Multivalent Cu-Doped ZnO Nanoparticles with Full Solar Spectrum Absorbance and Enhanced Photoactivity

Full solar spectrum absorbers are widely pursued for applications related to photocatalysis and photovoltaics. Here we report multivalent Cu-doped ZnO nanoparticles which exhibit full solar spectrum absorbance and high photoactivity. Metathesis-based, green-chemical approaches with synthesis yield of similar to 100% are used. Cu incorporation in ZnO results in an increase of average solar spectrum absorbance from a mere 0.4% to 34%. On the other hand, (Zn, Cu)0 composites result in materials with up to 64% average solar spectrum absorbance. Doped systems operate well under both visible and UV illumination. The nanomaterials prepared are characterized by using X-ray powder diffraction (XRD), scanning electron microscopy (SEM), Brunauer-Emmett-Teller (BET) surface area analysis, and X-ray photoelectron spectroscopy (XPS). Photocatalysts explored have particle sizes >= 50 nm. This is deliberately done in order to avoid the nanotoxic size regime of ZnO. Despite the large particle size and low specific surface area (<20 m(2).g(-1)), the best catalyst reported here compare favorably with recent reports on ZnO based systems. Using X-photoelectron spectroscopy and synthesis property correlations, we infer that the presence of multivalent Cu (most likely in the form of Cu1+delta) on ZnO surface is responsible for the observed photoactivity enhancement.

Density Functional Theoretical Modeling, Electrostatic Surface Potential and Surface Enhanced Raman Spectroscopic Studies on Biosynthesized Silver Nanoparticles: Observation of 400 pM Sensitivity to Explosives

Interaction of adsorbate on charged surfaces, orientation of the analyte on the surface, and surface enhancement aspects have been studied. These aspects have been explored in details to explain the surface-enhanced Raman spectroscopic (SERS) spectra of 2,4,6,8,10,12-hexanitro-2,4,6,8,10,12-hexaazaisowurtzitane (HNIW or CL-20), a well-known explosive, and 2,4,6-trinitrotoluene (TNT) using one-pot synthesis of silver nanoparticles via biosynthetic route using natural precursor extracts of clove and pepper. The biosynthesized silver nanoparticles (bio Ag Nps) have been characterized using UV-vis spectroscopy, scanning electron microscopy and atomic force microscopy. SERS studies conducted using bio Ag Nps on different water insoluble analytes, such as CL-20 and TNT, lead to SERS signals at concentration levels of 400 pM. The experimental findings have been corroborated with density functional computational results, electrostatic surface potential calculations, Fukui functions and potential measurements.

Metallic Nanoparticles Arranged in a Helical Geometry: Route Towards Strong and Broadband Chiro-optical Response

Recent advances in nanotechnology have paved ways to various techniques for designing and fabricating novel nanostructures incorporating noble metal nanoparticles, for a wide range of applications. The interaction of light with metal nanoparticles (NPs) can generate strongly localized electromagnetic fields (Localized Surface Plasmon Resonance, LSPR) at certain wavelengths of the incident beam. In assemblies or structures where the nanoparticles are placed in close proximity, the plasmons of individual metallic NPs can be strongly coupled to each other via Coulomb interactions. By arranging the metallic NPs in a chiral (e.g. helical) geometry, it is possible to induce collective excitations, which lead to differential optical response of the structures to right-and left circularly polarized light (e.g. Circular Dichroism - CD). Earlier reports in this field include novel techniques of synthesizing metallic nanoparticles on biological helical templates made from DNA, proteins etc. In the present work, we have developed new ways of fabricating chiral complexes made of metallic NPs, which demonstrate a very strong chiro-optical response in the visible region of the electromagnetic spectrum. Using DDA (Discrete Dipole Approximation) simulations, we theoretically studied the conditions responsible for large and broadband chiro-optical response. This system may be used for various applications, for example those related to polarization control of visible light, sensing of proteins and other chiral bio-molecules, and many more.

