Mapping the intriguing transient morphologies and the demixing behavior in PS/PVME blends in the presence of rod-like nanoparticles

The demixing behavior, transient morphologies and mechanism of phase separation in PS/PVME blends were greatly altered in the presence of a very low concentration of rod-like particles (multiwall carbon nanotubes, MWNTs). This phenomenon is due to the specific interaction of one of the phases (PVME) with the anisotropic MWNTs, which creates a heterogeneous environment in the blend. This specific interaction alters the chain dynamics in the interfacial region as against the bulk. A comprehensive analysis using isochronal temperature sweep was performed to understand the demixing temperature in the blends. The evolution of phase morphology as a function of time and temperature was assessed by polarizing optical microscopy (POM), atomic force microscopy (AFM) and scanning electron microscopy (SEM). The addition of MWNTs increased the rheological demixing temperature and the spinodal temperature in almost all the compositions. The intriguing transient morphologies were mapped, which varied from nucleation and growth to coalescence-induced viscoelastic phase separation (C-VPS) in PVME-rich blends, to spinodal decomposition in the near-critical compositions, to transient gel-induced VPS (T-VPS) in the PS-rich compositions. Mapping of the morphology development displayed two types of fracture mechanisms: ductile fracture for near-critical compositions and brittle fracture for off-critical composition. The change in the phase separation mechanism in the presence of MWNTs was due to the variation in dynamic asymmetry brought about by these anisotropic particles. All these observations were correlated by POM, SEM and AFM studies. The length of the cooperatively rearranging region (CRR), as evaluated using modulated differential scanning calorimetry (MDSC) measurements, was found to be composition-independent. The observed variation of effective glass transition of PVME (low T-g component) on blending with PS (high Tg component) and by the addition of MWNTs accounts for the dynamic heterogeneity introduced by MWNTs in the system.

Photocatalytic inactivation of E-Coli by ZnO-Ag nanoparticles under solar radiation

Porous and fluffy ZnO photocatalysts were successfully prepared via simple solution based combustion synthesis method. The photocatalytic inactivation of Escherichia coli bacteria was studied separately for both Ag substituted and impregnated ZnO under irradiation of natural solar light. A better understanding of substitution and impregnation of Ag was obtained by Raman spectrum and X-ray photoelectron analysis. The reaction parameters such as catalyst dose, initial bacterial concentration and effect of hydroxyl radicals via H2O2 addition were also studied for ZnO catalyst. Effective inactivation was observed with 0.25 g L-1 catalyst loading having 10(9) CFU mL(-1) bacterial concentration. With an increase in molarity of H2O2, photocatalytic inactivation was enhanced. The effects of different catalysts were studied, and highest bacterial killing was observed by Ag impregnated ZnO with 1 atom% Ag compared to Ag substituted ZnO. This enhanced activity can be attributed to effective charge separation that is supported by photoluminescence studies. The kinetics of reaction in the presence of different scavengers showed that reaction is significantly influenced by the presence of hole and hydroxyl radical scavenger with high efficiency.

Investigations on doping induced changes in structural, electronic structure and magnetic behavior of spintronic Cr-ZnS nanoparticles

Dilute magnetic semiconducting Zn1-xCrxS (x = 0.00, 0.01, 0.03, 0.05, 0.07) nanoparticles were synthesized by the co-precipitation technique using thioglycerol as the capping agent. Powder X-ray diffraction studies showed that Zn1-xCrxS nanoparticles exhibit zinc blende structure with no secondary phase, indicating that Cr ions are substituted at the Zn sites. Photoluminescence and Raman studies show the incorporation of Cr in ZnS nanoparticles. X-ray absorption studies depict that the valence of Zn remains unchanged and maintained in the divalent state, upon doping with Cr. The M-H curves at room temperature indicate the presence of weak ferromagnetism at room temperature due to structural defects. The increase in ferromagnetism with increasing Cr content up to 3%, demonstrates the possibility of tailoring the weak ferromagnetism in ZnS by appropriate Cr doping. (C) 2015 Elsevier Ltd. All rights reserved.

Boron and Nitrogen Co-doped Carbon Nanoparticles as Photoluminescent Probes for Selective and Sensitive Detection of Picric Acid

Here, we report the synthesis of boron and nitrogen Co-doped carbon nanoparticles (BN-CNPs) by a hydrothermal method using sucrose, boric acid, and urea as the precursors. The BN-CNPs show excellent photoluminescence with a quantum yield of similar to 14.2% in aqueous solution and can be used as photoluminescent probes for selective and sensitive detection of picric acid (PA). PA quenches the photoluminescence signal remarkably, while other explosives cause a little quenching confirming the high selectivity of BN-CNPs. The sensitivity toward PA sensing is high at pH 7 and increases with temperature. The detection limit as well as the sensitivity are shown to improve by adding NaCl to the PA. The low detection limit can be as low as 10 nM at room temperature and pH 7, which indicates the BN-CNPs are superior as compared to other luminescent probes reported in the literature.

