Evolution of structural phase coexistence in a half doped manganite Pr0.5Sr0.5MnO3: An evidence for magneto-structural coupling

Temperature dependent x-ray diffraction measurements have been performed to understand the implications of magnetic phase coexistence on crystallographic structure in a half-doped manganite Pr0.5Sr0.5MnO3. The compound shows a structural phase transition from high-temperature tetragonal-I4/mcm to low-temperature orthorhombic-Fmmm symmetry around the ferromagnetic to antiferro-magnetic transition. Rietveld analysis shows the coexistence of these two structures emerges at high temperature within the ferromagnetic state, and persists down to lowest temperature. Below around 40 K, however, this structural evolution stops, and a significant fraction (similar to 22%) of untransformed high-temperature phase remains. This agrees with earlier magnetization study, thus establishing its magneto-structural coupling. (C) 2012 Elsevier B.V. All rights reserved.

Silver nanoparticles modified nanocapsules for ultrasonically activated drug delivery

Novel ultrasound-sensitive nanocapsules were designed via layer-by-layer assembly (LbL) of polyelectrolytes for remote activated release of biomolecules/drug. Nanocapsules embedded with silver nanoparticles in the walls were synthesized by alternate assembly of poly(allylamine hydrochloride) (PAH) and dextran sulfate (DS) on silica template followed by nanoparticle synthesis and subsequent template removal thus yielding nanocapsules. The silver NPs were synthesized in situ within the capsule walls under controlled conditions. The nanocapsules were found to be well dispersed and the silver NPs were evenly distributed within the shell. FITC-dextran permeated easily into the capsules containing silver NP's due to the pores generated during the formation of NP's. When the loaded nanocapsules were sonicated, the presence of the silver NPs in the shell structure led to rupturing of the shell into smaller fragments thus releasing the FITC-dextran. Such nanocapsules have the potential to be used as drug delivery vehicles and offer the scope for further development in the areas of modern medicine, material science, and biochemistry. (C) 2012 Elsevier B.V. All rights reserved.

Magneto-Transport Study of Pure and Co Doped ZnO Thin Films

A detailed low temperature magneto-transport study is carried out to understand the transport mechanism in pure and Co doped ZnO thin films grown by pulsed laser deposition (PLD) technique. A negative transverse magneto-resistance (MR) (with a value similar to 4% at 4.5 K) which decreases monotonically with the increase in temperature, is observed for the undoped ZnO film. A competition between positive and negative MR is observed for the Co doped ZnO samples. In this case at higher field values negative MR contribution dominates over the positive MR, which gives rise to a slope change in the MR data. Our data for MR shows excellent agreement with the semi-empirical formula given by Khosla et al., which is originally proposed for the degenerate semiconductors. This formula incorporates the third order perturbation expansion of the s-d exchange scattering of the conduction electrons from the localised spins. We have also obtained the Hall mobility, carrier conc. and mean free path as function of temperature for the pure ZnO film.

Direct ultrafast laser written C-band waveguide amplifier in Er-doped chalcogenide glass

This paper reports the fabrication and characterization of an ultrafast laser written Er-doped chalcogenide glass buried waveguide amplifier; Er-doped GeGaS glass has been synthesized by the vacuum sealed melt quenching technique. Waveguides have been fabricated inside the 4 mm long sample by direct ultrafast laser writing. The total passive fiber-to-fiber insertion loss is 2.58 +/- 0.02 dB at 1600 nm, including a propagation loss of 1.6 +/- 0.3 dB. Active characterization shows a relative gain of 2.524 +/- 0.002 dB/cm and 1.359 +/- 0.005 dB/cm at 1541 nm and 1550 nm respectively, for a pump power of 500 mW at a wavelength of 980 nm. (C) 2012 Optical Society of America

Metal and Alloy Nanoparticles by Amine-Borane Reduction of Metal Salts by Solid-Phase Synthesis: Atom Economy and Green Process

