Highly dispersed ultrafine Pt and PtRu nanoparticles on graphene: formation mechanism and electrocatalytic activity

We demonstrate a robust strategy for obtaining a high dispersion of ultrafine Pt and PtRu nanoparticles on graphene by exploiting the nucleation of a metal precursor phase on graphite oxide surfaces. Our method opens up new possibilities to engineer graphene-based hybrids for applications in multifunctional nanoscale devices.

Ultrafast Microwave-Assisted Route to Surfactant-Free Ultrafine Pt Nanoparticles on Graphene: Synergistic Co-reduction Mechanism and High Catalytic Activity

We demonstrate an ultrafast method for the formation of, graphene supported Pt catalysts by the co-reduction of graphene oxide and Pt salt using ethylene glycol under microwave irradiation conditions. Detailed analysis of the mechanism of formation of the hybrids indicates a synergistic co-reduction mechanism whereby the presence of the Pt ions leads to a faster reduction of GO and the presence of the defect sites on the reduced GO serves as anchor points for the heterogeneous nucleation of Pt. The resulting hybrid consists of ultrafine nanoparticles of Pt uniformly distributed on the reduced GO susbtrate. We have shown that the hybrid exhibits good catalytic activity for methanol oxidation and hydrogen conversion reactions. The mechanism is general and applicable for the synthesis of other multifunctional hybrids based on graphene.

``Clickable'', Trifunctional Magnetite Nanoparticles and Their Chemoselective Biofunctionalization

A multifunctional iron oxide based nanoformulation for combined cancer-targeted therapy and multimodal imaging has been meticulously designed and synthesized using a chemoselective ligation approach. Novel superparamagnetic magnetite nanoparticles simultaneously functionalized with amine, carboxyl, and azide groups were fabricated through a sequence of stoichiometrically controllable partial succinylation and Cu (II) catalyzed diazo transfer on the reactive amine termini of 2-aminoethylphosphonate grafted magnetite nanoparticles (MNPs). Functional moieties associated with MNP surface were chemoselectively conjugated with rhodamine B isothiocyanate (RITC), propargyl folate (FA), and paclitaxel (PTX) via tandem nucleophic addition of amine to isothithiocyanates, Cu (I) catalyzed azide-alkyne click chemistry and carbodiimide-promoted esterification. An extensive in vitro study established that the bioactives chemoselectively appended to the magnetite core bequeathed multifunctionality to the nanoparticles without any loss of activity of the functional molecules. Multifunctional nanoparticles, developed in the course of the study, could selectively target and induce apoptosis to folate-receptor (FR) overexpressing cancer cells with enhanced efficacy as compared to the free drug. In addition, the dual optical and magnetic properties of the synthesized nanoparticles aided in the real-time tracking of their intracellular pathways also as apoptotic events through dual fluorescence and MR-based imaging.

Synthesis of mesoporous materials based on titanium(IV)oxide and titanium nitride

Nanoparticles of titania were obtained by the controlled hydrolysis of Ti(i-OC3H7)(4) in the reverse micelles of dodecylamine derived from dodecylamine-isopropanol-water solution (water/oil microemulsion). The mesolamellar phase based on titanium nitride (TiN) was obtained by first decomposing TiN atleast partially using the 1:1 solution of acid mixture (HF and HNO3 in the ratio of 9:1) in water and then templating onto the cationic surfactant namely, cetyltrimethylammaniumbromide (abbreviated as CTAB) at 80 degrees C. The synthesis of mesolamellar phase based on TiN involves the charge matched templating approach following the counter-ion mediated pathway. The samples thus obtained were characterized by small angle x-ray diffraction using Cuk(a) radiation, scanning electron microscopy and transmission electron microscopy, which indicated some satisfactory results. (C) 1999 Acta Metallurgica Inc.

Surfactant-mediated Synthesis of Functional Metal Oxide Nanostructures via Microwave Irradiation-assisted Chemical Synthesis