Cytotoxicity of Ultrasmall Gold Nanoparticles on Planktonic and Biofilm Encapsulated Gram-Positive Staphylococci

The emergence of multidrug resistant bacteria, especially biofilm-associated Staphylococci, urgently requires novel antimicrobial agents. The antibacterial activity of ultrasmall gold nanoparticles (AuNPs) is tested against two gram positive: S. aureus and S. epidermidis and two gram negative: Escherichia coli and Pseudomonas aeruginosa strains. Ultrasmall AuNPs with core diameters of 0.8 and 1.4 nm and a triphenylphosphine-monosulfonate shell (Au0.8MS and Au1.4MS) both have minimum inhibitory concentration (MIC) and minimum bactericidal concentration of 25 x 10(-6)m Au]. Disc agar diffusion test demonstrates greater bactericidal activity of the Au0.8MS nanoparticles over Au1.4MS. In contrast, thiol-stabilized AuNPs with a diameter of 1.9 nm (AuroVist) cause no significant toxicity in any of the bacterial strains. Ultrasmall AuNPs cause a near 5 log bacterial growth reduction in the first 5 h of exposure, and incomplete recovery after 21 h. Bacteria show marked membrane blebbing and lysis in biofilm-associated bacteria treated with ultrasmall AuNP. Importantly, a twofold MIC dosage of Au0.8MS and Au1.4MS each cause around 80%-90% reduction in the viability of Staphylococci enveloped in biofilms. Altogether, this study demonstrates potential therapeutic activity of ultrasmall AuNPs as an effective treatment option against staphylococcal infections.

Effect of ultra-fast mixing in a microchannel due to a soft wall on the room temperature synthesis of gold nanoparticles

The room-temperature synthesis of mono-dispersed gold nanoparticles, by the reduction of chlorauric acid (HAuCl4) with tannic acid as the reducing and stabilizing agent, is carried out in a microchannel. The microchannel is fabricated with one soft wall, so that there is a spontaneous transition to turbulence, and thereby enhanced mixing, when the flow Reynolds number increases beyond a critical value. The objective of the study is to examine whether the nanoparticle size and polydispersity can be modified by enhancing the mixing in the microchannel device. The flow rates are varied in order to study nanoparticle formation both in laminar flow and in the chaotic flow after transition, and the molar ratio of the chlorauric acid to tannic acid is also varied to study the effect of molar ratio on nanoparticle size. The formation of gold nanoparticles is examined by UV-visual spectroscopy and the size distribution is determined using scanning electron microscopy. The synthesized nanoparticles size decreases from a parts per thousand yen6 nm to a parts per thousand currency sign4 nm when the molar ratio of chlorauric acid to tannic acid is increased from 1 to 20. It is found that there is no systematic variation of nanoparticle size with flow velocity, and the nanoparticle size is not altered when the flow changes from laminar to turbulent. However, the standard deviation of the size distribution decreases by about 30% after transition, indicating that the enhanced mixing results in uniformity of particle size.

Temperature-Dependent Magnetic and EPR Studies of Bulk and Nanoparticles of Bi0.1Ca0.9MnO3

We report temperature-dependent magnetic and electron paramagnetic resonance (EPR) properties of bulk and nanoparticle samples of Bi0.1Ca0.9MnO3 (BCMO). The nanoparticles of BCMO (dia similar to 50 nm) were prepared by the standard sol-gel technique and bulk samples by solid-state reaction method. We have investigated the magnetic ordering in the two samples by carrying out temperature-dependent magnetic and EPR studies and compared their properties. According to earlier reports, antiferromagnetic and ferromagnetic orders coexist in the bulk sample of Bi0.1Ca0.9MnO3. Our magnetization and EPR results show the existence of ferromagnetism in the bulk sample which is present in the nanosample as well but with somewhat weakened strength with the size reduction.

Engineering Nanostructures by Decorating Magnetic Nanoparticles onto Graphene Oxide Sheets to Shield Electromagnetic Radiations

In this study, a minimum, reflection loss of 70 a was achieved, for a 6 mm thick shield (at 17.1 GHz frequency) employing a unique approach. This was accomplished by engineering nanostructures through decoration of magnetic nanopartides (nickel, Ni) onto graphene oxide (GO) sheets. Enhanced electromagnetic (EM) shielding was derived by selectively, localizing the nanoscopic particles in a specific phase of polyethylene (PE)/poly(ethylene oxide) (PEO) blends. By introduction of a conducting inclusion (like multiwall carbon nanotubes, MWNTs) together with the engineered nanostructures (nickel-decorated GO, (GO-Ni), the shielding efficiency can be enhanced significantly in contrast to physically mixing the particles in the blends. For instance, the composites showed a shielding efficiency >25 dB for a combination of MWNTS (3 wt %) and Ni nanoparticles (52 wt %) in PE/PEO blends. However, similar shielding effectiveness could be achieved for a combination of MWNTs (3 wt %) and 10 vol % of GO-Ni where in the effective concentration of Ni was only 19 wt %. The GO-Ni sheets facilitated in an efficient charge transfer as manifested from high electrical conductivity in the blends besides enhancing the permeability in the blends. It is envisioned that GO is simultaneously reduced in the process of synthesizing GO-Ni, and this facilitated in efficient charge transfer between the neighboring CNTs. More interestingly, the blends With MWNTs/GO-Ni attenuated the incoming EM radiation mostly by absorption. This study opens new avenues in designing polyolefin-based lightweight shielding materials by engineering nanostructures for numerous applications.

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.

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.

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.