A new solid state synthetic route has been developed toward metal and bimetallic alloy nanoparticles from metal salts employing amine-boranes, as the reducing agent. During the reduction, amine-borane plays a dual role: acts as a reducing agent and reduces the metal salts to their elemental form and simultaneously generates a stabilizing agent in situ which controls the growth of the particles and stabilizes them in the nanosize regime. Employing different amine-boranes with differing reducing ability (ammonia borane (AB), dimethylamine borane (DMAB), and triethylamine borane (TMAB)) was found to have a profound effect on the particle size and the size distribution. Usage of AB as the reducing agent provided the smallest possible size with best size distribution. Employment of TMAB also afforded similar results; however, when DMAB was used as the reducing agent it resulted in larger sized nanoparticles that are polydisperse too. In the AB mediated reduction, BNHx polymer generated in situ acts as a capping agent whereas, the complexing amine of the other amine-boranes (DMAB and TMAB) play the same role. Employing the solid state route described herein, monometallic Au, Ag, Cu, Pd, and Ir and bimetallic CuAg and CuAu alloy nanoparticles of <10 nm were successfully prepared. Nucleation and growth processes that control the size and the size distribution of the resulting nanoparticles have been elucidated in these systems.

Size-dependent density of nanoparticles and nanostructured materials

We discuss the size-dependent density of nanoparticles and nanostructured materials keeping the recent experimental results in mind. The density is predicted to increase with decreasing size for nanoparticles but it can decrease with size for nanostructured materials that corroborates the experimental results reported in the literature. (C) 2012 Elsevier B.V. All rights reserved.

Effect of high gold salt concentrations on the size and polydispersity of gold nanoparticles prepared by an extended Turkevich-Frens method

The Turkevich-Frens synthesis starting conditions are expanded, ranging the gold salt concentrations up to 2 mM and citrate/gold(III) molar ratios up to 18:1. For each concentration of the initial gold salt solution, the citrate/gold(III) molar ratios are systematically varied from 2:1 to 18:1 and both the size and size distribution of the resulting gold nanoparticles are compared. This study reveals a different nanoparticle size evolution for gold salt solutions ranging below 0.8 mM compared to the case of gold salt solutions above 0.8 mM. In the case of Au3+]<0.8 mM, both the size and size distribution vary substantially with the citrate/gold(III) ratio, both displaying plateaux that evolve inversely to Au3+] at larger ratios. Conversely, for Au3+]>= 0.8 mM, the size and size distribution of the synthesized gold nanoparticles continuously rise as the citrate/gold(III) ratio is increased. A starting gold salt concentration of 0.6 mM leads to the formation of the most monodisperse gold nanoparticles (polydispersity index<0.1) for a wide range of citrate/gold(III) molar ratios (from 4:1 to 18:1). Via a model for the formation of gold nanoparticles by the citrate method, the experimental trends in size could be qualitatively predicted:the simulations showed that the destabilizing effect of increased electrolyte concentration at high initial Au3+] is compensated by a slight increase in zeta potential of gold nanoparticles to produce concentrated dispersion of gold nanoparticles of small sizes.

Orthogonal biofunctionalization of magnetic nanoparticles via ``clickable'' poly(ethylene glycol) silanes: a ``universal ligand'' strategy to design stealth and target-specific nanocarriers

