Thermodynamic activities in the Pb(Zr1−XTiX)O3 solid solution at 1373K

Although Pb(Zr1−XTiX)O3 solid solution is the cornerstone of the piezoelectric ceramics, there is no information in the literature on thermodynamic activities of the component phases in the solid solution. Using inter-crystalline ion exchange equilibria between Pb(Zr1−XTiX)O3 solid solution with cubic perovskite structure and (Zr1−YTiY)O2 solid solutions with monoclinic and tetragonal structures, activities of PbTiO3 and PbZrO3 in the perovskite solid solution have been derived at 1373 K using the modified Gibbs–Duhem integration technique of Jacob and Jeffes. Tie-lines from the cubic solid solution are skewed towards the ZrO2 corner. Activities in the zirconia-rich (Zr1−YTiY)O2 solid solutions are taken from a recent emf study. The results for the perovskite solid solution at 1373 K can be represented by a sub-regular solution model:View the MathML sourcewhere ΔGE,M is the excess Gibbs energy of mixing of the cubic solid solution and Xi represents the mole fraction of component i. There is a significant positive deviation from ideality for PbTiO3-rich compositions and mild negative deviation near the PbZrO3 corner. The cubic solid solution is intrinsically stable against composition fluctuations at temperatures down to 840 K. The results contrast sharply with the recent calorimetric data on enthalpy of mixing which signal instability of the cubic perovskite solid solution.

Highly fluorescent GFPm2+-based genome integration-proficient promoter probe vector to study Mycobacterium tuberculosis promoters in infected macrophages

Study of activity of cloned promoters in slow-growing Mycobacterium tuberculosis during long-term growth conditions in vitro or inside macrophages, requires a genome-integration proficient promoter probe vector, which can be stably maintained even without antibiotics, carrying a substrate-independent, easily scorable and highly sensitive reporter gene. In order to meet this requirement, we constructed pAKMN2, which contains mycobacterial codon-optimized gfpm2+ gene, coding for GFPm2+ of highest fluorescence reported till date, mycobacteriophage L5 attP-int sequence for genome integration, and a multiple cloning site. pAKMN2 showed stable integration and expression of GFPm2+ from M. tuberculosis and M. smegmatis genome. Expression of GFPm2+, driven by the cloned minimal promoters of M. tuberculosis cell division gene, ftsZ (MtftsZ), could be detected in the M. tuberculosis/pAKMN2-promoter integrants, growing at exponential phase in defined medium in vitro and inside macrophages. Stable expression from genome-integrated format even without antibiotic, and high sensitivity of detection by flow cytometry and fluorescence imaging, in spite of single copy integration, make pAKMN2 useful for the study of cloned promoters of any mycobacterial species under long-term in vitro growth or stress conditions, or inside macrophages.

Electrochemical Integration of Graphene with Light-Absorbing Copper-Based Thin Films

We present an electrochemical route for the integration of graphene with light-sensitive copper-based alloys used in optoelectronic applications. Graphene grown using chemical vapor deposition (CVD) transferred to glass is found to be a robust substrate on which photoconductive CuxS films of 1-2 mu m thickness can be deposited. The effect of growth parameters on the morphology and photoconductivity of CuxS films is presented. Current-voltage (I-V) characterization and photoconductivity decay experiments are performed with graphene as one contact and silver epoxy as the other.

Fracture analysis of cracked plate panels using NI-MVCCI technique

The objective of this paper is to propose a numerically integrated modified virtual crack closure integral (NI-MVCCI) technique for fracture analysis of cracked plate panels. NI-MVCCI technique is generalized one and the expressions for computing the strain energy release rate (SERR) are independent of the finite element employed. NI-MVCCI technique has been demonstrated for 4-noded, 8-noded (regular and quarter-point) and 9-noded isoparametric finite elements. Numerical studies on fracture analysis of 2-D crack (mode-I and mode-II) problems have been conducted employing these elements. SERR and stress intensity factors (SIF) have been computed for these problems and found to be in good agreement with the respective analytical solutions available in the literature. The appropriate Gauss numerical integration order to be employed for each of these elements for accurate computation of SERR and SIF has been recommended based on the studies.

