Size dependence and dispersion behavior of the first hyperpolarizability of copper nanoparticles

We have probed the size dependency of the first hyperpolarizability (b) of copper nanoparticles by hyper-Rayleigh scattering (HRS). Our results indicate that second harmonic generation (SHG) originates predominantly at the surface of the nanoparticles as long as the size (d) remains small compared to the wavelength (k). However, volume contribution to the SH response due to the retardation effect becomes important when particle size grows beyond the `small particle limit'. There is a significant dispersion in the b values of copper nanoparticles owing tothe presence of the strong surface plasmon resonance (SPR) band.

Hybrid Materials Combining Photoactive 2,3-Didecyloxy Anthracene Physical Gels and Gold Nanoparticles

Organic/inorganic hybrid gels have been developed in order to control the three-dimensional structure of photoactive nanofibers and metallic nanoparticles (NPs). These materials are prepared by simultaneous self-assembly of the 2,3-didecyloxyanthracene (DDOA) gelator and of thiol-capped gold nanoparticles (AuNPs). TEM and fluorescence measurements show that alkane-thiol capped AuNPs are homogeneously dispersed and tightly attached to the thermoreversible fibrillar network formed by the organogelator in n-butanol or n-decanol. Rheology and thermal stability measurements reveal moreover that the mechanical and thermal stabilities of the DDOA organogels are not significantly altered and that they remain strong, viscoelastic materials. The hybrid materials display a variable absorbance in the visible range because of the AuNPs, whereas the strong luminescence of the DDOA nanofibers is efficiently quenched by micromolar amounts of AuNPs. Besides, we obtained hybrid aerogels using supercritical CO2. These arc very low-density porous materials showing fibrillar networks oil which fluorinated gold NPs arc dispersed. These hybrid materials are of high interest because of their tunable optical properties and are under investigation for efficient light scattering.

Electron spin resonance studies of d5 ions (Fe3+ and Mn2+) in lead oxide-lead halide glasses

Electron spin resonance (ESR) of d5 ions (Fe3+ and Mn2+) has been investigated in PbO---PbF2 and PbO---PbCl2 glasses in wide ranges of composition. ESR spectra of d5 ions in these glasses exhibit significant differences which we have attributed to at least three important causes: (i) The ionic potentials of Fe3+ and Mn2+ are different. Hence Fe3+ ions tend to acquire their own environment while Mn2+ ions take up substitutional (Pb2+ ion) positions. (ii) The sizes and nephelauxetic behaviours of O2- and F- ions are similar. Thus even when there is a mixed anionic coordination, the environment of Mn2+ ions is highly symmetrical in oxyfluoride glasses. The Mn2+ spectra in oxychloride glasses are considerably different. (iii) Increase in halide ion concentration increases the ionicity of lead-ligand bonding and favours a more symmetrical environment around dopant ions in halide-rich glasses. The features in ESR spectra have been interpreted in the light of known behaviour of d5 ions in glasses and also in the context of known structural features of PbO---PbX2 glasses. Dopant ions appear to cluster at high concentrations although isolated low-symmetry sites are still observed. Effects of crystallization and annealing upon ESR spectra have also been investigated.

Adsorption and release of biocides with mesoporous silica nanoparticles

In this proof-of-concept study, an agricultural biocide (imidacloprid) was effectively loaded into the mesoporous silica nanoparticles (MSNs) with different pore sizes, morphologies and mesoporous structures for termite control. This resulted in nanoparticles with a large surface area, tunable pore diameter and small particle size, which are ideal carriers for adsorption and controlled release of imidacloprid. The effect of pore size, surface area and mesoporous structure on uptake and release of imidacloprid was systematically studied. It was found that the adsorption amount and release profile of imidacloprid were dependent on the type of mesoporous structure and surface area of particles. Specifically, MCM-48 type mesoporous silica nanoparticles with a three dimensional (3D) open network structure and high surface area displayed the highest adsorption capacity compared to other types of silica nanoparticles. Release of imidacloprid from these nanoparticles was found to be controlled over 48 hours. Finally, in vivo laboratory testing on termite control proved the efficacy of these nanoparticles as delivery carriers for biopesticides. We believe that the present study will contribute to the design of more effective controlled and targeted delivery for other biomolecules.

