Phase transformation, improved ferroelectric and magnetic properties of (1-x) BiFeO3-xPb(Zr0.52Ti0.48)O-3 solid solutions

The authors prepared (1 - x) BiFeO3 - (x)Pb(Zr0.52Ti0.48)O-3 for x <= 0.30 by sol-gel method and investigated the material's structures, magnetic and electrical properties. Detailed Rietveld analysis of X-ray diffraction data revealed that the system retains distorted rhombohedral R3c structure for x <= 0.10 but transforms to monoclinic (Cc) structure for x > 0.10. Disappearance of some Raman modes corresponding to A1 modes and the decrease in the intensities of the remaining A1 modes with increasing x in the Raman spectra, which is a clear indication of structural modification and symmetry changes brought about by PZT doping. Enhanced magnetization with PZT doping content may be attributed to the gradual change and destruction in the spin cycloid structure of BiFeO3. The leakage current density at 3.5 kV/cm was reduced by approximately three orders of magnitude by doping PZT (x = 0.30), compared with BFO ceramics. (C) 2014 AIP Publishing LLC.

Cationic gemini lipids containing polyoxyethylene spacers as improved transfecting agents of plasmid DNA in cancer cells

Lipoplex nano-aggregates have been analyzed through biophysical characterization (electrostatics, structure, size and morphology), and biological studies (transfection efficiency and cell viability) in five cancer cell lines. Lipoplexes were prepared from pEGFP-C3 plasmid DNA (pDNA) and mixed liposomes, constituted by a zwitterionic lipid (DOPE) and a gemini cationic lipid (GCL) synthesized in this work, bis(hexadecyl dimethyl ammonium) oxyethylene], referred to as (C16Am)(2)(C2O)(n), (where n is the oxyethylene spacer length, n = 1, 2 or 3, between the ammonium heads). Cryo-TEM micrographs show nano-aggregates with two multilamellar structures, a cluster-type (at low-to-medium GCL composition) and a fingerprint-type that coexists with the cluster-type at medium GCL composition and appears alone at high GCL composition. SAXS diffractograms show that these lipoplexes present three lamellar structures, two of them coexisting at low and high GCL composition. The optimized transfection efficiency (TE) of pDNA was higher for lipoplexes containing GCLs with a longer (n = 3) or shorter (n = 1) polyoxyethylene spacer, at high GCL composition (alpha - 0.7) with low charge ratio (rho(eff) 2). In the all cancer cell lines studied, the TE of the optimized formulations was much better than those of both lipofectamine 2000 and lipoplexes with GCLs of the bis(hexadecyl dimethyl ammonium) alkane series recently reported. Probably, (a) the coexistence of two lamellar structures at high GCL composition synergizes the TE of these lipid vectors, (b) the orientation of the polyoxyethylene region in (C16Am)(2)(C2O)(3)/DOPE may occur in such a way that the spacing between two cationic heads becomes smaller than that in (C16Am)(2)(C2O)(2)/DOPE which is poor in terms of TE, and (c) the synergistic interactions between serum proteins and (C16Am)(2)(C2O)(n)/DOPE-pDNA lipoplexes containing a polyoxyethylene spacer improve TE, especially at high GCL content. Lipoplexes studied here show very low levels of toxicity, which confirm them as improved vectors of pDNA in gene therapy.

Reduced graphene oxide-supported nickel oxide catalyst with improved CO tolerance for formic acid electrooxidation

The superior catalytic activity along with improved CO tolerance for formic acid electro-oxidation has been demonstrated on a NiO-decorated reduced graphene oxide (rGO) catalyst. The cyclic voltammetry response of rGO-NiO/Pt catalyst elucidates improved CO tolerance and follows direct oxidation pathway. It is probably due to the beneficial effect of residual oxygen groups on rGO support which is supported by FT-IR spectrum. A strong interaction of rGO support with NiO nanoparticles facilitates the removal of CO from the catalyst surface. The chronoamperometric response indicates a higher catalytic activity and stability of rGO-NiO/Pt catalyst than the NiO/Pt and unmodified Pt electrode catalyst for a prolonged time of continuous oxidation of formic acid. Copyright (C) 2014, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights reserved.