Surface reconstruction from disparate shading: an integration of shape-from-shading and stereopsis

A cooperative integration of stereopsis and shape-from-shading is presented. The integration makes the process of D surface reconstruction better constrained and more reliable. It also obviates the need for surface boundary conditions, and explicit information about the surface albedo and the light source direction, which can now be estimated in an iterative manner

Acenaphtho[1,2-b]quinoxaline based low band gap copolymers for organic thin film transistor applications

We report the synthesis of a novel class of low band gap copolymers based on anacenaphtho[1,2-b]quinoxaline core and oligothiophene derivatives acting as the acceptor and the donor moieties, respectively. The optical properties of the copolymers were characterized by ultraviolet-visible spectroscopy while the electrochemical properties were determined by cyclic voltammetry. The band gap of these polymers was found to be in the range 1.8-2.0 eV as calculated from the optical absorption band edge. X-ray diffraction measurements show weak pi-pi stacking interactions between the polymer chains. The hole mobility of the copolymers was evaluated using field-effect transistor measurements yielding values in the range 10(-5)-10(-3) cm(2)/Vs.

Synthesis and characterization of carbon-covered alumina (CCA) supported TiO2 nanocatalysts with enhanced visible light photodegradation of Rhodamine B

The anatase phase of titania (TiO2) nano-photocatalysts was prepared using a modified sol gel process and thereafter embedded on carbon-covered alumina supports. The carbon-covered alumina (CCA) supports were prepared via the adsorption of toluene 2,4-diisocyanate (TDI) on the surface of the alumina. TDI was used as the carbon source for the first time for the carbon-covered alumina support system. The adsorption of TDI on alumina is irreversible; hence, the resulting organic moiety can undergo pyrolysis at high temperatures resulting in the formation of a carbon coating on the surface of the alumina. The TiO2 catalysts were impregnated on the CCA supports. X-ray diffraction analysis indicated that the carbon deposited on the alumina was not crystalline and also showed the successful impregnation of TiO2 on the CCA supports. In the Raman spectra, it could be deduced that the carbon was rather a conjugated olefinic or polycyclic hydrocarbons which can be considered as molecular units of a graphitic plane. The Raman analysis of the catalysed CCAs showed the presence of both the anatase titania and D and G band associated with the carbon of the CCAs. The scanning electron microscope micrographs indicated that the alumina was coated by a carbon layer and the energy dispersive X-ray spectra showed the presence of Al, O and C in the CCA samples, with the addition of Ti for the catalyst impregnated supports. The Brunauer Emmet and Teller surface area analysis showed that the incorporating of carbon on the alumina surface resulted in an increase in surface area, while the impregnation with TiO2 resulted in a further increase in surface area. However, a decrease in the pore volume and diameter was observed. The photocatalytic activity of the nanocatalysts was studied for the degradation of Rhodamine B dye. The CCA-TiO2 nanocatalysts were found to be more photocatalytically active under both visible and UV light irradiation compared to the free TIO2 nanocatalysts.

MicroRNA-155 Is Required for Mycobacterium bovis BCG-Mediated Apoptosis of Macrophages