In vivo delivery of bovine viral diahorrea virus, E2 protein using hollow mesoporous silica nanoparticles

Our work focuses on the application of mesoporous silica nanoparticles as a combined delivery vehicle and adjuvant for vaccine applications. Here we present results using the viral protein, E2, from bovine viral diarrhoea virus (BVDV). BVDV infection occurs in the target species of cattle and sheep herds worldwide and is therefore of economic importance. E2 is a major immunogenic determinant of BVDV and is an ideal candidate for the development of a subunit based nanovaccine using mesoporous silica nanoparticles. Hollow type mesoporous silica nanoparticles with surface amino functionalisation (termed HMSA) were characterised and assessed for adsorption and desorption of E2. A codon-optimised version of the E2 protein (termed Opti-E2) was produced in Escherichia coli. HMSA (120 nm) had an adsorption capacity of 80 [small mu ]g Opti-E2 per mg HMSA and once bound E2 did not dissociate from the HMSA. Immunisation studies in mice with a 20 [small mu ]g dose of E2 adsorbed to 250 [small mu ]g HMSA was compared to immunisation with Opti-E2 (50 [small mu ]g) together with the traditional adjuvant Quillaja saponaria Molina tree saponins (QuilA, 10 [small mu ]g). The humoral responses with the Opti-E2/HMSA nanovaccine although slightly lower than those obtained for the Opti-E2 + QuilA group demonstrated that HMSA particles are an effective adjuvant that stimulated E2-specific antibody responses. Importantly the cell-mediated immune responses were consistently high in all mice immunised with Opti-E2/HMSA nanovaccine formulation. Therefore we have shown the Opti-E2/HMSA nanoformulation acts as an excellent adjuvant that gives both T-helper 1 and T-helper 2 mediated responses in a small animal model. This study has provided proof-of-concept towards the development of an E2 subunit nanoparticle based vaccine.

Stable Dispersions of Metal Oxide Nanowires and Nanoparticles in Water, Dimethylformamide and Toluene

In view of the important need to generate well-dispersed inorganic nanostructures in various solvents, we have explored the dispersion of nanostructures of metal oxides such as TiO2, Fe3O4 and ZnO in solvents of differing polarity in the presence of several surfactants. The solvents used are water, dimethylformamide (DMF) and toluene. The surfactant-solvent combinations yielding the best dispersions are reported alongwith some of the characteristics of the nanostructures in the dispersions. The surfactants which dispersed TiO2 nanowires in water were polyethylene oxide (PEO), Triton X-100 (TX-100), polyvinyl alcohol (PVA) and sodium bis(2-ethylhexyl) sulphosuccinate (AOT). TiO2 nanoparticles could also be dispersed with AOT and PEO in water, and with AOT in toluene. In DMF, PVA, PEO and TX-100 were found to be effective, while in toluene, only AOT gave good dispersions. Fe3O4 nanoparticles were held for long periods of time in water by PEO, AOT, PVA and polyethylene glycol (PEG), and by AOT in toluene. In the case of ZnO nanowires, the best surfactant-solvent combinations were found to be, PEO, sodium dodecyl sulphate (SIDS) and AOT in water and AOT, PEG, PVA, PEO and TX-100 in DMF In toluene, stable dispersions of ZnO nanowires were obtained with PEO. We have also been able to disperse oxide nanostructures in non-polar solvents by employing a hydrophobic silane coating on the surface.

Atomic Layer Deposition of Electroluminescent ZnS, SrS, and BaS Thin Films

The light emitted by flat panel displays (FPD) can be generated in many different ways, such as for example alternating current thin film electroluminescence (ACTFEL), liquid crystal display (LCD), light emitting diode (LED), or plasma display panel (PDP) technologies. In this work, the focus was on ACTFEL devices and the goal was to develop new thin film processes for light emitting materials in ACTFEL devices. The films were deposited with the atomic layer deposition (ALD) method, which has been utilized in the manufacturing of ACTFEL displays since the mid-1980s. The ALD method is based on surface-controlled self-terminated reactions and a maximum of one layer of the desired material can be prepared during one deposition cycle. Therefore, the film thickness can be controlled simply by adjusting the number of deposition cycles. In addition, both large areas and deep trench structures can be covered uniformly. During this work, new ALD processes were developed for the following thin film materials: BaS, CuxS, MnS, PbS, SrS, SrSe, SrTe, SrS1-xSex, ZnS, and ZnS1-xSex. In addition, several ACTFEL devices were prepared where the light emitting material was BaS, SrS, SrS1-xSex, ZnS, or ZnS1-xSex thin film that was doped with Ce, Cu, Eu, Mn, or Pb. The sulfoselenide films were made by substituting the elemental selenium for sulfur on the substrate surface during film deposition. In this way, it was possible to replace a maximum of 90% of the sulfur with selenium, and the XRD analyses indicated that the films were solid solutions. The polycrystalline BaS, SrS, and ZnS thin films were deposited at 180-400, 120-460, and 280-500 °C, respectively, and the processes had a wide temperature range where the growth rate of the films was independent of the deposition temperature. The electroluminescence studies showed that the doped sulfoselenide films resulted in low emission intensity. However, the emission intensities and emission colors of the doped SrS, BaS, and ZnS films were comparable with those found in earlier studies. It was also shown that the electro-optical properties of the different ZnS:Mn devices were different as a consequence of different ZnS:Mn processes. Finally, it was concluded that because the higher deposition temperature seemed to result in a higher emission intensity, the thermal stability of the reactants has a significant role when the light emitting materials of ACTFEL devices are deposited with the ALD method.

