Water Dispersible, Positively and Negatively Charged MoS2 Nanosheets: Surface Chemistry and the Role of Surfactant Binding

Stable aqueous dispersions of atomically thin layered MoS2 nanosheets have been obtained by sonication in the presence of ionic surfactants. The dispersions are stabilized by electrostatic repulsion between the sheets, and we show that the sign of the charge on the MoS2 nanosheets, either positive or negative, can be can be controlled by the choice of the surfactant. Using techniques from solution NMR, we show that the surfactant chains are weakly bound to the MoS2 sheets and undergo rapid exchange with free surfactant chains present in the dispersion. In situ nuclear Overhauser effect spectroscopic measurements provide direct evidence that the surfactant chains lie flat, arranged randomly on the basal plane of the MoS2 nanosheets with their charged headgroup exposed. These results provide a chemical perspective for understanding the stability of these inorganic nanosheets in aqueous dispersions and the origin of the charge on the sheets.

Piezoelectric properties of individual nanocrystallites of Ba0.85Ca0.15Zr0.1Ti0.9O3 obtained by oxalate precursor route

Nanocrystalline Ba0.85Ca0.15Zr0.1Ti0.9O3 (BCZT) powder was synthesized via the complex oxalate precursor route at a relatively low temperature (800 degrees C/5 h). The phase formation temperature of BCZT at nanoscale was confirmed by thermogravimetric (TG), differential thermal analysis (DTA) followed by X-ray powder diffraction (XRD) studies. Fourier transform infrared (FTIR) spectroscopy was carried out to confirm the complete decomposition of oxalate precursor into BCZT phase. The XRD and profile fitting revealed the coexistence of cubic and tetragonal phases and was corroborated by Raman study. Transmission electron microscopy (TEM) carried out on 800 degrees C and 1000 degrees C/5 h heat treated BCZT powder revealed the crystallite size to be in the range of 20-50 nm and 40-200 nm respectively. The optical band gap for BCZT nanocrystalline powder was obtained using Kubelka Munk function and was found to be around 3.12 +/- 0.02 eV and 3.03 +/- 0.02 eV respectively for 800 degrees C (20-50 nm) and 1000 degrees C/5 h (40-200 nm) heat treated samples. The piezoelectric properties were studied for two different crystallite sizes (30 and 70 nm) using a piezoresponse force microscope (PFM). The d(33) coefficients obtained for 30 nm and 70 nm sized crystallites were 4 pm V-1 and 47 pm V-1 respectively. These were superior to that of BaTiO3 nanocrystal (approximate to 50 nm) and promising from a technological/industrial applications viewpoint.

Status of the crystallography beamlines at Elettra

Elettra is one of the first 3rd-generation storage rings, recently upgraded to routinely operate in top-up mode at both 2.0 and 2.4 GeV. The facility hosts four dedicated beamlines for crystallography, two open to the users and two under construction, and expected to be ready for public use in 2015. In service since 1994, XRD1 is a general-purpose diffraction beamline. The light source for this wide (4-21 keV) energy range beamline is a permanent magnet wiggler. XRD1 covers experiments ranging from grazing incidence X-ray diffraction to macromolecular crystallography, from industrial applications of powder diffraction to X-ray phasing with long wavelengths. The bending magnet powder diffraction beamline MCX has been open to users since 2009, with a focus on microstructural investigations and studies under non-ambient conditions. A superconducting wiggler delivers a high photon flux to a new fully automated beamline dedicated to macromolecular crystallography and to a branch beamline hosting a high-pressure powder X-ray diffraction station (both currently under construction). Users of the latter experimental station will have access to a specialized sample preparation laboratory, shared with the SISSI infrared beamline. A high throughput crystallization platform equipped with an imaging system for the remote viewing, evaluation and scoring of the macromolecular crystallization experiments has also been established and is open to the user community.

Sulfate Chemistry for High-Voltage Insertion Materials: Synthetic, Structural and Electrochemical Insights

Rechargeable batteries based on Li and Na ions have been growing leaps and bounds since their inception in the 1970s. They enjoy significant attention from both the fundamental science point of view and practical applications ranging from portable electronics to hybrid vehicles and grid storage. The steady demand for building better batteries calls for discovery, optimisation and implementation of novel positive insertion (cathode) materials. In this quest, chemists have tried to unravel many future cathode materials by taking into consideration their eco-friendly synthesis, material/process economy, high energy density, safety, easy handling and sustainability. Interestingly, sulfate-based cathodes offer a good combination of sustainable syntheses and high energy density owing to their high-voltage operation, stemming from electronegative SO42- units. This review delivers a sneak peak at the recent advances in the discovery and development of sulfate-containing cathode materials by focusing on their synthesis, crystal structure and electrochemical performance. Several family of cathodes are independently discussed. They are 1) fluorosulfates AMSO(4)F], 2) bihydrated fluorosulfates AMSO(4)F2H(2)O], 3) hydroxysulfate AMSO(4)OH], 4) bisulfates A(2)M(SO4)(2)], 5) hydrated bisulfates A(2)M(SO4)(2)nH(2)O], 6) oxysulfates Fe-2(SO4)(2)O] and 7) polysulfates A(2)M(2)(SO4)(3)]. A comparative study of these sulfate-based cathodes has been provided to offer an outlook on the future development of high-voltage polyanionic cathode materials for next-generation batteries.