Pathogenic rnycobacteria, including Mycobacterium tuberculosis and Mycobacterium bovis, cause significant morbidity and mortality worldwide. However, the vaccine strain Mycobacterium bovis BCG, unlike virulent strains, triggers extensive apoptosis of infected macrophages, a step necessary for the elicitation of robust protective immunity. We here demonstrate that M. bovis BCG triggers Toll-like receptor 2 (TLR2)-dependent microRNA-155 (miR-155) expression, which involves signaling cross talk among phosphatidylinositol 3-kinase (PI3K), protein kinase C delta (PKC delta), and mitogen-activated protein kinases (MAPKs) and recruitment of NF-kappa B and c-ETS to miR-155 promoter. Genetic and signaling perturbations presented the evidence that miR-155 regulates PKA signaling by directly targeting a negative regulator of PKA, protein kinase inhibitor alpha (PKI-alpha). Enhanced activation of PKA signaling resulted in the generation of PKA C-alpha; phosphorylation of MSK1, cyclic AMP response element binding protein (CREB), and histone H3; and recruitment of phospho-CREB to the apoptotic gene promoters. The miR-155-triggered activation of caspase-3, BAK1, and cytochrome c translocation involved signaling integration of MAPKs and epigenetic or posttranslational modification of histones or CREB. Importantly, M. bovis BCG infection-induced apoptosis was severely compromised in macrophages derived from miR-155 knockout mice. Gain-of-function and loss-of-function studies validated the requirement of miR-155 for M. bovis BCG's ability to trigger apoptosis. Overall, M. bovis BCG-driven miR-155 dictates cell fate decisions of infected macrophages, strongly implicating a novel role for miR-155 in orchestrating cellular reprogramming during immune responses to mycobacterial infection.

Layer-by-Layer Self-Assembled Metal-Ion- (Ag-, Co-, Ni-, and Pd-) Doped TiO2 Nanoparticles: Synthesis, Characterisation, and Visible Light Degradation of Rhodamine B

Metal-ion- (Ag, Co, Ni and Pd) doped titania nanocatalysts were successfully deposited on glass slides by layer-by-layer (LbL) self-assembly technique using a poly(styrene sulfonate sodium salt) (PSS) and poly(allylamine hydrochloride) (PAH) polyelectrolyte system. Solid diffuse reflectance (SDR) studies showed a linear increase in absorbance at 416 nm with increase in the number of m-TiO2 thin films. The LbL assembled thin films were tested for their photocatalytic activity through the degradation of Rhodamine B under visible-light illumination. From the scanning electron microscope (SEM), the thin films had a porous morphology and the atomic force microscope (AFM) studies showed ``rough'' surfaces. The porous and rough surface morphology resulted in high surface areas hence the high photocatalytic degradation (up to 97% over a 6.5 h irradiation period) using visible-light observed. Increasing the number of multilayers deposited on the glass slides resulted in increased film thickness and an increased rate of photodegradation due to increase in the availability of more nanocatalysts (more sites for photodegradation). The LbL assembled thin films had strong adhesion properties which made them highly stable thus displaying the same efficiencies after five (5) reusability cycles.

One step synthesis of monoclinic VO2 (B) bundles of nanorods: Cathode for Li ion battery

One of the metastable phases of vanadium dioxide, VO2(B) bundles of nanorods and microspheres have been synthesized through a simple hydrothermal method by dispersing V2O5 in aqueous quinol. The obtained products were characterized by X-ray diffraction (XRD), Fourier transform infrared (FTIR) spectroscopy, scanning electron microscopy (SEM) and electrochemical discharge-charge test for lithium battery. It was found that the morphologies of the obtained VO2(B) can be tuned by manipulating the relative amount of quinol. The electrochemical test found that the bundles of nanorods exhibit an initial discharge capacity of 171 mAh g(-1) and its almost stabilized capacity was reached to 108 mAh g(-1) after 47 cycles at a current density of 0.1 mA g(-1). The formation mechanism of the VO2(B) bundles of nanorods and microspheres was also discussed. (C) 2012 Elsevier Inc. All rights reserved.

An experimental study on cracking evolution in concrete and cement mortar by the b-value analysis of acoustic emission technique

Notched three point bend (TPB) specimens made with plain concrete and cement mortar were tested under crack mouth opening displacement (CMOD) control at a rate of 0.0004 mm/s and simultaneously acoustic emissions (AE) released were recorded during the experiments. Amplitude distribution analysis of AE released during concrete was carried out to study the development of fracture process in concrete and mortar specimens. The slope of the log-linear frequency-amplitude distribution of AE is known as the AE based b-value. The AE based b-value was computed in terms of physical process of time varying applied load using cumulative frequency distribution (Gutenberg-Richter relationship) and discrete frequency distribution (Aki's method) of AE released during concrete fracture. AE characteristics of plain concrete and cement mortar were studied and discussed and it was observed that the AE based b-value analysis serves as a tool to identify the damage in concrete structural members. (C) 2012 Elsevier Ltd. All rights reserved.