Improved Erlenmeyer Synthesis with 5-Thiazolone and Catalytic Mn(II) Acetate. Crystal Structure Confirmation of the Reaction Stereochemistry

2-Phenylthiazolin-5-one (5, a thioazlactone) condenses with various aldehydes in the presence of the mild base Mn(II) acetate as catalyst in CH2Cl2 solution. This leads to the corresponding Erlenmeyer reaction products (6) in excellent yields in the case of aromatic aldehydes and moderate yields in others. The mildness of the reaction conditions is apparently enabled by the aromaticity of the (putative) intermediate thiazolone anion. The structure and stereochemistry (Z) of the product derived from i-BuCHO was confirmed by single crystal X-ray diffraction. This study overcomes key limitations of the classical Erlenmeyer synthesis and also introduces the relatively nontoxic Mn(II) acetate as a reagent in heterocyclic chemistry.

Understanding Self-Segregation of Immiscible Peripheral Segments in Pseudodendritic Hyperbranched Polydithioacetals: Formation of Improved Janus Structures

Peripherally heterofunctionalized hyperbranched polymers (HBPs) undergo immiscibility-driven self-segregation of the outer segments to form Janus molecular entities (Macromolecules 2012, 45, 2348). In HBPs prepared via AB2 type self-condensation, single-step peripheral heterofunctionalization would lead to random distribution of the two types of terminal units, namely, homofunctionalized (homo-T) and heterofunctionalized (hetero-T) termini. Here, we examine the role of such hetero-T units on the self-segregation of heterofunctionalized pseudodendritic hyperbranched polydithioacetals. Three different heterofunctionalized HB dithioacetals bearing roughly 50 mol % each of docsyl (C-22) and MPEG-350 chains at the periphery were prepared: one of them carried a statistical distribution of homo-T and hetero-T units, and the other carried only two types of homo-T (-TR1R1 and -TR2R2) termini, whereas the third carried largely hetero-T (-TR1R2) termini. Careful examination of DSC and SAXS data reveals that the self-segregation is most effective in HBPs devoid of hetero-T units; interestingly, however, it also showed that randomly heterofunctionalized HBPs self-segregated nearly as effectively.

Improved quasiparticle wave functions and mean field for G(0)W(0) calculations: Initialization with the COHSEX operator

The GW approximation to the electron self-energy has become a standard method for ab initio calculation of excited-state properties of condensed-matter systems. In many calculations, the G W self-energy operator, E, is taken to be diagonal in the density functional theory (DFT) Kohn-Sham basis within the G0 W0 scheme. However, there are known situations in which this diagonal Go Wo approximation starting from DFT is inadequate. We present two schemes to resolve such problems. The first, which we called sc-COHSEX-PG W, involves construction of an improved mean field using the static limit of GW, known as COHSEX (Coulomb hole and screened exchange), which is significantly simpler to treat than GW W. In this scheme, frequency-dependent self energy E(N), is constructed and taken to be diagonal in the COHSEX orbitals after the system is solved self-consistently within this formalism. The second method is called off diagonal-COHSEX G W (od-COHSEX-PG W). In this method, one does not self-consistently change the mean-field starting point but diagonalizes the COHSEX Hamiltonian within the Kohn-Sham basis to obtain quasiparticle wave functions and uses the resulting orbitals to construct the G W E in the diagonal form. We apply both methods to a molecular system, silane, and to two bulk systems, Si and Ge under pressure. For silane, both methods give good quasiparticle wave functions and energies. Both methods give good band gaps for bulk silicon and maintain good agreement with experiment. Further, the sc-COHSEX-PGW method solves the qualitatively incorrect DFT mean-field starting point (having a band overlap) in bulk Ge under pressure.

An improved free surface modeling for incompressible SPH

In Incompressible Smooth Particle Hydrodynamics (ISPH), a pressure Poisson equation (PPE) is solved to obtain a divergence free velocity field. When free surfaces are simulated using this method a Dirichlet boundary condition for pressure at the free surface has to be applied. In existing ISPH methods this is achieved by identifying free surface particles using heuristically chosen threshold of a parameter such as kernel sum, density or divergence of the position, and explicitly setting their pressure values. This often leads to clumping of particles near the free surface and spraying off of surface particles during splashes. Moreover, surface pressure gradients in flows where surface tension is important are not captured well using this approach. We propose a more accurate semi-analytical approach to impose Dirichlet boundary conditions on the free surface. We show the efficacy of the proposed algorithm by using test cases of elongation of a droplet and dam break. We perform two dimensional simulations of water entry and validate the proposed algorithm with experimental results. Further, a three dimensional simulation of droplet splash is shown to compare well with the Volume-of-Fluid simulations. (C) 2014 Elsevier Ltd. All rights reserved.

