Ag@AgI, Core@Shell Structure in Agarose Matrix as Hybrid: Synthesis, Characterization, and Antimicrobial Activity

A novel in situ core@shell structure consisting of nanoparticles of Ag (Ag Nps) and AgI in agarose matrix (Ag@ AgI/agarose) has been synthesized as a hybrid, in order to have an efficient antibacterial agent for repetitive usage with no toxicity. The synthesized core@shell structure is very well characterized by XRD, UV-visible, photoluminescence, and TEM. A detailed antibacterial studies including repetitive cycles are carried out on Gram-negative Escherichia coli (E. coli) and Gram-positive Staphylococcus aureus (S. aureus) bacteria in saline water, both in dark and on exposure to visible light. The hybrid could be recycled for the antibacterial activity and is nontoxic toward human cervical cancer cells (HeLa cells). The water insoluble Ag@AgI in agarose matrix forms a good coating on quartz, having good mechanical strength. EPR and TEM studies are carried out on the Ag@AgI/agarose and the bacteria, respectively, to elucidate a possible mechanism for killing of the bacteria.

On the microstructure-tensile property correlations in bulk metallic glass matrix composites with crystalline dendrites

Bulk metallic glass (BMG) matrix composites with crystalline dendrites as reinforcements exhibit a wide variance in their microstructures (and thus mechanical properties), which in turn can be attributed to the processing route employed, which affects the size and distribution of the dendrites. A critical investigation on the microstructure and tensile properties of Zr/Ti-based BMG composites of the same composition, but produced by different routes, was conducted so as to identify ``structure-property'' connections in these materials. This was accomplished by employing four different processing methods-arc melting, suction casting, semi-solid forging and induction melting on a water-cooled copper boat-on composites with two different dendrite volume fractions, V-d. The change in processing parameters only affects microstructural length scales such as the interdendritic spacing, lambda, and dendrite size, delta, whereas compositions of the matrix and dendrite are unaffected. Broadly, the composite's properties are insensitive to the microstructural length scales when V-d is high (similar to 75%), whereas they become process dependent for relatively lower V-d (similar to 55%). Larger delta in arc-melted and forged specimens result in higher ductility (7-9%) and lower hardening rates, whereas smaller dendrites increase the hardening rate. A bimodal distribution of dendrites offers excellent ductility at a marginal cost of yield strength. Finer lambda result in marked improvements in both ductility and yield strength, due to the confinement of shear band nucleation sites in smaller volumes of the glassy phase. Forging in the semi-solid state imparts such a microstructure. (c) 2012 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

Synthesis of zinc oxide porous structures by anodization with water as an electrolyte

We report a simple, reliable and one-step method of synthesizing ZnO porous structures at room temperature by anodization of zinc (Zn) sheet with water as an electrolyte and graphite as a counter electrode. We observed that the de-ionized (DI) water used in the experiment is slightly acidic (pH=5.8), which is due to the dissolution of carbon dioxide from the atmosphere forming carbonic acid. Porous ZnO is characterized by scanning electron microscopy (SEM), transmission electron microscopy (TEM), Raman spectroscopy and photoluminescence (PL) studies. The current-transient measurement is carried out using a Gamry Instruments Reference 3000 and the thickness of the deposited films is measured using a Dektak surface profilometer. The PL, Raman and X-ray photoelectron spectroscopy are used to confirm the presence of ZnO phase. We have demonstrated that the hybrid structures of ZnO and poly (3,4-ethylenedioxythiophene):poly (styrene sulfonate) (PEDOT:PSS) exhibit good rectifying characteristics. The evaluated barrier height and the ideality factor are 0.45 eV and 3.6, respectively.

Porous Three Dimensional Arrays of Plasmonic Nanoparticles

Plasmonic interactions in a well-defined array of metallic nanoparticles can lead to interesting optical effects, such as local electric field enhancement and shifts in the extinction spectra, which are of interest in diverse technological applications, including those pertaining to biochemical sensing and photonic circuitry. Here, we report on a single-step wafer scale fabrication of a three-dimensional array of metallic nanoparticles whose sizes and separations can be easily controlled to be anywhere between fifty to a few hundred nanometers, allowing the optical response of the system to be tailored with great control in the visible region of the spectrum. The substrates, apart from having a large surface area, are inherently porous and therefore suitable for optical sensing applications, such as surface enhanced Raman scattering, containing a high density of spots with enhanced local electric fields arising from plasmonic couplings.

