Highly efficient WO3-ZnO mixed oxides for photocatalysis

Monoclinic nanocuboid WO3 enhanced the photocatalyst efficiency of quasi nanobelt zinc oxide for dye degradation in the presence of visible light radiation. Combustion synthesized ZnO resulted in a belt-like morphology through in situ cluster formation of near spherical particles but homogenously disperses and strongly adheres to nanocuboid WO3 during physical mixing. Cationic methylene blue (MB) and anionic orange G (OG) undergo degradation through a charge transfer mechanism in the presence of WO3-ZnO (1 : 9 weight percentage ratio) mixture. The photocatalytic reaction was enhanced due to the reduction in the recombination of photogenerated electron-holes. The high degree of 90% degradation of both dyes is due to the activity of the mixed oxides, which is much higher than that obtained either with WO3 or ZnO individually.

Designing Elastic Organic Crystals: Highly Flexible Polyhalogenated N-Benzylideneanilines

The intermolecular interactions and structural features in crystals of seven halogenated N-benzylideneanilines (Schiff bases), all of which exhibit remarkable flexibility, were examined to identify the common packing features that are the raison d'etre for the observed elasticity. The following two features, in part related, were identified as essential to obtain elastic organic crystals: 1)A multitude of weak and dispersive interactions, including halogen bonds, which may act as structural buffers for deformation through easy rupture and reformation during bending; and 2)corrugated packing patterns that would get interlocked and, in the process, prevent long-range sliding of molecular planes.

Highly sensitive and rapid detection of acetylcholine using an ITO plate modified with platinum-graphene nanoparticles

Determining the concentrations of acetylcholine (ACh) and choline (Ch) is clinically important. ACh is a neurotransmitter that acts as a key link in the communication between neurons in the spinal cord and in nerve skeletal junctions in vertebrates, and plays an important role in transmitting signals in the brain. A bienzymatic sensor for the detection of ACh was prepared by co-immobilizing choline oxidase (ChO) and acetylcholinesterase (AChE) on graphene matrix/platinum nanoparticles, and then electrodepositing them on an ITO-coated glass plate. Graphene nanoparticles were decorated with platinum nanoparticles and were electrodeposited on a modified ITO-coated glass plate to form a modified electrode. The modified electrode was characterized by scanning electron microscopy (SEM), cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS) studies. The optimum response of the enzyme electrode was obtained at pH 7.0 and 35 degrees C. The response time of this ACh-sensing system was shown to be 4 s. The linear range of responses to ACh was 0.005-700 mu M. This biosensor exhibits excellent anti-interferential abilities and good stability, retaining 50% of its original current even after 4 months. It has been applied for the detection of ACh levels in human serum samples.

Simultaneous measurements of thickness and temperature profile of the lubricant film at chip-tool interface during machining process using luminescent sensors

Simultaneous measurements of thickness and temperature profile of the lubricant film at chip-tool interface during machining have been studied in this experimental programme. Conventional techniques such as thermography can only provide temperature measurement under controlled environment in a laboratory and without the addition of lubricant. The present study builds on the capabilities of luminescent sensors in addition to direct image based observations of the chip-tool interface. A suite of experiments conducted using different types of sensors are reported in this paper, especially noteworthy are concomitant measures of thickness and temperature of the lubricant. (C) 2014 Elsevier Ltd.

Highly Dense ZnO Nanowires Grown on Graphene Foam for Ultraviolet Photodetection

Growth of highly dense ZnO nanowires (ZnO NWs) is demonstrated on three-dimensional graphene foam (GF) using resistive thermal evaporation technique. Photoresponse of the as-grown hybrid structure of ZnO NWs on GF (ZnO NWs/GF) is evaluated for ultraviolet (UV) detection. Excellent photoresponse with fast response and recovery times of 9.5 and 38 s with external quantum efficiency of 2490.8% is demonstrated at low illumination power density of 1.3 mW/cm(2). In addition, due to excellent charge carrier transport, mobility of graphene reduces the recombination rate of photogenerated charge carriers, hence the lifetime of photogenerated free charge carriers enhances in the photodetectors.