An Improved Dead-Time Compensation Scheme for Voltage Source Inverters Considering the Device Switching Transition Times

Inverter dead-time, which is meant to prevent shoot-through fault, causes harmonic distortion and change in the fundamental voltage in the inverter output. Typical dead-time compensation schemes ensure that the amplitude of the fundamental output current is as desired, and also improve the current waveform quality significantly. However, even with compensation, the motor line current waveform is observed to be distorted close to the current zero-crossings. The IGBT switching transition times being significantly longer at low currents than at high currents is an important reason for this zero-crossover distortion. Hence, this paper proposes an improved dead-time compensation scheme, which makes use of the measured IGBT switching transition times at low currents. Measured line current waveforms in a 2.2 kW induction motor drive with the proposed compensation scheme are compared against those with the conventional dead-time compensation scheme and without dead-time compensation. The experimental results on the motor drive clearly demonstrate the improvement in the line current waveform quality with the proposed method.

Improved tuning of the extended concentric tube resonator for wide-band transmission loss

Transmission loss (TL) of a simple expansion chamber (SEC) consists of periodic domes with sharp troughs. This limits practical application of the SEC in the variable-speed automobile exhaust systems. Three-fourths of the troughs of the SEC can be lifted by appropriate tuning of the extended inlet/outlet lengths. However, such mufflers suffer from high back pressure and generation of aerodynamic noise due to free shear layers at the area discontinuities. Therefore, a perforate bridge is made between the extended inlet and outlet. It is shown that the TL curve of a concentric tube resonator (CTR) can also be lifted in a similar way by proper tuning of the extended unperforated lengths. Differential lengths have to be used to correct the inlet/outlet lengths in order to account for the perforate inertance. The resonance peak frequencies calculated by means of the 1-D analysis are compared with those of the 3-D FEM, and appropriate differential lengths are calculated. It is shown how different geometric characteristics of the muffler and mean flow affect the differential lengths. A general correlation is obtained for the differential lengths by considering seven relevant geometric and environmental parameters in a comprehensive parametric study. The resulting expressions would help in design of extended-tube CTR for wide-band TL. (C) 2014 Institute of Noise Control Engineering.

Improved subject-independent acoustic-to-articulatory inversion

In subject-independent acoustic-to-articulatory inversion, the articulatory kinematics of a test subject are estimated assuming that the training corpus does not include data from the test subject. The training corpus in subject-independent inversion (SII) is formed with acoustic and articulatory kinematics data and the acoustic mismatch between training and test subjects is then estimated by an acoustic normalization using acoustic data drawn from a large pool of speakers called generic acoustic space (GAS). In this work, we focus on improving the SII performance through better acoustic normalization and adaptation. We propose unsupervised and several supervised ways of clustering GAS for acoustic normalization. We perform an adaptation of acoustic models of GAS using the acoustic data of the training and test subjects in SII. It is found that SII performance significantly improves (similar to 25% relative on average) over the subject-dependent inversion when the acoustic clusters in GAS correspond to phonetic units (or states of 3-state phonetic HMMs) and when the acoustic model built on GAS is adapted to training and test subjects while optimizing the inversion criterion. (C) 2014 Elsevier B.V. All rights reserved.

An Improved Outer Bound on the Storage-Repair-Bandwidth Tradeoff of Exact-Repair Regenerating Codes

While the tradeoff between the amount of data stored and the repair bandwidth of an (n, k, d) regenerating code has been characterized under functional repair (FR), the case of exact repair (ER) remains unresolved. It is known that there do not exist ER codes which lie on the FR tradeoff at most of the points. The question as to whether one can asymptotically approach the FR tradeoff was settled recently by Tian who showed that in the (4, 3, 3) case, the ER region is bounded away from the FR region. The FR tradeoff serves as a trivial outer bound on the ER tradeoff. In this paper, we extend Tian's results by establishing an improved outer bound on the ER tradeoff which shows that the ER region is bounded away from the FR region, for any (n; k; d). Our approach is analytical and builds upon the framework introduced earlier by Shah et. al. Interestingly, a recently-constructed, layered regenerating code is shown to achieve a point on this outer bound for the (5, 4, 4) case. This represents the first-known instance of an optimal ER code that does not correspond to a point on the FR tradeoff.