Sources of black carbon aerosols in South Asia and surrounding regions during the Integrated Campaign for Aerosols, Gases and Radiation Budget (ICARB)

This study examines differences in the surface black carbon (BC) aerosol loading between the Bay of Bengal (BoB) and the Arabian Sea (AS) and identifies dominant sources of BC in South Asia and surrounding regions during March-May 2006 (Integrated Campaign for Aerosols, Gases and Radiation Budget, ICARB) period. A total of 13 BC tracers are introduced in the Weather Research and Forecasting Model coupled with Chemistry to address these objectives. The model reproduced the temporal and spatial variability of BC distribution observed over the AS and the BoB during the ICARB ship cruise and captured spatial variability at the inland sites. In general, the model underestimates the observed BC mass concentrations. However, the model-observation discrepancy in this study is smaller compared to previous studies. Model results show that ICARB measurements were fairly well representative of the AS and the BoB during the pre-monsoon season. Elevated BC mass concentrations in the BoB are due to 5 times stronger influence of anthropogenic emissions on the BoB compared to the AS. Biomass burning in Burma also affects the BoB much more strongly than the AS. Results show that anthropogenic and biomass burning emissions, respectively, accounted for 60 and 37% of the average +/- standard deviation (representing spatial and temporal variability) BC mass concentration (1341 +/- 2353 ng m(-3)) in South Asia. BC emissions from residential (61 %) and industrial (23 %) sectors are the major anthropogenic sources, except in the Himalayas where vehicular emissions dominate. We find that regional-scale transport of anthropogenic emissions contributes up to 25% of BC mass concentrations in western and eastern India, suggesting that surface BC mass concentrations cannot be linked directly to the local emissions in different regions of South Asia.

Dendron conjugation to graphene oxide using click chemistry for efficient gene delivery

Owing to its large surface area and rapid cellular uptake, graphene oxide (GO) is emerging as an attractive candidate material for delivery of drugs and genes. The inherent sp(2) pi-pi interaction of GO helps to carry drugs and single stranded RNA (ssRNA) but there is no such interaction with double stranded DNA (dsDNA). In this work, a polyamidoamine (PAMAM) dendron was conjugated with nano GO (nGO) through ``click'' chemistry to improve the DNA complexation capability of GO as well as its transfection efficiency. The DNA complexation capability of GO was significantly enhanced after dendronization of GO yielding spherical nanosized (250-350 nm) particles of the dendronized GO (DGO)/pDNA complex with a positive zeta potential. The transfection efficiency of GO dramatically increased after conjugation of the PAMAM dendron. Transfection efficiency of 51% in HeLa cells with cell viability of 80% was observed. The transfection efficiency was significantly higher than that of polyethyleneimine 25 kDa (27% efficiency) and also surpassed that of lipofectamine 2000 (47% efficiency). The uptake of the DGO/pDNA complex by the caveolae mediated endocytosis pathway may significantly contribute to the high transfection efficiency. Thus, dendronized GO is shown to be an efficient gene carrier with minimal toxicity and is a promising candidate for use as a nonviral carrier for gene therapy.

Imidazolium based ionic liquid type surfactant improves activity and thermal stability of lipase of Rhizopus oryzae

Lipase and surfactant together form a potent pair in various biotransformation, industrial application and biotechnological studies. The present investigation deals with changes in the activity, stability and structure of lipase from Rhizopus oryzae NRRL 3562 in presence of long chain ionic liquid-type imidazolium surfactant. Both the activity and stability were found to be enhanced in presence of the surfactant at low concentration (1-125 mu M) followed by inhibition at high concentration. The activity increased by 80% and thermal deactivation temperature raised by 2.5 degrees C. Investigations by ultraviolet-visible spectroscopy and circular dichroism revealed structural changes leading to rise in beta-sheet content and lowering of a-helix at low surfactant concentrations. Deactivation at high concentration correlated with greater structural changes depicted by spectroscopic studies. Isothermal titration calorimetric studies showed the binding to be spontaneous in nature involving non-covalent interactions. High negative value of entropy signifies exposure of hydrophobic domains and increase in structural rigidity, which correlates with active site being more accessible and rigid in presence of the surfactant. Application of these surfactants hold greater potential in the field of lipase based biotransformations, enzyme structural modifications and studies. (C) 2015 Elsevier B.V. All rights reserved.

