Bio-inspired route for the synthesis of spherical shaped MgO:Fe3+ nanoparticles: Structural, photoluminescence and photocatalytic investigation

MgO:Fe3+ (0.1-5 mol%) nanoparticles (NPs) were synthesized via eco-friendly, inexpensive and simple low temperature solution combustion route using Aloe vera gel as fuel. The final products were characterized by SEM, TEM and HRTEM. PXRD data and Rietveld analysis revealed the formation of cubic system. The influence of Fe3+ ion concentration on the structure morphology, UV absorption, PL emission and photocatalytic activity of MgO:Fe3+ NPs were investigated. The yellow emission with CIE chromaticity coordinates (0.44, 0.52) and average correlated color temperature value was found to be 3540 K which corresponds to warm light of NPs. The control of Fe3+. on MgO matrix influences the photocatalytic decolorization of methylene blue (MB) under UV light. The enhanced photocatalytic activity of MgO:Fe3+ (4 mol%) was attributed to dopant concentration, effective crystallite size, textural properties, decreased band gap and capability for reducing the electron hole pair recombination. Further, the trends of inhibitory effect in the presence of different radical scavengers were explored. These findings open up new avenues for the exploration of Fe-doped MgO in eco-friendly water applications and in the process of display devices. (C) 2015 Elsevier B.V. All rights reserved.

Enhancement in Strain Hardening on Boron Addition in As-Cast Ti-6Al-4V Alloy

It has been previously reported that the addition of boron to Ti-6Al-4V results in significant refinement of the as-cast microstructure and enhancement in the strain hardening. However, the mechanism for the latter effect has not been adequately studied. The aim of this study was to understand the reasons for the enhancement in room temperature strain hardening on addition of boron to as cast Ti-6Al-4V alloy. A study was conducted on slip transmission using SEM, TEM, optical profilometry and four point probe resistivity measurements on un-deformed and deformed samples of Ti-6Al-4V-xB with five levels of boron. Optical profilometry was used to quantify the magnitude of offsets on slip traces which in turn provided information about the extent of planar or multiple slip. Studies on deformed samples reveal that while lath boundaries appear to easily permit dislocation slip transmission, colony boundaries are potent barriers to slip. From TEM studies it was also observed that while alloys containing lower boron underwent planar slip, deformation was more homogeneous in higher boron alloys due to multiple slip resulting from large number of colony boundaries. Multiple slip is also proposed to be the prime cause of the enhanced strain hardening.

Wear Behavior of Cooling Slope Rheocast A356 Al Alloy

In the present study, the dry sliding wear behavior of rheocast A356 Al alloys, cast using a cooling slope, as well as gravity cast A356 Al alloy have been investigated at a low sliding speed of 1ms(-1), against a hardened EN 31 disk at different loads. The wear mechanism involves microcutting-abrasion and adhesion at lower load for all of the alloys studied in the present work. On the other hand, at higher load, mainly adhesive wear along with oxide formation is observed for gravity cast A356 Al alloy and rheocast A356 Al alloy, cast using a 45 degrees slope angle. Unlike other alloys, 60 degrees slope rheocast A356 Al alloy is found to undergo mainly abrasive wear at higher load. Accordingly, the rheocast sample, cast using a 60 degrees cooling slope, exhibits a remarkably lower wear rate at higher load compared to gravity cast and 45 degrees slope rheocast samples. This is attributed to the dominance of abrasive wear at higher load in the case of rheocast A356 Al alloy cast using a 60 degrees slope. The presence of finer and more spherical primary Al grain morphology is found to resist adhesive wear in case of 60 degrees cooling slope processed rheocast alloy and thereby delay the transition of the wear regime from normal wear to severe wear.

Suspensions of polymer-grafted nanoparticles with added polymers-Structure and effective pair-interactions

