomial multiplier, achieves significantly higher performance compared to a purely software technique and other hybrid techniques. We also show that the hybrid accelerated approach to modular field multiplication is significantly faster than the Montgomery algorithm based integrated multiplication approach.

Morphology dependent oxygen reduction activity of titanium carbide: bulk vs. nanowires

Titanium carbide (TiC) possesses fascinating properties like high electrical conductivity and high mechanical strength coupled with high corrosion resistance and stability in acidic and alkaline environments. The present study demonstrates the tunability of mechanistic aspects of oxygen reduction reaction (ORR) using TiC nanostructures. One dimensional TiC nanostructures (TiC-NW) have been synthesized using a simple, hydrothermal method and used as a catalyst for ORR. Shape dependent electroactivity is demonstrated by comparing the activity of TiC-NW with its bulk counterparts. Comparative studies reveal higher ORR activities in the case of 1D TiC-NW involving similar to 4 electrons showing efficient reduction of molecular oxygen. Excellent stability and high methanol tolerance with good selectivity for ORR is reported.

Role of Fly Ash Pozzolanic Reactions in Controlling Fluoride Release from Phosphogypsum

Phosphogypsum is added to building materials to accelerate fly ash pozzolanic reaction and contributes to early strength development of concrete. The release of unacceptable fluoride levels by phoshogypsum on contact with water is a major impediment in its usage to manufacture building products because excess fluoride consumption causes dental and skeletal fluorosis. This paper examines the efficacy of fly ash pozzolanic reactions in controlling fluoride release by phosphogypsum. Fly ash (FA), sand (S), lime (L), and phosphogypsum (G) (FA-S-L-G) slurries are cured for various periods, and the fluoride released by the mix is monitored as a function of time. A substantial reduction in fluoride release was observed and is attributed to entrapment of phosphogypsum particles in a cementious matrix formed by fly ash-lime pozzolanic reactions coupled with consumption of fluoride in formation of insoluble compounds. The compressive strength developed by compacted FA-S-L-G specimens with time was observed to be a three-stage process; maximum strength mobilization occurred during 14 and 28days of curing at room temperature. Exposure of the compacted FA-S-L-G specimens to acidic and alkaline environments for 9 days did not impact their compressive strengths. (C) 2013 American Society of Civil Engineers.

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.

Instantaneous reduction of graphene oxide at room temperature

We report an environment friendly and green approach to obtain few-layer graphene by the almost instantaneous reduction of graphene oxide using Mg ribbons in acidic solution with a hydrogen spillover mechanism. The typical time is 1-5 min, which is much faster than the reduction by other metal catalysts.