Achieving Highly Efficient, Selective, and Stable CO2 Reduction on Nitrogen-Doped Carbon Nanotubes

The challenge in the electrosynthesis of fuels from CO2 is to achieve durable and active performance with cost-effective catalysts. Here, we report that carbon nanotubes (CNTs), doped with nitrogen to form resident electron-rich defects, can act as highly efficient and, more importantly, stable catalysts for the conversion of CO2 to CO. The unprecedented overpotential (-0.18 V) and selectivity (80%) observed on nitrogen-doped CNTs (NCNTs) are attributed to their unique features to facilitate the reaction, including (i) high electrical conductivity, (ii) preferable catalytic sites (pyridinic N defects), and (iii) low free energy for CO2 activation and high barrier for hydrogen evolution. Indeed, DFT calculations show a low free energy barrier for the potential-limiting step to form key intermediate COOH as well as strong binding energy of adsorbed CON and weak binding energy for the adsorbed CO. The highest selective site toward CO production is pyridinic N, and the NCNT-based electrodes exhibit no degradation over 10 h of continuous operation, suggesting the structural stability of the electrode.

Simultaneous Determination of Catecholamines in Presence of Uric Acid and Ascorbic Acid at a Highly Sensitive Electrochemically Activated Carbon Paste Electrode

A simple yet remarkable, electrochemically activated carbon paste electrode (EACPE) was prepared by successive potential cycling of carbon paste in a 0.1 M NaOH solution and was effectively used for the simultaneous determination of catecholamines such as dopamine (DA), epinephrine (E) and Norepinephrine (NE) in presence of uric acid (UA) and ascorbic acid (AA). Taking DA as the ideal catecholamine, the electrochemical behaviors of DA, UA and AA such as scan rate and pH variation was studied by cyclic voltammetry (CV) in phosphate buffer solution (PBS, pH 7.1). This electrochemical sensor exhibited strong electrocatalytic activity towards the oxidation of a mixture of catecholamines, UA and AA with apparent reduction of overpotentials. Crider optimum conditions, limit of detection (S/N = 3) of DA, E, NE, UA and AA was found to be 0.08, 0.08, 0.07, 0.1 and 6.0 mu M, respectively by differential pulse voltammetry (DPV). The analytical performance of this modified electrode as a biosensor was also demonstrated for the determination of DA, UA and AA in dopamine injection, human urine and vitamin C tablets, respectively, in presence of other interfering substances. (C) 2015 The Electrochemical Society. All-rights reserved.

GRMHD formulation of highly super-Chandrasekhar magnetized white dwarfs: stable configurations of non-spherical white dwarfs

The topic of magnetized super-Chandrasekhar white dwarfs is in the limelight, particularly in the last few years, since our proposal of their existence. By full-scale general relativistic magnetohydrodynamic (GRMHD) numerical analysis, we confirm in this work the existence of stable, highly magnetized, significantly super-Chandrasekhar white dwarfs with mass more than 3 solar mass. While a poloidal field geometry renders the white dwarfs oblate, a toroidal field makes them prolate retaining an overall quasi-spherical shape, as speculated in our earlier work. These white dwarfs are expected to serve as the progenitors of over-luminous type Ia supernovae.

Highly Efficient Glutathione Peroxidase and Peroxiredoxin Mimetics Protect Mammalian Cells against Oxidative Damage

Novel isoselenazoles with high glutathione peroxidase (GPx) and peroxiredoxin (Prx) activities provide remarkable cytoprotection to human cells, mainly by exhibiting antioxidant activities in the presence of cellular thiols. The cytotoxicity of the isoselenazoles is found to be significantly lower than that of ebselen, which is being clinically evaluated by several groups for the treatment of reperfusion injuries and stroke, hearing loss, and bipolar disorder. The compounds reported in this paper have the potential to be used as therapeutic agents for disorders mediated by reactive oxygen species.