Nanostructured materials have attracted considerable interest in recent years due to their properties which differ strongly from their bulk phase and potential applications in nanoscale electronic and optoelectronic devices. Metal oxide nanostructures can be synthesized by variety of different synthesis techniques developed in recent years such as thermal decomposition, sol-gel technique, chemical coprecipitation, hydrothermal process, solvothermal process, spray pyrolysis, polyol process etc. All the above processes go through a tedious synthesis procedure followed by prolonged heat treatment at elevated temperature and are time consuming. In the present work we describe a rapid microwave irradiation-assisted chemical synthesis technique for the growth of nanoparticles, nanorods, and nanotubes of a variety of metal oxides in the presence of an appropriate surfactant, without the use of any templates The method is simple, inexpensive, and helps one to prepare nanostructures in a very simple way, and in a very short time, measured in minutes. The synthesis procedure employs high quality metalorganic complexes (typically -diketonates) featuring a direct metal-to-oxygen bond in its molecular structure. The complex is dissolved in a suitable solvent, often with a surfactant added, and the solution then subjected to microwave irradiation in a domestic microwave oven operating at 2.45 GHz frequency with power varying from 160-800 W, from a few seconds to a few minutes, leading to the formation of corresponding metal oxides. This method has been used successfully to synthesize nanostructures of a variety of binary and ternary metal oxides such as ZnO, CdO, Fe2O3, CuO, Ga2O3, Gd2O3, ZnFe2O4, etc. There is an observed variation in the morphology of the nanostructures with the change of different parameters such as microwave power, irradiation time, appropriate solvent, surfactant type and concentration. Cationic, anionic, nonionic and polymeric surfactants have been used to generate a variety of nanostructures. Even so, to remove the surfactant, there is either no need of heat treatment or a very brief exposure to heat suffices, to yield highly pure and crystalline oxide materials as prepared. By adducting the metal complexes, the shape of the nanostructures can be controlled further. In this manner, very well formed, single-crystalline, hexagonal nanorods and nanotubes of ZnO have been formed. Adducting the zinc complex leads to the formation of tapered ZnO nanorods with a very fine tip, suitable for electron emission applications. Particle size and their monodispersity can be controlled by a suitable choice of a precursor complex, the surfactant, and its concentration. The resulting metal oxide nanostructures have been characterized by X-ray diffraction, field emission scanning electron microscopy, transmission electron microscopy, FTIR spectroscopy, photoluminescence, and electron emission measurements.

Cyclodextrin functionalized magnetic iron oxide nanocrystals: a host-carrier for magnetic separation of non-polar molecules and arsenic from aqueous media

A single-step magnetic separation procedure that can remove both organic pollutants and arsenic from contaminated water is clearly a desirable goal. Here we show that water dispersible magnetite nanoparticles prepared by anchoring carboxymethyl-beta-cyclodextrin (CMCD) cavities to the surface of magnetic nanoparticles are suitable host carriers for such a process. Monodisperse, 10 nm, spherical magnetite, Fe3O4, nanocrystals were prepared by the thermal decomposition of FeOOH. Trace amounts of antiferromagnet, FeO, present in the particles provides an exchange bias field that results in a high superparamagnetic blocking temperature and appreciable magnetization values that facilitate easy separation of the nanocrystals from aqueous dispersions on application of modest magnetic fields. We show here that small molecules like naphthalene and naphthol can be removed from aqueous media by forming inclusion complexes with the anchored cavities of the CMCD-Fe3O4 nanocrystals followed by separation of the nanocrystals by application of a magnetic field. The adsorption properties of the iron oxide surface towards As ions are unaffected by the CMCD capping so it too can be simultaneously removed in the separation process. The CMCD-Fe3O4 nanocrystals provide a versatile platform for magnetic separation with potential applications in water remediation.

Zinc Oxide Modified Au Electrode as Sensor for an Efficient Detection of Hydrazine

ZnO nanoparticles (ZnO NPs) prepared by microwave heating technique are used to modify a gold electrode (ZnO/Au) for the hydrazine detection study. The synthesized product is well characterized by various techniques. Detailed electrochemical investigation of the oxidation of hydrazine on the ZnO/Au electrode in 0.02 M phosphate buffer solution (PBS) of pH 7.4 was carried out. A very low detection limit of 66 nM (S/N=4) and a wide linearity in current for a concentration range from 66.0X10-3 to 415 mu M was achieved by amperometry. The electrode was found to be stable for over a month when preserved in PBS.

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.

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.

Synthesis of pure iron magnetic nanoparticles in large quantity

Free nanoparticles of iron (Fe) and their colloids with high saturation magnetization are in demand for medical and microfluidic applications. However, the oxide layer that forms during processing has made such synthesis a formidable challenge. Lowering the synthesis temperature decreases rate of oxidation and hence provides a new way of producing pure metallic nanoparticles prone to oxidation in bulk amount (large quantity). In this paper we have proposed a methodology that is designed with the knowledge of thermodynamic imperatives of oxidation to obtain almost oxygen-free iron nanoparticles, with or without any organic capping by controlled milling at low temperatures in a specially designed high-energy ball mill with the possibility of bulk production. The particles can be ultrasonicated to produce colloids and can be bio-capped to produce transparent solution. The magnetic properties of these nanoparticles confirm their superiority for possible biomedical and other applications.

Reduced graphene oxide-supported nickel oxide catalyst with improved CO tolerance for formic acid electrooxidation

The superior catalytic activity along with improved CO tolerance for formic acid electro-oxidation has been demonstrated on a NiO-decorated reduced graphene oxide (rGO) catalyst. The cyclic voltammetry response of rGO-NiO/Pt catalyst elucidates improved CO tolerance and follows direct oxidation pathway. It is probably due to the beneficial effect of residual oxygen groups on rGO support which is supported by FT-IR spectrum. A strong interaction of rGO support with NiO nanoparticles facilitates the removal of CO from the catalyst surface. The chronoamperometric response indicates a higher catalytic activity and stability of rGO-NiO/Pt catalyst than the NiO/Pt and unmodified Pt electrode catalyst for a prolonged time of continuous oxidation of formic acid. Copyright (C) 2014, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights reserved.