Improved design methodology for the development of electrically actuated MEMS structures

A comprehensive design flow is proposed for the design of Micro Electro Mechanical Systems that are fabricated using SOIMUMPs process. Many of the designers typically do not model the temperature dependency of electrical conductivity, thermal conductivity and convection coefficient, as it is very cumbersome to create/incorporate the same in the existing FEM simulators. Capturing these dependencies is very critical particularly for structures that are electrically actuated. Lookup tables that capture the temperature dependency of electrical conductivity, thermal conductivity and convection coefficient are created. These look up tables are taken as inputs for a commercially available FEM simulator to model the semiconductor behavior. It is demonstrated that when temperature dependency for all the above mentioned parameters is not captured, then the error in estimation of the maximum temperature (for a given structure) could be as high as 30%. Error in the estimated resistance value under the same conditions is as high as 40%. When temperature dependency of the above mentioned parameters is considered then error w.r.t the measured values is less than 5%. It is evident that error in temperature estimates leads to erroneous results from mechanical simulations as well.

Prediction of Queue Waiting Times for Metascheduling on Parallel Batch Systems

Prediction of queue waiting times of jobs submitted to production parallel batch systems is important to provide overall estimates to users and can also help meta-schedulers make scheduling decisions. In this work, we have developed a framework for predicting ranges of queue waiting times for jobs by employing multi-class classification of similar jobs in history. Our hierarchical prediction strategy first predicts the point wait time of a job using dynamic k-Nearest Neighbor (kNN) method. It then performs a multi-class classification using Support Vector Machines (SVMs) among all the classes of the jobs. The probabilities given by the SVM for the class predicted using k-NN and its neighboring classes are used to provide a set of ranges of predicted wait times with probabilities. We have used these predictions and probabilities in a meta-scheduling strategy that distributes jobs to different queues/sites in a multi-queue/grid environment for minimizing wait times of the jobs. Experiments with different production supercomputer job traces show that our prediction strategies can give correct predictions for about 77-87% of the jobs, and also result in about 12% improved accuracy when compared to the next best existing method. Experiments with our meta-scheduling strategy using different production and synthetic job traces for various system sizes, partitioning schemes and different workloads, show that the meta-scheduling strategy gives much improved performance when compared to existing scheduling policies by reducing the overall average queue waiting times of the jobs by about 47%.

Tetrahydrofuran amino acid-containing gramicidin S analogues with improved biological profiles

Gramicidin S (GS) is a cyclic cationic antimicrobial peptide (CAP) with a wide spectrum of antibiotic activities whose usage has been limited to topical applications owing to its cytotoxic side effects. We have synthesized tetrahydrofuran amino acid (Taa)-containing GS analogues, and we have carried out conformational analysis and explored their structure activity relationships by evaluating their antitubercular, antibacterial and cytotoxic properties. Two of these analogues showed impressive as well as selective activity against Mycobacterium tuberculosis (MTB) without toxicity towards mammalian Vero cells or human RBCs, and are promising as potential leads.

Improved capacity and stability of integrated Li and Mn rich layered-spinel Li1.17Ni0.25Mn1.08O3 cathodes for Li-ion batteries

A Li-rich layered-spinel material with a target composition Li1.17Ni0.25Mn1.08O3 (xLiLi1/3Mn2/3]O-2.(1 - x) LiNi0.5Mn1.5O4, (x = 0.5)) was synthesized by a self-combustion reaction (SCR), characterized by XRD, SEM, TEM, Raman spectroscopy and was studied as a cathode material for Li-ion batteries. The Rietveld refinement results indicated the presence of monoclinic (LiLi1/3Mn2/3]O-2) (52%), spinel (LiNi0.5Mn1.5O4) (39%) and rhombohedral LiNiO2 (9%). The electrochemical performance of this Li-rich integrated cathode material was tested at 30 degrees C and compared to that of high voltage LiNi0.5Mn1.5O4 spinel cathodes. Interestingly, the layered-spinel integrated cathode material exhibits a high specific capacity of about 200 mA h g(-1) at C/10 rate as compared to 180 mA h g(-1) for LiNi0.5Mn1.5O4 in the potential range of 2.4-4.9 V vs. Li anodes in half cells. The layered-spinel integrated cathodes exhibited 92% capacity retention as compared to 82% for LiNi0.5Mn1.5O4 spinel after 80 cycles at 30 degrees C. Also, the integrated cathode material can exhibit 105 mA h g(-1) at 2 C rate as compared to 78 mA h g(-1) for LiNi0.5Mn1.5O4. Thus, the presence of the monoclinic phase in the composite structure helps to stabilize the spinel structure when high specific capacity is required and the electrodes have to work within a wide potential window. Consequently, the Li1.17Ni0.25Mn1.08O3 composite material described herein can be considered as a promising cathode material for Li ion batteries.