Total synthesis of (+)-phomopsolide B

An enantiospecific total synthesis of polyhydroxy delta-pyrone natural product phomopsolide B is accomplished. The main feature of the synthesis is the installation of the required E-olefin by Horner-Emmons-Wordsworth reaction and the formation of the lactone involving Still-Gennari olefination followed by lactonization. (C) 2012 Elsevier Ltd. All rights reserved.

Comparison of rhodamine B degradation under UV irradiation by two phases of titania nano-photocatalyst

Titania (TiO2) nano-photocatalysts, with different phases, prepared using a modified sol-gel process were employed in the degradation of rhodamine at 10 mg L-1 concentration. The degradation efficiency of these nano-photocatalysts was compared to that of commercial Degussa P25 titania. It was found that the nanocatalysts calcined at 450 degrees C and the Degussa P25 titania had similar photoreactivity profiles. The commercial Degussa P25 nanocatalysts had an overall high apparent rate constant of (K-app) of 0.023 min(-1). The other nanocatalyst had the following rate constants: 0.017, 0.0089, 0.003 and 0.0024 min(-1) for 450, 500, 550 and 600 degrees C calcined catalysts, respectively. This could be attributed to the phase of the titania as the anatase phase is highly photoactive than the other phases. Furthermore, characterisation by differential scanning calorimetry showed the transformation of titania from amorphous to anatase and finally to rutile phase. SEM and TEM characterisations were used to study the surface morphology and internal structure of the nanoparticles. BET results show that as the temperature of calcinations was raised, the surface area reduced marginally. X-ray diffraction was used to confirm the different phases of titania. This study has led to a conclusion that the anatase phase of the titania is the most photoactive nanocatalyst. It also had the highest apparent rate constant of 0.017 min(-1), which is similar to that of the commercial titania.

Path-integral formulation for Levy flights: Evaluation of the propagator for free, linear, and harmonic potentials in the over- and underdamped limits

Levy flights can be described using a Fokker-Planck equation, which involves a fractional derivative operator in the position coordinate. Such an operator has its natural expression in the Fourier domain. Starting with this, we show that the solution of the equation can be written as a Hamiltonian path integral. Though this has been realized in the literature, the method has not found applications as the path integral appears difficult to evaluate. We show that a method in which one integrates over the position coordinates first, after which integration is performed over the momentum coordinates, can be used to evaluate several path integrals that are of interest. Using this, we evaluate the propagators for (a) free particle, (b) particle subjected to a linear potential, and (c) harmonic potential. In all the three cases, we have obtained results for both overdamped and underdamped cases. DOI: 10.1103/PhysRevE.86.061105

B-H Bond Activation Using an Electrophilic Metal Complex: Insights into the Reaction Pathway

A highly electrophilic ruthenium center in the RuCl(dppe)(2)]OTf] complex brings about the activation of the B H bond in ammonia borane (H3N center dot BH3, AB) and dimethylamine borane (Me2HN center dot BH3, DMAB). At room temperature, the reaction between RuCl(dppe)(2)]OTf] and AB or DMAB results in trans-RuH(eta(2)-H-2)(dppe)(2)]OTf] trans-RuCl(eta(2)-H-2)(dppe)(2)]OTf], and trans-RuH(Cl)(dppe)(2)], as noted in the NMR spectra. Mixing the ruthenium complex and AB or DMAB at low temperature (198/193 K) followed by NMR spectral measurements as the reaction mixture was warmed up to room temperature allowed the observation of various species formed enroute to the final products that were obtained at room temperature. On the basis of the variable-temperature multinuclear NMR spectroscopic studies of these two reactions, the mechanistic insights for B-H bond activation were obtained. In both cases, the reaction proceeds via an eta(1)-B-H moiety bound to the metal center. The detailed mechanistic pathways of these two reactions as studied by NMR spectroscopy are described.