In-situ Stabilization of Tin Nanoparticles in Porous Carbon Matrix derived from Metal Organic Framework: High Capacity and High Rate Capability Anodes for Lithium-ion Batteries

It is a formidable challenge to arrange tin nanoparticles in a porous matrix for the achievement of high specific capacity and current rate capability anode for lithium-ion batteries. This article discusses a simple and novel synthesis of arranging tin nanoparticles with carbon in a porous configuration for application as anode in lithium-ion batteries. Direct carbonization of synthesized three-dimensional Sn-based MOF: K2Sn2(1,4-bdc)(3)](H2O) (1) (bdc = benzenedicarboxylate) resulted in stabilization of tin nanoparticles in a porous carbon matrix (abbreviated as Sn@C). Sn@C exhibited remarkably high electrochemical lithium stability (tested over 100 charge and discharge cycles) and high specific capacities over a wide range of operating currents (0.2-5 Ag-1). The novel synthesis strategy to obtain Sn@C from a single precursor as discussed herein provides an optimal combination of particle size and dispersion for buffering severe volume changes due to Li-Sn alloying reaction and provides fast pathways for lithium and electron transport.

Antimicrobial and conducting polymer substrate derived from hybrid structures of silver nanoparticles and multiwall carbon nanotubes

Hybrid nanocomposites of polycaprolactone (PCL) with multiwall carbon nanotubes (MWNTs) and silver nanoparticles (nAg) were prepared by melt mixing. Synergetic effect of the two nanofillers (MWNT and nAg) in PCL matrix was evaluated for dielectric and antibacterial properties. Dielectric results showed that the addition of nAg as filler in PCL matrix (PCL/nAg) had no effect on conductivity, whereas addition of MWNT in PCL matrix (PCL/MWNT) caused a sharp increase in conductivity of PCL. Interestingly, the hybrid nanocomposite (PCL/MWNT/nAg) incorporating MWNT and nAg also exhibited high electrical conductivity. The hybrid composite was found to have antibacterial property similar to that of PCL/nAg composite for lower loading of nAg. This study demonstrates that the synergetic interaction of the nanofillers in the hybrid nanocomposite improves both electrical conductivity and antibacterial properties of PCL.

Synthesis and Mechanism of Composition and Size Dependent Morphology Selection in Nanoparticles of Ag-Cu Alloys Processed by Laser Ablation Under Liquid Medium

We have synthesized Ag-Cu alloy nanoparticles of four different compositions by using the laser ablation technique with the target under aqueous medium. Following this, we report a morphological transition in the nanoparticles from a normal two-phase microstructure to a structure with random segregation and finally a core shell structure at small sizes as a function of Cu concentration. To illustrate the composition dependence of morphology, we report observations carried out on nanoparticles of two different sizes: similar to 5 and similar to 20 nm. The results could be rationalized through the thermodynamic modeling of free energy of phase mixing and wettability of the alloying phases.

Digestive ripening facilitated atomic diffusion at nanosize regime: Case of AuIn2 and Ag3In intermetallic nanoparticles

Monodisperse colloidal gold-indium (AuIn2) intermetallic nanoparticles have been synthesized from Au and In colloids using the digestive ripening process. Formation of the intermetallic proceeds via digestive ripening facilitated atomic diffusion of Au and In atoms from the Au and In nanoparticles followed simultaneously by their growth in the solution. Optimization of the reaction temperature was found to be crucial for the formation of AuIn2 intermetallic from gold and indium nanoparticles. Transmission electron microscopy revealed the presence of nearly monodisperse nanoparticles of Au and AuIn2 with particle size distribution of 3.7 +/- 1.0 nm and 5.0 +/- 1.6 nm, respectively. UV-visible spectral studies brought out the absence of SPR band in pure AuIn2 intermetallic nanoparticles. Optical study and electron microscopy, in combination with powder X-ray diffraction established phase pure AuIn2 intermetallic nanoparticles unambiguously. The potential of such an unprecedented approach has been further exploited in the synthesis of Ag3In intermetallic nanoparticles with the dimension of less than 10 nm. (C) 2014 Elsevier B.V. All rights reserved.