Redox-Active Metal-Organic Frameworks: Highly Stable Charge-Separated States through Strut/Guest-to-Strut Electron Transfer

Molecular organization of donor and acceptor chromophores in self-assembled materials is of paramount interest in the field of photovoltaics or mimicry of natural light-harvesting systems. With this in mind, a redox-active porous interpenetrated metal-organic framework (MOF), {Cd(bpdc)(bpNDI)]4.5H(2)ODMF}(n) (1) has been constructed from a mixed chromophoric system. The -oxo-bridged secondary building unit, {Cd-2(-OCO)(2)}, guides the parallel alignment of bpNDI (N,N-di(4-pyridyl)-1,4,5,8-naphthalenediimide) acceptor linkers, which are tethered with bpdc (bpdcH(2)=4,4-biphenyldicarboxylic acid) linkers of another entangled net in the framework, resulting in photochromic behaviour through inter-net electron transfer. Encapsulation of electron-donating aromatic molecules in the electron-deficient channels of 1 leads to a perfect donor-acceptor co-facial organization, resulting in long-lived charge-separated states of bpNDI. Furthermore, 1 and guest encapsulated species are characterised through electrochemical studies for understanding of their redox properties.

Probing the role of highly conserved residues in triosephosphate isomerase-analysis of site specific mutants at positions 64 and 75 in the Plasmodial enzyme

Highly conserved residues in enzymes are often found to be clustered close to active sites, suggesting that functional constraints dictate the nature of amino acid residues accommodated at these sites. Using the Plasmodiumfalciparum triosephosphate isomerase (PfTIM) enzyme () as a template, we have examined the effects of mutations at positions 64 and 75, which are not directly involved in the proton transfer cycle. Thr (T) occurring at position 75 is completely conserved, whereas only Gln (Q) and Glu (E) are accommodated at position 64. Biophysical and kinetic data are reported for four T75 (T75S/V/C/N) and two Q64 (Q64N/E) mutants. The dimeric structure is weakened in the Q64E and Q64N mutants, whereas dimer integrity is unimpaired in all four T75 mutants. Measurement of the concentration dependence of enzyme activity permits an estimate of K-d values for dimer dissociation (Q64N=73.79.2nm and Q64E=44.6 +/- 8.4nm). The T75S/V/C mutants have activities comparable to the wild-type enzyme, whereas a fourfold drop is observed for T75N. All four T75 mutants show a dramatic fall in activity between 35 degrees C and 45 degrees C. Crystal structure determination of the T75S/V/N mutants provides insights into the variations in local interactions, with the T75N mutant showing the largest changes. Hydrogen-bond interactions determine dimer stability restricting the choice of residues at position 64 to Gln (Q) and Glu (E). At position 75, the overwhelming preference for Thr (T) may be dictated by the imperative of maintaining temperature stability of enzyme activity.

GRMHD formulation of highly super-Chandrasekhar rotating magnetized white dwarfs: stable configurations of non-spherical white dwarfs

Here we extend the exploration of significantly super-Chandrasekhar magnetized white dwarfs by numerically computing axisymmetric stationary equilibria of differentially rotating magnetized polytropic compact stars in general relativity (GR), within the ideal magnetohydrodynamic regime. We use a general relativistic magnetohydrodynamic (GRMHD) framework that describes rotating and magnetized axisymmetric white dwarfs, choosing appropriate rotation laws and magnetic field profiles (toroidal and poloidal). The numerical procedure for finding solutions in this framework uses the 3 + 1 formalism of numerical relativity, implemented in the open source XNS code. We construct equilibrium sequences by varying different physical quantities in turn, and highlight the plausible existence of super-Chandrasekhar white dwarfs, with masses in the range of 2-3 solar mass, with central (deep interior) magnetic fields of the order of 10(14) G and differential rotation with surface time periods of about 1-10 s. We note that such white dwarfs are candidates for the progenitors of peculiar, overluminous Type Ia supernovae, to which observational evidence ascribes mass in the range 2.1-2.8 solar mass. We also present some interesting results related to the structure of such white dwarfs, especially the existence of polar hollows in special cases.