Photocatalytic degradation of gaseous toluene by using immobilized titania/silica on aluminum sheets

The aim of this study was to prepare a highly active immobilized titania/silica photocatalyst and to test its performance in situ toward degradation of toluene as one of the major toxic indoor contaminants. In this work, two different titania layers immobilized on Al sheets were synthesized via low temperature sol-gel method employing presynthesized highly active titania powders (Degussa P25 and Millennium PC500, mass ratio 1:1): (a) with a silica/titania binder and a protective layer and (b) without the binder. The photocatalysts were characterized by X-ray diffraction, nitrogen sorption measurements, scanning electron microscopy (SEM), infrared spectroscopy, and UV-vis diffuse reflectance spectroscopy (DRS). The in situ photocatalytic degradation of gaseous toluene was selected as a probe reaction to test photocatalytic activity and to verify the potential application of these materials for air remediation. Results show that nontransparent highly photocatalytically active coatings based on the silica/titania binder and homogeneously dispersed TiO2 powders were obtained on the Al sheets. The crystalline structure of titania was not altered upon addition of the binder, which also prevented inhomogeneous agglomeration of particles on the photocatalyst surface. The photoactivity results indicate that the adsorption properties and photocatalytic activity of immobilized photocatalysts with the silica/titania binder and an underlying protective layer were very effective and additionally, they exhibited considerably improved adhesion and uniformity. We present a new highly photocatalytically active immobilized catalyst on a convenient metallic support, which has a potential application in an air cleaning device.

Development of experimental setup for study of adsorption characteristics of porous materials down to 4.2 K

The knowledge of adsorption characteristics of activated carbon (porous material) in the temperature range from 5 to 20 K is essential when used in cryosorption pumps for nuclear fusion applications. However, such experimental data are very scarce in the literature, especially below 77 K. So, an experimental system is designed and fabricated to measure the adsorption characteristics of porous materials under variable cryogenic temperatures (from 5 K to 100 K). This is based on the commercially available micropore-analyser coupled to a closed helium cycle two-stage Gifford McMahon (GM) Cryocooler, which allows the sample to be cooled to 4.2 K. The sample port is coupled to the Cryocooler through a heat switch, which isolates this port from the cold head of the Cryocooler. By this, the sample temperature can now be varied without affecting the Cryocooler. The setup enables adsorption studies in the pressure range from atmospheric down to 10(-4) Pa. The paper describes the details of the experimental setup and presents the results of adsorption studies at 77 K for activated carbon with nitrogen as adsorbate. The system integration is now completed to enable adsorption studies at 4.2 K.

Nonlocal continuum mechanics based ultrasonic flexural wave dispersion characteristics of a monolayer graphene embedded in polymer matrix

Wave propagation in graphene sheet embedded in elastic medium (polymer matrix) has been a topic of great interest in nanomechanics of graphene sheets, where the equivalent continuum models are widely used. In this manuscript, we examined this issue by incorporating the nonlocal theory into the classical plate model. The influence of the nonlocal scale effects has been investigated in detail. The results are qualitatively different from those obtained based on the local/classical plate theory and thus, are important for the development of monolayer graphene-based nanodevices. In the present work, the graphene sheet is modeled as an isotropic plate of one-atom thick. The chemical bonds are assumed to be formed between the graphene sheet and the elastic medium. The polymer matrix is described by a Pasternak foundation model, which accounts for both normal pressure and the transverse shear deformation of the surrounding elastic medium. When the shear effects are neglected, the model reduces to Winkler foundation model. The normal pressure or Winkler elastic foundation parameter is approximated as a series of closely spaced, mutually independent, vertical linear elastic springs where the foundation modulus is assumed equivalent to stiffness of the springs. For this model, the nonlocal governing differential equations of motion are derived from the minimization of the total potential energy of the entire system. An ultrasonic type of flexural wave propagation model is also derived and the results of the wave dispersion analysis are shown for both local and nonlocal elasticity calculations. From this analysis we show that the elastic matrix highly affects the flexural wave mode and it rapidly increases the frequency band gap of flexural mode. The flexural wavenumbers obtained from nonlocal elasticity calculations are higher than the local elasticity calculations. The corresponding wave group speeds are smaller in nonlocal calculation as compared to local elasticity calculation. The effect of y-directional wavenumber (eta(q)) on the spectrum and dispersion relations of the graphene embedded in polymer matrix is also observed. We also show that the cut-off frequencies of flexural wave mode depends not only on the y-direction wavenumber but also on nonlocal scaling parameter (e(0)a). The effect of eta(q) and e(0)a on the cut-off frequency variation is also captured for the cases of with and without elastic matrix effect. For a given nanostructure, nonlocal small scale coefficient can be obtained by matching the results from molecular dynamics (MD) simulations and the nonlocal elasticity calculations. At that value of the nonlocal scale coefficient, the waves will propagate in the nanostructure at that cut-off frequency. In the present paper, different values of e(0)a are used. One can get the exact e(0)a for a given graphene sheet by matching the MD simulation results of graphene with the results presented in this article. (c) 2012 Elsevier Ltd. All rights reserved.