A radial differential mobility analyzer for the size-classification of gas-phase synthesized nanoparticles at low pressures

Differential mobility analyzers (DMAs) are commonly used to generate monodisperse nanoparticle aerosols. Commercial DMAs operate at quasi-atmospheric pressures and are therefore not designed to be vacuum-tight. In certain particle synthesis methods, the use of a vacuum-compatible DMA is a requirement as a process step for producing high-purity metallic particles. A vacuum-tight radial DMA (RDMA) has been developed and tested at low pressures. Its performance has been evaluated by using a commercial NANO-DMA as the reference. The performance of this low-pressure RDMA (LP-RDMA) in terms of the width of its transfer function is found to be comparable with that of other NANO-DMAs at atmospheric pressure and is almost independent of the pressure down to 30 mbar. It is shown that LP-RDMA can be used for the classification of nanometer-sized particles (5-20 nm) under low pressure condition (30 mbar) and has been successfully applied to nanoparticles produced by ablating FeNi at low pressures.

Haloarchaeal gas vesicle nanoparticles displaying Salmonella SopB antigen reduce bacterial burden when administered with live attenuated bacteria

Innovative vaccines against typhoid and other Salmonella diseases that are safe, effective, and inexpensive are urgently needed. In order to address this need, buoyant, self-adjuvating gas vesicle nanoparticles (GVNPs) from the halophilic archaeon Halobacterium sp. NRC-1 were bioengineered to display the highly conserved Salmonella enterica antigen SopB, a secreted inosine phosphate effector protein injected by pathogenic bacteria during infection into the host cell. Two highly conserved sopB gene segments near the 3'-coding region, named sopB4 and B5, were each fused to the gvpC gene, and resulting GVNPs were purified by centrifugally accelerated flotation. Display of SopB4 and B5 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 recombinant GVNPs to BALB/c mice which had been immunized with S. enterica serovar Typhimurium 14028 Delta pmrG-HM-D (DV-STM-07), a live attenuated vaccine strain. Proinflammatory cytokines IFN-gamma, IL-2, and IL-9 were significantly induced in mice boosted with SopB5-GVNPs, consistent with a robust Th1 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 SopB5-GVNPs, indicating that the C-terminal portions of SopB displayed on GVNPs elicit a protective response to Salmonella infection in mice. SopB antigen-GVNPs were found to be stable at elevated temperatures for extended periods without refrigeration in Halobacterium cells. The results all together show that bioengineered GVNPs are likely to represent a valuable platform for the development of improved vaccines against Salmonella diseases. (C) 2014 Elsevier Ltd. All rights reserved.

Size Modulation of Colloidal Au Nanoparticles via Digestive Ripening in Conjunction with a Solvated Metal Atom Dispersion Method: An Insight Into Mechanism

Digestive ripening, a postsynthetic treatment of colloidal nanoparticles, is a versatile method to produce monodisperse nanoparticles and to prepare various bimetallic nanostructures. The mechanism of this process is largely unknown. Herein, we present a systematic study conducted using Au nanoparticles prepared by a solvated metal atom dispersion method to probe the mechanistic aspects of digestive ripening. In our study, experimental conditions such as concentration of capping agent, reaction time, and temperature, were found to influence the course of the digestive ripening process. Here it is shown that, during digestive ripening under reflux, nanoparticles within an optimum size window are conserved, and surface etching facilitated mass transfer resulted in monodisperse nanoparticles. Overall, digestive ripening can be considered as a kinetically controlled thermodynamic process.

Qualitative toxicity assessment of silver nanoparticles on the fresh water bacterial isolates and consortium at low level of exposure concentration

Silver nanoparticles (AgNPs) pose a high risk of exposure to the natural environment owing to their extensive usage in various consumer products. In the present study we attempted to understand the harmful effect of AgNPs at environmentally relevant low concentration levels (<= 1 ppm) towards two different freshwater bacterial isolates and their consortium. The standard plate count assay suggested that the AgNPs were toxic towards the fresh water bacterial isolates as well as the consortium, though toxicity was significantly reduced for the cells in the consortium. The oxidative stress assessment and membrane permeability studies corroborated with the toxicity data. The detailed electron microscopic studies suggested the cell degrading potential of the AgNPs, and the FT-IR studies confirmed the involvement of the surface groups in the toxic effects. No significant ion leaching from the AgNPs was observed at the applied concentration levels signifying the dominant role of the particle size, and size distribution in bacterial toxicity. The reduced toxicity for the cells in the consortium than the individual isolates has major significance in further studies on the ecotoxicity of the AgNPs. (C) 2014 Elsevier Inc. All rights reserved.