Combinatorial effect of rolling and carbonaceous nanoparticles on the evolution of crystallographic texture and structural properties of ultra high molecular weight polyethylene

Ultra high molecular weight polyethylene (PE) is a structural polymer widely used in biomedical implants. The mechanical properties of PE can be improved either by controlled crystalline orientation (texture) or by the addition of reinforcing agents. However, the combinatorial effect has not received much attention. The objective of this study was to characterize the structure and mechanical properties of PE composites incorporating multiwall carbon nanotubes (MWCNT) and reduced graphene oxide (RGO) subjected to hot rolling. The wide angle X-ray diffraction studies revealed that mechanical deformation resulted in a mixture of orthorhombic and monoclinic crystals. Furthermore, the presence of nanoparticles resulted in lower crystallinity in PE with smaller crystallite size, more so in RGO than in MWCNT composites. Rolling strengthened the texture of both orthorhombic and the monoclinic phases in PE. Presence of RGO weakened the texture of both phases of PE after rolling whereas MWCNT only mildly weakened the texture. This resulted in a reduction in the elastic modulus of RGO composites whereas moduli of neat polymer and the MWCNT composite increased after rolling. This study provides new insight into the role of nanoparticles in texture evolution during polymer processing with implications for processing of structural polymer composites.

Graphene Oxide-MnFe2O4 Magnetic Nanohybrids for Efficient Removal of Lead and Arsenic from Water

We show that the hybrids of single-layer graphene oxide with manganese ferrite magnetic nanoparticles have the best adsorption properties for efficient removal of Pb(II), As(III), and As(V) from contaminated water. The nanohybrids prepared by coprecipitation technique were characterized using atomic force and scanning electron microscopies, Fourier transformed infrared spectroscopy, Raman spectroscopy, X-ray diffraction, and surface area measurements. Magnetic character of the nanohybrids was ascertained by a vibrating sample magnetometer. Batch experiments were carried out to quantify the adsorption kinetics and adsorption capacities of the nanohybrids and compared with the bare nanoparticles of MnFe2O4. The adsorption data from our experiments fit the Langmuir isotherm, yielding the maximum adsorption capacity higher than the reported values so far. Temperature-dependent adsorption studies have been done to estimate the free energy and enthalpy of adsorption. Reusability, ease of magnetic separation, high removal efficiency, high surface area, and fast kinetics make these nanohybrids very attractive candidates for low-cost adsorbents for the effective coremoval of heavy metals from contaminated water.

High Value of Proton Relaxivity Achieved by Graphene Oxide-Cobalt Ferrite Nanoparticle Composite: A Potential Contrast Agent in Magnetic Resonance Imaging

This work investigates the potential of graphene oxide-cobalt ferrite nanoparticle (GO-CoFe2O4) composite as image contrast enhancing material in Magnetic Resonance Imaging (MRI). In the preset work, GO-CoFe2O4 composites were produced by a two-step synthesis process. In the first step, graphene oxide (GO) was synthesized, and in the second step CoFe2O4 nanoparticles were synthesized in a reaction mixture containing GO to yield graphene GO-CoFe2O4 composite. Proton relaxivity value obtained from the composite was 361 mM(-1)s(-1). This value of proton relaxivity is higher than a majority of reported relaxivity values obtained using several ferrite based contrast agents.

Electromagnetic interference shielding through MWNT grafted Fe3O4 nanoparticles in PC/SAN blends

In this study, multiwall carbon nanotubes (MWNTs) were chemically grafted onto dopamine anchored iron oxide (Fe3O4) nanoparticles via diazotization reaction to design electromagnetic (EM) shielding materials based on PC (polycarbonate)/SAN poly (styrene-co-acrylonitrile)] blends. A two step mixing protocol was adopted to selectively localize the nanoparticles in a given phase of the blends. In the first step, MWNT-g-Fe3O4 nanoparticles were solution blended with PC, followed by dilution with SAN during melt mixing in the subsequent step. This strategy, besides improving the quality of dispersion of MWNTs in the blends, facilitated enhanced EM interference shielding effectiveness (SE). Both, the MWNTs and the modified MWNTs, selectively localized in the PC phase and led to high electrical conductivity, in striking contrast to PC filled MWNT composites. The SE was measured on toroidal samples over a broad range of frequencies; X-band (8.2-12 GHz) and K-u-band (12-18 GHz). It was observed that the shielding mechanism mostly involved reflection in the blends with MWNTs, whereas absorption dominated in the case of blends with MWNT-g-Fe3O4. To realize the efficacy of this strategy, a few compositions were prepared by physical mixing MWNTs with Fe3O4 nanoparticles. Intriguingly, blends with MWNT-g-Fe3O4 nanoparticles manifested enhanced microwave absorption over physically mixed nanoparticles. An SE of -32.5 dB was observed (at 18 GHz) for MWNT (3 wt%)-g-Fe3O4 (3 vol%) in PC/SAN blends.