The present work demonstrates a novel strategy to synthesize orthogonally bio-engineered magnetonanohybrids (MNPs) through the design of versatile, biocompatible linkers whose structure includes: (i) a robust anchor to bind with metal-oxide surfaces; (ii) tailored surface groups to act as spacers and (iii) a general method to implement orthogonal functionalizations of the substrate via ``click chemistry''. Ligands that possess the synthetic generality of features (i)-(iii) are categorized as ``universal ligands''. Herein, we report the synthesis of a novel, azido-terminated poly(ethylene glycol) (PEG) silane that can easily self-assemble on MNPs through hetero-condensation between surface hydroxyl groups and the silane end of the ligand, and simultaneously provide multiple clickable sites for high density, chemoselective bio-conjugation. To establish the universal-ligand-strategy, we clicked alkyl-functionalized folate onto the surface of PEGylated MNPs. By further integrating a near-infrared fluorescent (NIRF) marker (Alexa-Fluor 647) with MNPs, we demonstrated their folate-receptor mediated internalization inside cancer cells and subsequent translocation into lysosomes and mitochondria. Ex vivo NIRF imaging established that the azido-PEG-silane developed in course of the study can effectively reduce the sequestration of MNPs by macrophage organs (viz. liver and spleen). These folate-PEG-MNPs were not only stealth and noncytotoxic but their dual optical and magnetic properties aided in tracking their whereabouts through combined magnetic resonance and optical imaging. Together, these results provided a strong motivation for the future use of the ``universal ligand'' strategy towards development of ``smart'' nanohybrids for theragnostic applications.

Grafting of Dispersants on MoS2 Nanoparticles in Base Oil Lubrication of Steel

Solid lubricant nanoparticles in suspension in oil are good lubricating options for practical machinery. In this article, we select a range of dispersants, based on their polar moieties, to suspend 50-nm molybdenum disulfide particles in an industrial base oil. The suspension is used to lubricate a steel on steel sliding contact. A nitrogen-based polymeric dispersant (aminopropyl trimethoxy silane) with a free amine group and an oxygen-based polymeric dispersant (sorbital monooleate) when grafted on the particle charge the particle negatively and yield an agglomerate size which is almost the same as that of the original particle. Lubrication of the contact by these suspensions gives a coefficient of friction in the similar to 0.03 range. The grafting of these surfactants on the particle is shown here to be of a chemical nature and strong as the grafts survive mechanical shear stress in tribology. Such grafts are superior to those of other silane-based test surfactants which have weak functional groups. In the latter case, the particles bereft of strong grafts agglomerate easily in the lubricant and give a coefficient of friction in the 0.08-0.12 range. This article investigates the mechanism of frictional energy dissipation as influenced by the chemistry of the surfactant molecule.

Synthesis and characterization of Fe- and Co-based ferrite nanoparticles and study of the T-1 and T-2 relaxivity of chitosan-coated particles

In pursuit of newer and more effective contrast agents for magnetic resonance imaging, we report in this article the use of biocompatible chitosan-coated ferrite nanoparticles of different kinds with a view to determine their potential applications as the contrast agents in the field of nuclear magnetic resonance. The single-phase ferrite particles were synthesized by chemical co-precipitation (CoFe2O4 and Fe3O4) and by applying ultrasonic vibration (CoFe2O4 and Co0.8Zn0.2Fe2O4). Although magnetic anisotropy of CoFe2O4 nanoparticle leads to finite coercivity even for nanoensembles, it has been reduced significantly to a minimum level by applying ultrasonic vibration. Fe3O4 synthesized by chemical co-precipitation yielded particles which already possess negligible coercivity and remanence. Substitution of Co by Zn in CoFe2O4 increases the magnetization significantly with a small increase in coercivity and remanence. Particles synthesized by the application of ultrasonic vibration leads to the higher values of T-2 relaxivities than by chemical coprecipitation. We report that the T-2 relaxivities of these particles are of two orders of magnitude higher than corresponding T-1 relaxivities. Thus, these particles are evidently suitable as contrast agent for T-2 weighted MR images.

