Vanadium Catalysis in Bromoperoxidation Reaction

Peroxidative bromination of phenol red to its tetrabromo derivative, bromophenol blue, required vanadate in addition to H2O2 when carried out in the pH range of 5-7. Excess H2O2, with ratio of H2O2:vanadate of 2:1 and above, prevented the reaction. Diperoxovanadate, known to be formed in such reaction mixtures, was ineffective by itself and needed uncomplexed vanadate (V-v) or vanadyl (V-iv) to support bromination. Bromide-assisted reduction of the excess vanadate to vanadyl appeared to be an essential secondary reaction. In the absence of phenol red oxygen was released, and concomitantly bromide was oxidized to a form competent to brominate phenol red added after termination of oxygen release. These findings indicated participation of reactions leading to an intermediate derived from vanadyl and diperoxovanadate, previously described from this laboratory (Arch. Biochem. Biophys. 316, 319-326, 1995). Continuous bromination of phenol red occurred when glucose oxidase-glucose system was used as a source of continuous flow of H2O2. A scheme of reactions involving peroxovanadates (mono-, di-, mu-, and bromo-) is proposed for the formation and utilization of an active brominating species and for the recycling of the product, mono-peroxovanadate, by H2O2, which explains the catalytic role of vanadium in the bromoperoxidation reaction.

Thermoelectric Properties of Co4Sb12 Skutterudite Materials with Partial In Filling and Excess In Additions

The properties of Co4Sb12 with various In additions were studied. X-ray diffraction revealed the presence of the pure δ-phase of In0.16Co4Sb12, whereas impurity phases (γ-CoSb2 and InSb) appeared for x = 0.25, 0.40, 0.80, and 1.20. The homogeneity and morphology of the samples were observed by Seebeck microprobe and scanning electron microscopy, respectively. All the quenched ingots from which the studied samples were cut were inhomogeneous in the axial direction. The temperature dependence of the Seebeck coefficient (S), electrical conductivity (σ), and thermal conductivity (κ) was measured from room temperature up to 673 K. The Seebeck coefficient of all In-added Co4Sb12 materials was negative. When the filler concentration increases, the Seebeck coefficient decreases. The samples with In additions above the filling limit (x = 0.22) show an even lower Seebeck coefficient due to the formation of secondary phases: InSb and CoSb2. The temperature variation of the electrical conductivity is semiconductor-like. The thermal conductivity of all the samples decreases with temperature. The central region of the In0.4Co4Sb12 ingot shows the lowest thermal conductivity, probably due to the combined effect of (a) rattling due to maximum filling and (b) the presence of a small amount of fine-dispersed secondary phases at the grain boundaries. Thus, regardless of the non-single-phase morphology, a promising ZT (S 2 σT/κ) value of 0.96 at 673 K has been obtained with an In addition above the filling limit.

Signalling in Malaria Parasites the Malsig Consortium

Depending on their developmental stage in the life cycle, malaria parasites develop within or outside host cells, and in extremely diverse contexts such as the vertebrate liver and blood circulation, or the insect midgut and hemocoel. Cellular and molecular mechanisms enabling the parasite to sense and respond to the intra- and the extra-cellular environments are therefore key elements for the proliferation and transmission of Plasmodium, and therefore are, from a public health perspective, strategic targets in the fight against this deadly disease. The MALSIG consortium, which was initiated in February 2009, was designed with the primary objective to integrate research ongoing in Europe and India on i) the properties of Plasmodium signalling molecules, and ii) developmental processes occurring at various points of the parasite life cycle. On one hand, functional studies of individual genes and their products in Plasmodium falciparum (and in the technically more manageable rodent model Plasmodium berghei) are providing information on parasite protein kinases and phosphatases, and of the molecules governing cyclic nucleotide metabolism and calcium signalling. On the other hand, cellular and molecular studies are elucidating key steps of parasite development such as merozoite invasion and egress in blood and liver parasite stages, control of DNA replication in asexual and sexual development, membrane dynamics and trafficking, production of gametocytes in the vertebrate host and further parasite development in the mosquito. This article, which synthetically reviews such signalling molecules and cellular processes, aims to provide a glimpse of the global frame in which the activities of the MALSIG consortium will develop over the next three years.