We present the results of combined experimental and theoretical (molecular dynamics simulations and integral equation theory) studies of the structure and effective interactions of suspensions of polymer grafted nanoparticles (PGNPs) in the presence of linear polymers. Due to the absence of systematic experimental and theoretical studies of PGNPs, it is widely believed that the structure and effective interactions in such binary mixtures would be very similar to those of an analogous soft colloidal material-star polymers. In our study, polystyrene-grafted gold nanoparticles with functionality f = 70 were mixed with linear polystyrene (PS) of two different molecular weights for obtaining two PGNP: PS size ratios, xi = 0.14 and 2.76 (where, xi = M-g/M-m, M-g and M-m being the molecular weights of grafting and matrix polymers, respectively). The experimental structure factor of PGNPs could be modeled with an effective potential (Model-X), which has been found to be widely applicable for star polymers. Similarly, the structure factor of the blends with xi = 0.14 could be modeled reasonably well, while the structure of blends with xi = 2.76 could not be captured, especially for high density of added polymers. A model (Model-Y) for effective interactions between PGNPs in a melt of matrix polymers also failed to provide good agreement with the experimental data for samples with xi = 2.76 and high density of added polymers. We tentatively attribute this anomaly in modeling the structure factor of blends with xi = 2.76 to the questionable assumption of Model-X in describing the added polymers as star polymers with functionality 2, which gets manifested in both polymer-polymer and polymer-PGNP interactions especially at higher fractions of added polymers. The failure of Model-Y may be due to the neglect of possible many-body interactions among PGNPs mediated by matrix polymers when the fraction of added polymers is high. These observations point to the need for a new framework to understand not only the structural behavior of PGNPs but also possibly their dynamics and thermo-mechanical properties as well. (C) 2015 AIP Publishing LLC.

Ir nanoparticles-anchored reduced graphene oxide as a catalyst for oxygen electrode in Li-O-2 cells

Iridium nanoparticles-anchored reduced graphene oxide (Ir-RGO) was prepared by simultaneous reduction of graphene oxide and Ir3+ ions and its catalytic activity for oxygen electrode in Li-O-2 cells was demonstrated. Ir particles with an average size of 3.9 nm were uniformly distributed on RGO sheets. The oxygen reduction reaction (ORR) was studied on an Ir-RGO catalyst in non-aqueous electrolytes using cyclic voltammetry and rotating disk electrode techniques. Li-O-2 cells with Ir-RGO as a bifunctional oxygen electrode catalyst were subjected to charge-discharge cycling at several current densities. A discharge capacity of 9529 mA h g(-1) (11.36 mA h cm(-2)) was obtained initially at a current density of 0.5 mA cm(-2) (393 mA g(-1)). A decrease in capacity was observed on increasing the current density. Although there was a decrease in capacity on repeated discharge-charge cycling initially, a stable capacity was observed for about 30 cycles. The results suggest that Ir-RGO is a useful catalyst for rechargeable Li-O-2 cells.

Haloarchaeal gas vesicle nanoparticles displaying Salmonella antigens as a novel approach to vaccine development

A safe, effective, and inexpensive vaccine against typhoid and other Salmonella diseases is urgently needed. In order to address this need, we are developing a novel vaccine platform employing buoyant, self-adjuvanting gas vesicle nanoparticles (GVNPs) from the halophilic archaeon Halobacterium sp. NRC-1, bioengineered to display highly conserved Salmonella enterica antigens. As the initial antigen for testing, we selected SopB, a secreted inosine phosphate effector protein injected by pathogenic S. enterica bacteria during infection into the host cells. Two highly conserved sopB gene segments near the 3'- region, named sopB4 and sopB5, were each fused to the grIpC gene, and resulting SopB-GVNPs were purified by centrifugally accelerated flotation. Display of SopB4 and SopB5 antigenic epitopes on GVNPs was established by Western blotting analysis using antisera raised against short synthetic peptides of SopB. Immunostimulatory activities of the SopB4 and B5 nanoparticles were tested by intraperitoneal administration of SopB-GVNPs to BALB/c mice which had been immunized with S. enterica serovar Typhimurium 14028 ApmrG-H111-D (DV-STM-07), a live attenuated vaccine strain. Proinflammatory cytokines IFN-y, IL-2, and IL-9 were significantly induced in mice boosted with SopB5-GVNPs, consistent with a robust Thl response. After challenge with virulent S. enterica serovar Typhimurium 14028, bacterial burden was found to be diminished in spleen of mice boosted with SopB4-GVNPs and absent or significantly diminished in liver, mesenteric lymph node, and spleen of mice boosted with SopB5GVNPs, indicating that the C-terminal portions of SopB displayed on GVNPs elicit a protective response to Salmonella infection in mice. SopB antigen-GVNPs were also found to be stable at elevated temperatures for extended periods without refrigeration. The results show that bioengineered GVNPs are likely to represent a valuable platform for antigen delivery and development of improved vaccines against Salmonella and other diseases.