Synthesis of zero valent iron nanoparticles and application to removal of arsenic(III) and arsenic(V) from water

Recently nano scale zero valent iron particles (nZVI) have been considered as smart adsorbent for environmental and groundwater remediation. Although several synthetic methods are available for the preparation of nZVI, air stable nZVI are not available for remediation works. Further, challenges demand synthesis of nZVI without stabilizers and capping agents. A modified methodology for the synthesis of air stable nZVI has been developed without any capping agents and characterized by powder X-Ray Diffraction (XRD), Scanning Electron Microscopy Energy-dispersive X-Ray (SEM-EDS), Transmission Electron Microscopy (TEM) and X-Ray Photoelectron Spectroscopy (XPS). The results of the present study suggest that the synthetic nZVI are air-stable over a period of one year and consists of particles of 30-40 nm in diameter. Although a layer of less than 3 am thick oxide/hydroxide is observed by TEM and XPS, it appears to be due to oxidation of outer surface during analysis. Adsorption study has shown that the synthetic nZVI are more effective adsorbent than the commercial nZVI and can remove simultaneously arsenite As-III] and arsenate As-V] from water without prior reduction of As-V to As-III. The removal process is adsorptive rather than precipitative and the removal of As-III is greater than that of As-V.

A simple method of synthesis and optical properties of Mn doped ZnO nanocups

A combination of chemical and thermal annealing techniques has been employed to synthesize a rarely reported nanocup structure of Mn doped ZnO with good yield. Nanocup structures are obtained by thermally annealing the powder samples consisting of nanosheets, synthesized chemically at room temperature, isochronally in a furnace at 200-500 degrees C temperature range for 2 h. Strong excitonic absorption in the UV and photoluminescence (PL) emission in UV-visible regions are observed in all the samples at room temperature. The sample obtained at 300 degrees C annealing temperature exhibits strong PL emission in the UV due to near-band-edge emission along with very week defect related emissions in the visible regions. The synthesized samples have been found to be exhibiting stable optical properties for 10 months which proved the unique feature of the presented technique of synthesis of nanocup structures. (C) 2012 Elsevier B.V. All rights reserved.

Compositionally Graded Microstructure for Ag-Fe Nanoparticles

Ag-Fe nanoparticles with a highly Ag rich average composition were synthesized by the sonochemical route. Silver-iron system exhibits a wide miscibility gap in the bulk materials. Interestingly, a graded compositional profile along the nanoparticle radius was observed. Regions at and near the surface of the nanoparticle contained both Ag and Fe atoms. The composition got relatively deficient Fe towards the center of the particle with particle core made up of pure Ag. Alloying of Ag and Fe is confirmed by the absence of diffraction signal corresponding to pure Fe phase and presence of a paramagnetic phase in nanoparticles containing a diamagnetic (Ag) and ferromagnetic (Fe) elements.

Doping by diffusion of dopants from the substrate: synthesis of doped ZnO nanowires

We report on the substrate assisted doping of ZnO nanowires grown by a vapor transport technique. The nanowires were grown non-catalytically on multiwalled carbon nanotubes (MWCNTs) and soda lime glass (SLG). Carbon from MWCNTs and sodium from SLG diffuse into ZnO during the growth and are distributed uniformly and provide doping. An advantage associated with the technique is that no conventional external dopant source is required to obtain doped ZnO nanowires. The diameter, length and hence the aspect ratio can easily be varied by changing the growth conditions. The transport studies on both carbon and sodium doped ZnO support the p-type nature of ZnO. The p-type nature of carbon doped ZnO is stable for at least eight months.

Magnetization in electron- and Mn- doped SrTiO3

Mn- doped SrTiO3.0, when synthesized free of impurities, is a paramagnetic insulator with interesting dielectric properties. Since delocalized charge carriers are known to promote ferromagnetism in a large number of systems via diverse mechanisms, we have looked for the possibility of any intrinsic, spontaneous magnetization by simultaneous doping of Mn ions and electrons into SrTiO3 via oxygen vacancies, thereby forming SrTi1-xMnxO3-delta, to the extent of making the doped system metallic. We find an absence of any enhancement of the magnetization in the metallic sample when compared with a similarly prepared Mn doped, however, insulating sample. Our results, thus, are not in agreement with a recent observation of a weak ferromagnetism in metallic Mn doped SrTiO3 system.