Anomalous dynamical charges, phonons, and the origin of negative thermal expansion in Y2W3O12

We use a combination of classical model and first-principles density functional theory calculations to study lattice dynamics of Y2W3O12 and identify phonons responsible for its negative thermal expansion (NTE). Born dynamical charges of various atoms are found to deviate anomalously from their nominal values. We find that the phonons with energy from 4 to 10 meV are the primary contributors to its NTE. These phonons involve rotations of the YO6 octahedra and WO4 tetrahedra in mutually opposite sense and collective translational atomic displacements, reflecting a strong mixing between acoustic and optic modes.

A Concise Synthesis of Substituted Thiourea Derivatives in Aqueous Medium

An efficient method for the synthesis of symmetrical and unsymmetrical substituted thiourea derivatives by means of simple condensation between available building blocks such Lis airlines and carbon disulfide in aqueous medium is presented. This protocol works smoothly with aliphatic primary amines to afford various di- and trisubstituted thiourea derivatives. The present method is also useful ill synthesizing various substituted 2-mercapto imidazole heterocycles. This method proceeds through a xanthate (amino dithiol deivative) intermediate, unlike isothiocyanate as in all earlier known method.

Stabilisation and characterisation of N,N′-dibenzylidene-o-phenylenediamine as a copper(I) perchlorate complex

QUITE OFTEN, metal ions profoundly affect the condensation of carbonyl compounds with primary amines to form Schiff bases as well as their subsequent reactions[I-4]. Condensation of benzaldehyde with o-phenylenediamine (opd) in glacial acetic acid[5] or in absolute alcohol[6] gives benzimidazole derivative, 1-benzyl-2-phenylbenzimidazole (bpbi). In this reaction, the Schiff base N,N'-dibenzylidene-o-phenylenedianfme (dbpd) has been postulated as an intermediate, which cyclises to give bpbi. It was found that the reaction of opd in presence of copperO1) perchlorate with benzaldehyde gave dbpd complex of copper(l) perchlorate instead of bpbi.

Parametric Analysis Of Turbulent Wall Jets

The concept of a fully-developed flow based on the hypothesis of selective memory is here applied to general wall-jet type flows. In the presence of a (constant) external stream, the free-stream velocity and the jet momentum flux are taken to be the chief quantities governing the development of the wall jet: two additional nondimensional parameters, representing a momentum flux Reynolds number and the relative momentum defect in the initial boundary layer, are shown to have only a secondary effect on the fully-developed flow. The standard correlations so determined are also found to predict quite well the flow development in Gartshore and Newman's experiments on wall jets in adverse pressure gradients; possible reasons for this somewhat surprising result are discussed. Finally it is shown, by application to the still-air case, that the parameters discovered in incompressible flow are, with appropriate but straightforward modification, successful in describing compressible wall jets also.

Solution-Combustion Synthesized Nanocrystalline Li4Ti5O12 As High-Rate Performance Li-Ion Battery Anode

Nanocrystalline Li4Ti5O12 (LTO) crystallizing in cubic spinel-phase has been synthesized by single-step-solution-combustion method in less than one minute. LTO particles thus synthesized are flaky and highly porous in nature with a surface area of 12 m(2)/g. Transmission electron micrographs indicate the primary particles to be agglomerated crystallites of varying size between 20 and 50 nm with a 3-dimensional interconnected porous network. During their galvanostatic charge-discharge at varying rates, LTO electrodes yield a capacity value close to the theoretical value of 175 mA h/g at C/2 rate. The electrodes also exhibit promising capacity retention with little capacity loss over 100 cycles at varying discharge rates together with attractive discharge-rate capabilities yielding capacity values of 140 mA h/g and 70 mA h/g at 10 and 100 C discharge rates, respectively. The ameliorated electrode-performance is ascribed to nano and highly porous morphology of the electrodes that provide short diffusion-paths for Li in conjunction with electrolyte percolation through the electrode pores ensuring a high flux of Li.