Interplay of electrostatics and lipid packing determines the binding of charged polymer coated nanoparticles to model membranes

Understanding of nanoparticle-membrane interactions is useful for various applications of nanoparticles like drug delivery and imaging. Here we report on the studies of interaction between hydrophilic charged polymer coated semiconductor quantum dot nanoparticles with model lipid membranes. Atomic force microscopy and X-ray reflectivity measurements suggest that cationic nanoparticles bind and penetrate bilayers of zwitterionic lipids. Penetration and binding depend on the extent of lipid packing and result in the disruption of the lipid bilayer accompanied by enhanced lipid diffusion. On the other hand, anionic nanoparticles show minimal membrane binding although, curiously, their interaction leads to reduction in lipid diffusivity. It is suggested that the enhanced binding of cationic QDs at higher lipid packing can be understood in terms of the effective surface potential of the bilayers which is tunable through membrane lipid packing. Our results bring forth the subtle interplay of membrane lipid packing and electrostatics which determine nanoparticle binding and penetration of model membranes with further implications for real cell membranes.

Cell-Membrane-Mimicking Lipid-Coated Nanoparticles Confer Raman Enhancement to Membrane Proteins and Reveal Membrane-Attached Amyloid-beta Conformation

Identifying the structures of membrane bound proteins is critical to understanding their function in healthy and diseased states. We introduce a surface enhanced Raman spectroscopy technique which can determine the conformation of membrane-bound proteins, at low micromolar concentrations, and also in the presence of a substantial membrane-free fraction. Unlike conventional surface enhanced Raman spectroscopy, our approach does not require immobilization of molecules, as it uses spontaneous binding of proteins to lipid bilayer-encapsulated Ag nanoparticles. We apply this technique to probe membrane-attached oligomers of Amyloid-beta(40) (A beta(40)), whose conformation is keenly sought in the context of Alzheimer's disease. Isotope-shifts in the Raman spectra help us obtain secondary structure information at the level of individual residues. Our results show the presence of a beta-turn, flanked by two beta-sheet regions. We use solid-state NMR data to confirm the presence of the beta-sheets in these regions. In the membrane-attached oligomer, we find a strongly contrasting and near-orthogonal orientation of the backbone H-bonds compared to what is found in the mature, less-toxic A beta fibrils. Significantly, this allows a ``porin'' like beta-barrel structure, providing a structural basis for proposed mechanisms of A beta oligomer toxicity.

Corrosion behaviour of creep-resistant AE42 magnesium alloy-based hybrid composites developed for powertrain applications

The corrosion behaviour of AE42 magnesium alloy and its composites reinforced with Saffil short fibres and SiC particles in various combinations was investigated. The corrosion rate of the unreinforced alloy was the lowest. The composite reinforced with Saffil short fibre alone exhibited slightly lower corrosion rate than the hybrid composites containing both Saffil short fibres and SiC particles. However, there was no specific trend observed in the corrosion rate of the hybrid composites with respect to the SiC particle content. The degradation of corrosion resistance of the composites was mainly attributed to the irregular and loose surface films.

Structural modification and enhanced magnetic properties with two phonon modes in Ca-Co codoped BiFeO3 nanoparticles

Bi1-xCaxFe1-xCoxO3 nanoparticles with x=0.0, 0.05, 0.10 and 0.15 were successfully synthesized by cost effective tartaric acid based sol gel route. The alkali earth metal Ca2+ ions and transition metal Co3+ ions codoping at A and B-sites of BiFeO3 results in structural distortion and phase transformation. Rietveld refinement of XRD patterns suggested the coexistence of rhombohedral and orthorhombic phases in codoped BiFeO3 samples. Both XRD and Raman scattering studies showed the compressive lattice distortion in the samples induced by codoping of Ca2+ and Co3+ ions. Two-phonon Raman spectra exhibited the improvement of magnetization in these samples. X-ray photoelectron spectroscopy (XPS) showed the dominancy of Fe3+ and Co3+ oxidation states along with the shifting of the binding energy of Bi 4f orbital which confirms the substitution Ca2+ at Bi-site. The magnetic study showed the enhancement in room temperature ferromagnetic behavior with co-substitution consistent with Rama analysis. The gradual change in line shape of electron spin resonance spectra indicated the local distortion induced by codoping. (C) 2015 Published by Elsevier Ltd and Techna Group S.r.l.