Ag nanoparticles-anchored reduced graphene oxide catalyst for oxygen electrode reaction in aqueous electrolytes and also a non-aqueous electrolyte for Li-O-2 cells

Silver nanoparticles-anchored reduced graphene oxide (Ag-RGO) is prepared by simultaneous reduction of graphene oxide and Ag+ ions in an aqueous medium by ethylene glycol as the reducing agent. Ag particles of average size of 4.7 nm were uniformly distributed on the RGO sheets. Oxygen reduction reaction (ORR) is studied on Ag-RGO catalyst in both aqueous and non-aqueous electrolytes by using cyclic voltammetry and rotating disk electrode techniques. As the interest in non-aqueous electrolyte is to study the catalytic performance of Ag-RGO for rechargeable Li-O-2 cells, these cells are assembled and characterized. Li-O-2 cells with Ag-RGO as the oxygen electrode catalyst are subjected to charge-discharge cycling at several current densities. A discharge capacity of 11 950 mA h g(-1) (11.29 mA h cm(-2)) is obtained initially at low current density. Although there is a decrease in the capacity on repeated discharge-charge cycling initially, a stable capacity is observed for about 30 cycles. The results indicate that Ag-RGO is a suitable catalyst for rechargeable Li-O-2 cells.

An unusual demixing behavior in PS-PVME blends in the presence of nanoparticles

The effect of silver nanoparticles (sNP) on the demixing and the evolution of morphology in off-critical blends of 90/10 and 10/90 (wt/wt) PS/PVME polystyrene/poly(vinyl methyl ether)] was probed here using shear rheology and optical microscopy. The faster component (PVME) has a higher molecular weight (80 kDa) than the slower component (PS, 35 kDa), which makes this system quite interesting to study with respect to the evolving morphology, as the blends transit through the binodal and the spinodal envelopes. An unusual demixing behavior was observed in both PVME rich and PS rich blends. Temperature modulated differential scanning calorimetry measurements showed that the T-g value for the blends with sNP was slightly lower than that of the neat blends. A decreased volume of cooperativity at T-g suggests confined segmental dynamics in the presence of sNP. Although, the addition of sNP had no influence on the thermodynamic demixing temperature, it significantly altered the elasticity of the minor component during the transition of the blend from the homogeneous to the heterogeneous state. This is manifested from energetically driven localization of the sNP in the PVME phase during demixing. As a direct consequence of this, the formation of the microstructures upon demixing was observed to be delayed in the presence of sNP. Interestingly, in the intermediate quench depth, the higher viscoelastic phase evolved as an interconnected network, which subsequently coarsened into discrete droplets in the late stages for the 90/10 PS/PVME blends. Similar observations were made for 10/90 PS/PVME blends where threads of PVME appeared at deeper quench depths in the presence of sNP. The interconnected network formation of the minor phase (here PVME), which is also the faster component in the blend, was different from the usual demixing behavior.

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.

STM verification of the reduction of the Young's modulus of CdS nanoparticles at smaller sizes

We demonstrate the first STM evaluation of the Young's modulus (E) of nanoparticles (NPs) of different sizes. The sample deformation induced by tip-sample interaction has been determined using current-distance (I-Z) spectroscopy. As a result of tip-sample interaction, and the induced surface deformations, the I-z curves deviates from pure exponential dependence. Normally, in order to analyze the deformation quantitatively, the tip radius must be known. We show, that this necessity is eliminated by measuring the deformation on a substrate with a known Young's modulus (Au(111)) and estimating the tip radius, and afterwards, using the same tip (with a known radius) to measure the (unknown) Young's modulus of another sample (nanoparticles of CdS). The Young's modulus values found for 3 NP's samples of average diameters of 3.7, 6 and 7.5 nm, were E similar to 73%, 78% and 88% of the bulk value, respectively. These results are in a good agreement with the theoretically predicted reduction of the Young's modulus due to the changes in hydrostatic stresses which resulted from surface tension in nanoparticles with different sizes. Our calculation using third order elastic constants gives a reduction of E which scales linearly with 1/r (r is the NP's radius). This demonstrates the applicability of scanning tunneling spectroscopy for local mechanical characterization of nanoobjects. The method does not include a direct measurement of the tip-sample force but is rather based on the study of the relative elastic response. (C) 2014 Elsevier B.V. All rights reserved.