Biodiesel Exhaust Treatment with Dielectric Barrier Discharges Coupled with Industrial Waste Byproducts

Biodiesel run engines are gaining popularity since the last few years as a viable alternative to conventional petro-diesel based engines. In biodiesel exhaust the content of volatile organic compounds, oil mist, and mass of particulate matter is considerably lower. However, the concentration of oxides of nitrogen (NOx) is relatively higher. In this paper the biodiesel exhaust from a stationary engine is treated under controlled laboratory conditions for removal of NOx using dielectric barrier discharge plasma in cascade with adsorbents prepared from abundantly available industrial waste byproducts like red mud and copper slag. Results were compared with gamma-alumina, a commercial adsorbent. Two different dielectric barrier discharge (DBD) reactors were tested for their effectiveness under Repetitive pulses /AC energization. NOx removal as high as 80% was achieved with pulse energized reactors when cascaded with red mud as adsorbent.

Effective Degradation of Aqueous Nitrobenzene Using the SrFeO3-delta Photocatalyst under UV Illumination and Its Kinetics and Mechanistic Studies

In this article, the SrFeO3-delta photocatalyst was synthesized by a solution combustion method and applied for the photocatalytic degradation of aqueous nitrobenzene in the presence and absence of H2O2. The SrFeO3-delta photocatalyst was characterized by XRD, FT-IR, FE-SEM, TEM, TG-DTG, XPS, and UV visible spectroscopy. The band gap energy of SrFeO3-delta was found to be 3.75 eV which lies in the UV region. The XPS results indicate that the oxidation state of Sr and Fe in SrFeO3-delta was 2+ and 3+, respectively, and the surface atomic ratio of Sr and Fe is 0.995. The photocatalytic activity reveals that the degradation of nitrobenzene over the SrFeO3-delta catalyst itself (UV/SFO) is superior compared to SrFeO3-delta in the presence of H2O2 (UV/SFO/H2O2) with a degradation efficiency of 99-96%. The degradation of nitrobenzene obeys first-order kinetics in both UV/SFO and UV/SFO/H2O2 processes. The decrease in degradation efficiency with UV/SFO/H2O2 was attributed due to the formation of strontium carbonate on the photocatalyst surface.

Novel AgBr/Ag3PO4 Decorated Ceria Nanoflake Composites for Enhanced Photocatalytic Activity toward Dyes and Bacteria under Visible Light

The aim of this study was to develop heterogeneous visible light active photocatalysts using AgBr and Ag3PO4 using CeO2 nanoflakes as an efficient substrate. Ascorbic acid was employed as a fuel to synthesize fine ceria nanoflakes by a facile solution combustion process. AgBr and Ag3PO4 were decorated on ceria to prepare AgBr/Ag3PO4/ceria nanocomposites. The structure of the composite was determined by X-ray diffraction analysis. Novel flakelike morphology was revealed using electron microscopy techniques. The nanocomposites exhibit excellent photocatalytic activity under visible light compared to pristine ceria nanoparticles. The nanocomposite catalyst particles degraded both anionic and cationic dyes. It also exhibited efficient antimicrobial activity under visible light. The AgBr/Ag3PO4/ceria nanocomposite was characterized using X-ray diffraction analysis, diffuse reflectance spectroscopy, electron microscopy, BET surface area analysis, and X-ray photoelectron spectroscopy, and the reasons for enhanced photocatalytic activity were elucidated. The presence of silver based semiconductors on ceria has shown to decrease charge recombination through photoluminescence analysis that attributed for enhanced photocatalytic activity. The AgBr/Ag3PO4/ceria nanocomposite has shown a stable performance after many repeated cycles.

TURBULENCE-TRANSPORT-CHEMISTRY INTERACTION IN STATISTICALLY PLANAR PREMIXED FLAMES AND IGNITION KERNELS IN NEAR ISOTROPIC TURBULENCE