Flow Cytometry Analysis of Cytotoxicity In Vitro and Long-Term Toxicity of HA-40wt% BaTiO3 Nanoparticles In Vivo

The development of new implantable biomaterials requires bone-mimicking physical properties together with desired biocompatible property. In continuation to our earlier published research to establish compositional dependent multifunctional bone-like properties and cytocompatibility response of hydroxyapatite (HA)-BaTiO3 composites, the toxicological property evaluation, both invitro and invivo, were conducted on HA-40wt% BaTiO3 and reported in this work. In particular, this work reports invitro cytotoxicity of mouse myoblast cells as well as invivo long-term tissue and nanoparticles interaction of intra-articularly injected HA-40wt% BaTiO3 and BaTiO3 up to the concentration of 25mg/mL in physiological saline over 12weeks in mouse model. The careful analysis of flow cytometry results could not reveal any statistically significant difference in terms of early/late apoptotic cells or necrotic cells over 8d in culture. Extensive histological analysis could not record any signature of cellular level toxicity or pronounced inflammatory response in vital organs as well as at knee joints of Balb/c mice after 12weeks. Taken together, this study establishes nontoxic nature of HA-40wt% BaTiO3 and therefore, HA-40wt% BaTiO3 can be used safely for various biomedical applications.

Nickel substitution induced effects on gas sensing properties of cobalt ferrite nanoparticles

Ni2+ ion induced unusual conductivity reversal and an enhancement in the gas sensing properties of ferrites based gas sensors, is reported. The Co1-xNixFe2O4 (for x = 0, 0.5 and 1) nanoparticles were synthesized by wet chemical co-precipitation method and gas sensing properties were studied as a function of composition and temperature. The structural, morphological and microstructural characterization revealed crystallite size of in the range 10-20 nm with porous morphology consisting of nano-sized grains. The Energy Dispersive X-ray (EDX) mapping confirms homogeneous distribution of Co, Ni, Fe and O elements in the ferrites. The non-stoichiometry of the inverse spinel type ferrites and the relative concentration of Ni3+/Co3+ defects were studied using X-ray photoelectron spectroscopy. It is found that the addition of Ni2+ ions into cobalt ferrite shows preferred selectivity towards CO gas at high temperature (325 degrees C) and ethanol gas at low temperature (250 degrees C), unlike undoped cobalt ferrite or undoped nickel ferrite, which show similar response for both these gases. Moreover, an unusual conductivity reversal is observed, except cobalt ferrite due to the difference in reactivity of the gases as well as characteristic non-stoichiometry of ferrites. This behavior is highly gas ambient dependent and hence can be well-exploited for selective detection of gases. (C) 2015 Elsevier B.V. All rights reserved.

Ultra-small sulphur nanoparticles configured inside a flexible organic mixed conducting network as a cathode for lithium-sulphur batteries

The major challenges in Li-S batteries are the formation of soluble polysulphides during the reversible conversion of S-8 <-> Li2S, large changes in sulphur particle volume during lithiation and extremely poor charge transport in sulphur. We demonstrate here a novel and simple strategy to overcome these challenges towards practical realization of a stable high performance Li-S battery. For the first time, a strategy is developed which does away with the necessity of pre-fabricated high surface area hollow-structured adsorbates and also multiple nontrivial synthesis steps related to sulphur loading inside such adsorbates. A lithiated polyethylene glycol (PEG) based surfactant tethered on ultra-small sulphur nanoparticles and wrapped up with polyaniline (PAni) (abbreviated as S-MIEC) is demonstrated here as an exceptional cathode for Li-S batteries. The PEG and PAni network around the sulphur nanoparticles serves as an efficient flexible trap for sulphur and polysulphides and also provides distinct pathways for electrons (through PAni) and ions (through PEG) during battery operation. Contrary to the cathodes demonstrated based on various carbon-sulphur composites, the mixed conducting S-MIEC showed an extremely high loading of 75%. The S-MIEC exhibited a stable capacity of nearly 900 mA h g(-1) at the end of 100 cycles at a 1C current rate.

Die Filling Behaviour of Semi Solid A356 Al Alloy Slurry During Rheo Pressure Die Casting

The present work discusses the findings obtained from simulations of semi solid die filling of a steering knuckle, prior to actual component development using in-house developed rheo pressure die casting system. Die filling capability of A356 Al alloy at semi-solid state has been investigated using commercial software Flow-3Dcast to optimise the pouring temperature of semi-solid slurry into the die cavity, while all other variables such as gating design, die preheat temperature and injection velocity are kept constant based on the prior knowledge obtained from trial numerical simulations and experimentation. Efforts have been made to nullify the essence of costly, time consuming experiments towards obtaining high-quality castings out of the findings obtained from numerical simulations. The optimum pouring temperature identified in the present study is 610 A degrees C, which facilitates smoother slurry flow, minimum surface defect concentration, uniform temperature field and solid fraction distribution within the component cavity.