Morphology Controlled Growth of Meso-Porous Co3O4 Nanostructures and Study of Their Electrochemical Capacitive Behavior

The morphology of nanocrystalline Co3O4 synthesized through microwave irradiation of a solution of a cobalt complex is found to depend reproducibly on the conditions of synthesis and, in particular, on the composition of the solvent used. Despite the rapidity of the process, oriented aggregation occurs under certain conditions, depending on solvent composition. Annealing the oriented samples leads to microstructures with significant porosity, rendering the material suitable as electrodes for electrochemical capacitors. Electrochemical analysis of the oxide samples was carried out in 0.1M Na2SO4 electrolyte vs. Ag/AgCl electrode. A stable specific capacitance of 221 F/g was measured for a meso-porous sample displaying oriented aggregation. Stability of these oxide materials were checked for longer charge-discharge cycling. (C) 2012 The Electrochemical Society. DOI: 10.1149/2.002210jes] All rights reserved.

Temporal Moments for Reactive Transport through Fractured Impermeable/Permeable Formations

The transport of reactive solutes through fractured porous formations has been analyzed. The transport through the porous block is represented by a general multiprocess nonequilibrium equation (MPNE), which, for the fracture, is represented by an advection-dispersion equation with linear equilibrium sorption and first-order transformation. An implicit finite-difference technique has been used to solve the two coupled equations. The transport characteristics have been analyzed in terms of zeroth, first, and second temporal moments of the solute in the fracture. The solute behavior for fractured impermeable and fractured permeable formations are first compared and the effects of various fracture and matrix transport parameters are analyzed. Subsequently, the transport through a fractured permeable formation is analyzed to ascertain the effect of equilibrium sorption, rate-limited sorption, and the multiprocess nonequilibrium transport process. It was found that the temporal moments were nearly identical for the fractured impermeable and permeable formations when both the diffusion coefficient and the first-order transformation coefficient were relatively large. The multiprocess nonequilibrium model resulted in a smaller mass recovery in the fracture and higher dispersion than the equilibrium and rate-limited sorption models. DOI: 10.1061/(ASCE)HE.19435584.0000586. (C) 2012 American Society of Civil Engineers.

A 12 V Substrate-Integrated PbO2-Activated Carbon Asymmetric Hybrid Ultracapacitor with Silica-Gel-Based Inorganic-Polymer Electrolyte

A 12 V Substrate-Integrated PbO2-Activated Carbon hybrid ultracapacitor (SI-PbO2-AC HUCs) with silica-gel sulfuric acid electrolyte is developed and performance tested. The performance of the silica-gel based hybrid ultracapacitor is compared with flooded and AGM-based HUCs. These HUCs comprise substrate-integrated PbO2 (SI-PbO2) as positive electrodes and high surface-area activated carbon with dense graphite-sheet substrate as negative electrodes. 12 V SI-PbO2-AC HUCs with flooded, AGM and gel electrolytes are found to have capacitance values of 308 F, 184 F, and 269 F at C-rate and can be pulse charged and discharged for 100,000 cycles with only a nominal decrease in their capacitance values. The best performance is exhibited by gel-electrolyte HUCs.