Turbulence-transport-chemistry interaction plays a crucial role on the flame surface geometry, local and global reactionrates, and therefore, on the propagation and extinction characteristics of intensely turbulent, premixed flames encountered in LPP gas-turbine combustors. The aim of the present work is to understand these interaction effects on the flame surface annihilation and extinction of lean premixed flames, interacting with near isotropic turbulence. As an example case, lean premixed H-2-air mixture is considered so as to enable inclusion of detailed chemistry effects in Direct Numerical Simulations (DNS). The work is carried out in two phases namely, statistically planar flames and ignition kernel, both interacting with near isotropic turbulence, using the recently proposed Flame Particle Tracking (FPT) technique. Flame particles are surface points residing and commoving with an iso-scalar surface within a premixed flame. Tracking flame particles allows us to study the evolution of propagating surface locations uniquely identified with time. In this work, using DNS and FPT we study the flame speed, reaction rate and transport histories of such flame particles residing on iso-scalar surfaces. An analytical expression for the local displacement flame speed (SO is derived, and the contribution of transport and chemistry on the displacement flame speed is identified. An examination of the results of the planar case leads to a conclusion that the cause of variation in S-d may be attributed to the effects of turbulent transport and heat release rate. In the second phase of this work, the sustenance of an ignition kernel is examined in light of the S-curve. A newly proposed Damkohler number accounting for local turbulent transport and reaction rates is found to explain either the sustenance or otherwise propagation of flame kernels in near isotropic turbulence.

Bioinspired Reductionistic Peptide Engineering for Exceptional Mechanical Properties

A simple solution-processing and self-assembly approach that exploits the synergistic interactions between multiple hydrogen bonded networks and aromatic interactions was utilized to synthesize molecular crystals of cyclic dipeptides (CDPs), whose molecular weights (similar to 0.2 kDa) are nearly three orders of magnitude smaller than that of natural structural proteins (50-300 kDa). Mechanical properties of these materials, measured using the nanoindentation technique, indicate that the stiffness and strength are comparable and sometimes better than those of natural fibres. The measured mechanical responses were rationalized by recourse to the crystallographic structural analysis and intermolecular interactions in the self-assembled single crystals. With this work we highlight the significance of developing small molecule based bioinspired design strategies to emulate biomechanical properties. A particular advantage of the successfully demonstrated reductionistic strategy of the present work is its amenability for realistic industrial scale manufacturing of designer biomaterials with desired mechanical properties.

Cybernetic Modeling Revisited: A Method for Inferring the Cybernetic Variables u(i) from Experimental Data

The cybernetic modeling framework for the growth of microorganisms provides for an elegant methodology to account for the unknown regulatory phenomena through the use of cybernetic variables for enzyme induction and activity. In this paper, we revisit the assumption of limited resources for enzyme induction (Sigma u(i) = 1) used in the cybernetic modeling framework by presenting a methodology for inferring the individual cybernetic variables u(i) from experimental data. We use this methodology to infer u(i) during the simultaneous consumption of glycerol and lactose by Escherichia coli and then model the fitness trade-offs involved in the recently discovered predictive regulation strategy of microorganisms.

Strategy for Obtaining Bimodal Bubble Size Distribution in Water Blown Polyurethane Foams

Polyurethane foams with multimodal cell distribution exhibit superior mechanical and thermal properties. A technique for generating bimodal bubble size distribution exists in the literature, but it uses supercritical conditions. In the present work, an alternative based on milder operating conditions is proposed. It is a modification of reaction injection molding (RIM), using reactants already seeded with bubbles. The number density of the seeds determines if two nucleating events can occur. A bimodal bubble size distribution is obtained when this happens A mathematical model is used to test this hypothesis by simulating water blown free rise polyurethane foams. The effects of initial concentration of bubbles, temperature of the reactants, and the weight fraction of water are studied. The study reveals that for certain concentrations of initial number of bubbles, when initial temperature and weight fraction of water are high, it is possible to obtain a second nucleation event, leading to bimodal bubble size distribution.

Phase Inversion of Agitated Liquid-Liquid Dispersions in the Presence of Micrometer-Sized Particles

We have investigated the impact of partially wetting particles of tens of micrometers on inversion instability of agitated liquid liquid dispersions. Particles of this size can be easily separated from the exit streams to avoid downstream processing-related issues. The results show that the presence of hydrophilic particles in small quantities (volume fraction range of 2 X 10(-4) to 1.25 x 10(-2)) significantly decreases the dispersed phase fraction at which water-in-oil (w/o) dispersions invert but leaves the inversion of oil-in-water (o/w) dispersions nearly unaffected. The addition of the same particles after they are hydrophobized decreases the dispersed phase fraction at which o/w dispersions invert but leaves the inversion of w/o dispersions unaffected. These findings suggest an increased rate of coalescence of drops when particles wet drops preferentially and a marginal decrease when they wet the continuous phase preferentially. High-speed conductivity measurements on w/o dispersion show transient conduction of a few hundred milliseconds duration through voltage pulses. Close to the inversion point, voltage pulses appear at high frequency for even 7 cm separation between the electrodes. The presence of hydrophilic particles produces a nearly identical signal at a significantly lower dispersed phase fraction itself, close to the new lowered inversion point in the presence of particles. We propose formation of elongated domains of the conducting dispersed phase through a rapid coalescence-deformation-breakup process to explain the new observations. The voltage signal appears as a forerunner of inversion instability.