Finite Signal-set Capacity of Two-user Gaussian Multiple Access Channel

The capacity region of a two-user Gaussian Multiple Access Channel (GMAC) with complex finite input alphabets and continuous output alphabet is studied. When both the users are equipped with the same code alphabet, it is shown that, rotation of one of the user’s alphabets by an appropriate angle can make the new pair of alphabets not only uniquely decodable, but will result in enlargement of the capacity region. For this set-up, we identify the primary problem to be finding appropriate angle(s) of rotation between the alphabets such that the capacity region is maximally enlarged. It is shown that the angle of rotation which provides maximum enlargement of the capacity region also minimizes the union bound on the probability of error of the sumalphabet and vice-verse. The optimum angle(s) of rotation varies with the SNR. Through simulations, optimal angle(s) of rotation that gives maximum enlargement of the capacity region of GMAC with some well known alphabets such as M-QAM and M-PSK for some M are presented for several values of SNR. It is shown that for large number of points in the alphabets, capacity gains due to rotations progressively reduce. As the number of points N tends to infinity, our results match the results in the literature wherein the capacity region of the Gaussian code alphabet doesn’t change with rotation for any SNR.

Effect of strain rate and temperature on the plastic deformation behaviour of a bulk metallic glass composite

The composites consisting of amorphous matrix reinforced with crystalline dendrites offer extraordinary combinations of strength, stiffness, and toughness and can be processed in bulk. Hence, they have been receiving intense research interest, with a primary focus to study their mechanical properties. In this paper, the temperature and strain rate effects on the uniaxial compression response of a tailored bulk metallic glass (BMG) composite has been investigated. Experimental results show that at temperatures ranging between ambient to 500 K and at all strain rates; the onset of plastic deformation in the composite is controlled by that in the dendrites. As the temperature is increased to the glass transition temperature of the matrix and beyond, flow in the amorphous matrix occurs readily and hence it dictates the composite's response. The role of the constituent phases in controlling the deformation mechanism of the composite has been verified by assessing the strain rate sensitivity and the activation volume for deformation. The composite is rate sensitive at room temperature with values of strain rate sensitivity and activation volume being similar to that of the dendrites. At test temperatures near to the glass transition temperature, the composite however becomes rate-insensitive corresponding to that of the matrix phase. At low strain rates, serrated flow akin to that of dynamic strain ageing in crystalline alloys was observed and the serration magnitude decreases with increasing temperature. Initiation of the shear bands at the dendrite/matrix interface and propagation of them through the matrix ligaments until their arrest at another interface is the responsible mechanism for this. (C) 2011 Elsevier B.V. All rights reserved.

Lexicon-free, novel segmentation of online handwritten indic words

Research in the field of recognizing unlimited vocabulary, online handwritten Indic words is still in its infancy. Most of the focus so far has been in the area of isolated character recognition. In the context of lexicon-free recognition of words, one of the primary issues to be addressed is that of segmentation. As a preliminary attempt, this paper proposes a novel script-independent, lexicon-free method for segmenting online handwritten words to their constituent symbols. Feedback strategies, inspired from neuroscience studies, are proposed for improving the segmentation. The segmentation strategy has been tested on an exhaustive set of 10000 Tamil words collected from a large number of writers. The results show that better segmentation improves the overall recognition performance of the handwriting system.