Ordered Pd2Ge Intermetallic Nanoparticles as Highly Efficient and Robust Catalyst for Ethanol Oxidation

Pd2Ge nanoparticles were synthesized by superhydride reduction of K2PdCl4 and GeCl4. The syntheses were performed using a solvothermal method in the absence of surfactants, and the size of the nanoparticles was controlled by varying the reaction time. The powder X-ray diffraction (PXRD) and transmission electron microscopy data suggest that Pd2Ge nanoparticles were formed as an ordered intermetallic phase. In the crystal structure, Pd and Ge atoms occupy two different crystallographic positions with a vacancy in one of the Ge sites, which was proved by PXRD and energy-dispersive X-ray analysis. The catalyst is highly efficient for the electrochemical oxidation of ethanol and is stable up to the 250th cycle in alkaline medium. The electrochemical active surface area and current density values obtained, 1.41 cm(2) and 4.1 mA cm(-2), respectively, are superior to those of the commercial Pd on carbon. The experimentally observed data were interpreted in terms of the combined effect of adsorption energies of CH3CO and OH radical, d-band center model, and work function of the corresponding catalyst surfaces.

Structure-mechanical property correlations in mechanochromic luminescent crystals of boron difluoride dibenzoylmethane derivatives

The structure and mechanical properties of crystalline materials of three boron difluoride dibenzoylmethane (BF(2)dbm) derivatives were investigated to examine the correlation, if any, among mechanochromic luminescence (ML) behaviour, solid-state structure, and the mechanical behaviour of single crystals. Qualitative mechanical deformation tests show that the crystals of BF(2)dbm(Bu-t)(2) can be bent permanently, whereas those of BF(2)dbm(OMe)(2) exhibit an inhomogeneous shearing mode of deformation, and finally BF(2)dbmOMe crystals are brittle. Quantitative mechanical analysis by nanoindentation on the major facets of the crystals shows that BF(2)dbm(Bu-t)(2) is soft and compliant with low values of elastic modulus, E, and hardness, H, confirming its superior suceptibility for plastic deformation, which is attributed to the presence of a multitude of slip systems in the crystal structure. In contrast, both BF(2)dbm(OMe)(2) and BF(2)dbmOMe are considerably stiffer and harder with comparable E and H, which are rationalized through analysis of the structural attributes such as the intermolecular interactions, slip systems and their relative orientation with respect to the indentation direction. As expected from the qualitative mechanical behaviour, prominent ML was observed in BF(2)dbm(Bu-t)(2), whereas BF(2)dbm(OMe)(2) exhibits only a moderate ML and BF(2)dbmOMe shows no detectable ML, all examined under identical conditions. These results confirm that the extent of ML in crystalline organic solid-state fluorophore materials can be correlated positively with the extent of plasticity (low recovery). In turn, they offer opportunities to design new and improved efficient ML materials using crystal engineering principles.

ZnO quantum dots and graphene based heterostructure for excellent photoelastic and highly sensitive ultraviolet photodetector

Heterostructures comprised of zinc oxide quantum dots (ZnO QDs) and graphene are presented for ultraviolet photodetectors (UV PD). Graphene-ZnO QDs-graphene (G-ZnO QDs-G) based PD demonstrated an excellent UV photoresponse with outstanding photoelastic characteristics when illuminated for several cycles with a periodicity 5 s. PD demonstrated faster detection ability with the response and recovery times of 0.29 s in response to much lower UV illumination. A direct variation in photoresponse is revealed with the bias voltage as well as UV illumination intensity. A drastic reduction in the dark current is noticed due to potential barrier formation between adjacent ZnO QDs and the recombination rate reduces by directly transferring photogenerated charge carriers from ZnO QDs to graphene for enhanced the charge mobility.