Wave propagation in a porous composite beam: Porosity determination, location and quantification

A wave-based method is developed to quantify the defect due to porosity and also to locate the porous regions, in a composite beam-type structure. Wave propagation problem for a porous laminated composite beam is modeled using spectral finite element method (SFEM), based on the modified rule of mixture approach, which is used to include the effect of porosity on the stiffness and density of the composite beam structure. The material properties are obtained from the modified rule of mixture model, which are used in a conventional SFEM to develop a new model for solving wave propagation problems in porous laminated composite beam. The influence of the porosity content on the group speed and also the effect of variation in theses parameters on the time responses are studied first, in the forward problem. The change in the time responses with the change in the porosity of the structure is used as a parameter to find the porosity content in a composite beam. The actual measured response from a structure and the numerically obtained time responses are used for the estimation of porosity, by solving a nonlinear optimization problem. The effect of the length of the porous region (in the propagation direction), on the time responses, is studied. The damage force indicator technique is used to locate the porous region in a beam and also to find its length, using the measured wave propagation responses. (C) 2012 Elsevier Ltd. All rights reserved.

Fast acoustic likelihood computation using low-rank matrix approximation

Acoustic modeling using mixtures of multivariate Gaussians is the prevalent approach for many speech processing problems. Computing likelihoods against a large set of Gaussians is required as a part of many speech processing systems and it is the computationally dominant phase for LVCSR systems. We express the likelihood computation as a multiplication of matrices representing augmented feature vectors and Gaussian parameters. The computational gain of this approach over traditional methods is by exploiting the structure of these matrices and efficient implementation of their multiplication.In particular, we explore direct low-rank approximation of the Gaussian parameter matrix and indirect derivation of low-rank factors of the Gaussian parameter matrix by optimum approximation of the likelihood matrix. We show that both the methods lead to similar speedups but the latter leads to far lesser impact on the recognition accuracy. Experiments on a 1138 word vocabulary RM1 task using Sphinx 3.7 system show that, for a typical case the matrix multiplication approach leads to overall speedup of 46%. Both the low-rank approximation methods increase the speedup to around 60%, with the former method increasing the word error rate (WER) from 3.2% to 6.6%, while the latter increases the WER from 3.2% to 3.5%.

Proton Conduction in Metal-Organic Frameworks and Related Modularly Built Porous Solids

Proton-conducting materials are an important component of fuel cells. Development of new types of proton-conducting materials is one of the most important issues in fuel-cell technology. Herein, we present newly developed proton-conducting materials, modularly built porous solids, including coordination polymers (CPs) or metalorganic frameworks (MOFs). The designable and tunable nature of the porous materials allows for fast development in this research field. Design and synthesis of the new types of proton-conducting materials and their unique proton-conduction properties are discussed.

Polyvinylbutyral based hybrid organic/inorganic films as a moisture barrier material

Flexible and thermally stable, freestanding hybrid organic/inorganic based polymer-composite films have been fabricated using a simple solution casting method. Polyvinylbutyral and amine functionalized mesoporous silica were used to synthesize the composite. An additional polyol-''tripentaerythritol''-component was also used to increase the -OH group content in the composite matrix. The moisture permeability of the composites was investigated by following a calcium degradation test protocol. This showed a reduction in the moisture permeability with the increase in functionalized silica loadings in the matrix. A reduction in permeability was observed for the composites as compared to the neat polymer film. The thermal and mechanical properties of these composites were also investigated by various techniques like thermogravimetric analysis, differential scanning calorimetry, tensile experiments, and dynamic mechanical analysis. It was observed that these properties detonate with the increase in the functionalized silica content and hence an optimized loading is required in order to retain critical properties. This deterioration is due to the aggregation of the fillers in the matrix. Furthermore, the films were used to encapsulate P3HT (poly 3 hexyl thiophene) based organic Schottky structured diodes, and the diode characteristics under accelerated aging conditions were studied. The weathered diodes, encapsulated with composite film showed an improvement in the lifetime as compared to neat polymer film. The initial investigation of these films suggests that they can be used as a moisture barrier layer for organic electronics encapsulation application.

Hybrid online non-negative matrix factorization for clustering of documents

When document corpus is very large, we often need to reduce the number of features. But it is not possible to apply conventional Non-negative Matrix Factorization(NMF) on billion by million matrix as the matrix may not fit in memory. Here we present novel Online NMF algorithm. Using Online NMF, we reduced original high-dimensional space to low-dimensional space. Then we cluster all the documents in reduced dimension using k-means algorithm. We experimentally show that by processing small subsets of documents we will be able to achieve good performance. The method proposed outperforms existing algorithms.