Rrp1B gene polymorphism (1307T > C) in metastatic progression of breast cancer

Rrp1B (ribosomal RNA processing1 homolog B) is a novel candidate metastasis modifier gene in breast cancer. Functional gene assays demonstrated that a physical and functional interaction existing between Rrp1b and metastasis modifier gene SIPA1 causes reduction in the tumor growth and metastatic potential. Ectopic expression of Rrp1B modulates various metastasis predictive extra cellular matrix (ECM) genes associated with tumor suppression. The aim of this study is to determine the functional significance of single nucleotide polymorphism (SNP) in human Rrp1B gene (1307 T > C; rs9306160) with breast cancer development and progression. The study consists of 493 breast cancer cases recruited from Nizam's Institute of Medical Sciences, Hyderabad, and 558 age-matched healthy female controls from rural and urban areas. Genomic DNA was isolated by non-enzymatic method. Genotyping was done by amplification refractory mutation system (ARMS-PCR) method. Genotypes were reconfirmed by sequencing and results were analyzed statistically. We have performed Insilco analysis to know the RNA secondary structure by using online tool m fold. The TT genotype and T allele frequencies of Rrp1B1307 T > C polymorphism were significantly elevated in breast cancer (chi (2); p = < 0.008) cases compared to controls under different genetic models. The presence of T allele had conferred 1.75-fold risk for breast cancer development (OR = 1.75; 95 % CI = 1.15-2.67). The frequency of TT genotype of Rrp1b 1307T > C polymorphism was significantly elevated in obese patients (chi (2); p = 0.008) and patients with advanced disease (chi (2); p = 0.01) and with increased tumor size (chi (2); p = 0.01). Moreover, elevated frequency of T allele was also associated with positive lymph node status (chi (2); p = 0.04) and Her2 negative receptor status (chi (2); p = 0.006). Presence of Rrp1b1307TT genotype and T allele confer strong risk for breast cancer development and progression.

Coupled Mechanisms of Precipitation and Atomization in Burning Nanofluid Fuel Droplets

Understanding the combustion characteristics of fuel droplets laden with energetic nanoparticles (NP) is pivotal for lowering ignition delay, reducing pollutant emissions and increasing the combustion efficiency in next generation combustors. In this study, first we elucidate the feedback coupling between two key interacting mechanisms, namely, secondary atomization and particle agglomeration; that govern the effective mass fraction of NPs within the droplet. Second, we show how the initial NP concentration modulates their relative dominance leading to a masterslave configuration. Secondary atomization of novel nanofuels is a crucial process since it enables an effective transport of dispersed NPs to the flame (a pre-requisite condition for NPs to burn). Contrarily, NP agglomeration at the droplet surface leads to shell formation thereby retaining NPs inside the droplet. In particular, we show that at dense concentrations shell formation (master process) dominates over secondary atomization (slave) while at dilute particle loading it is the high frequency bubble ejections (master) that disrupt shell formation (slave) through its rupture and continuous outflux of NPs. This results in distinct combustion residues at dilute and dense concentrations, thereby providing a method of manufacturing flame synthesized microstructures with distinct morphologies.

Error exponent analysis of energy-based Bayesian decentralized spectrum sensing under fading

This paper considers decentralized spectrum sensing, i.e., detection of occupancy of the primary users' spectrum by a set of Cognitive Radio (CR) nodes, under a Bayesian set-up. The nodes use energy detection to make their individual decisions, which are combined at a Fusion Center (FC) using the K-out-of-N fusion rule. The channel from the primary transmitter to the CR nodes is assumed to undergo fading, while that from the nodes to the FC is assumed to be error-free. In this scenario, a novel concept termed as the Error Exponent with a Confidence Level (EECL) is introduced to evaluate and compare the performance of different detection schemes. Expressions for the EECL under general fading conditions are derived. As a special case, it is shown that the conventional error exponent both at individual sensors, and at the FC is zero. Further, closed-form lower bounds on the EECL are derived under Rayleigh fading and lognormal shadowing. As an example application, it answers the question of whether to use pilot-signal based narrowband sensing, where the signal undergoes Rayleigh fading, or to sense over the entire bandwidth of a wideband signal, where the signal undergoes lognormal shadowing. Theoretical results are validated using Monte Carlo simulations. (C) 2015 Elsevier B.V. All rights reserved.