Polymer Protected Gold Nanoparticles

Polymer protected gold nanoparticles have successfully been synthesized by both "grafting-from" and "grafting-to" techniques. The synthesis methods of the gold particles were systematically studied. Two chemically different homopolymers were used to protect gold particles: thermo-responsive poly(N-isopropylacrylamide), PNIPAM, and polystyrene, PS. Both polymers were synthesized by using a controlled/living radical polymerization process, reversible addition-fragmentation chain transfer (RAFT) polymerization, to obtain monodisperse polymers of various molar masses and carrying dithiobenzoate end groups. Hence, particles protected either with PNIPAM, PNIPAM-AuNPs, or with a mixture of two polymers, PNIPAM/PS-AuNPs (i.e., amphiphilic gold nanoparticles), were prepared. The particles contain monodisperse polymer shells, though the cores are somewhat polydisperse. Aqueous PNIPAM-AuNPs prepared using a "grafting-from" technique, show thermo-responsive properties derived from the tethered PNIPAM chains. For PNIPAM-AuNPs prepared using a "grafting-to" technique, two-phase transitions of PNIPAM were observed in the microcalorimetric studies of the aqueous solutions. The first transition with a sharp and narrow endothermic peak occurs at lower temperature, and the second one with a broader peak at higher temperature. In the first transition PNIPAM segments show much higher cooperativity than in the second one. The observations are tentatively rationalized by assuming that the PNIPAM brush can be subdivided into two zones, an inner and an outer one. In the inner zone, the PNIPAM segments are close to the gold surface, densely packed, less hydrated, and undergo the first transition. In the outer zone, on the other hand, the PNIPAM segments are looser and more hydrated, adopt a restricted random coil conformation, and show a phase transition, which is dependent on both particle concentration and the chemical nature of the end groups of the PNIPAM chains. Monolayers of the amphiphilic gold nanoparticles at the air-water interface show several characteristic regions upon compression in a Langmuir trough at room temperature. These can be attributed to the polymer conformational transitions from a pancake to a brush. Also, the compression isotherms show temperature dependence due to the thermo-responsive properties of the tethered PNIPAM chains. The films were successfully deposited on substrates by Langmuir-Blodgett technique. The sessile drop contact angle measurements conducted on both sides of the monolayer deposited at room temperature reveal two slightly different contact angles, that may indicate phase separation between the tethered PNIPAM and PS chains on the gold core. The optical properties of amphiphilic gold nanoparticles were studied both in situ at the air-water interface and on the deposited films. The in situ SPR band of the monolayer shows a blue shift with compression, while a red shift with the deposition cycle occurs in the deposited films. The blue shift is compression-induced and closely related to the conformational change of the tethered PNIPAM chains, which may cause a decrease in the polarity of the local environment of the gold cores. The red shift in the deposited films is due to a weak interparticle coupling between adjacent particles. Temperature effects on the SPR band in both cases were also investigated. In the in situ case, at a constant surface pressure, an increase in temperature leads to a red shift in the SPR, likely due to the shrinking of the tethered PNIPAM chains, as well as to a slight decrease of the distance between the adjacent particles resulting in an increase in the interparticle coupling. However, in the case of the deposited films, the SPR band red-shifts with the deposition cycles more at a high temperature than at a low temperature. This is because the compressibility of the polymer coated gold nanoparticles at a high temperature leads to a smaller interparticle distance, resulting in an increase of the interparticle coupling in the deposited multilayers.

Role of Capping Ligands on the Nanoparticles in the Modulation of Properties of a Hybrid Matrix of Nanoparticles in a 2D Film and in a Supramolecular Organogel

We incorporate various gold nanoparticles (AuNPs) capped with different ligands in two-dimensional films and three-dimensional aggregates derived from N-stearoyl-L-alanine and N-lauroyl-L-alanine, respectively. The assemblies of N-stearoyl-L-alanine afforded stable films at the air-water interface. More compact assemblies were formed upon incorporation of AuNPs in the air-water interface of N-stearoyl-L-alanine. We then examined the effects of incorporation of various AuNPs functionalized with different capping ligands in three-dimensional assemblies of N-lauroyl-L-alanine, a compound that formed a gel in hydrocarbons. The profound influence of nanoparticle incorporation into physical gels was evident from evaluation of various microscopic and bulk properties. The interaction of AuNPs with the gelator assembly was found to depend critically on the capping ligands protecting the Au surface of the gold nanoparticles. Transmission electron microscopy (TEM) showed a long-range directional assembly of certain AuNPs along the gel fibers. Scanning electron microscopy (SEM) images of the freeze-dried gels and nanocomposites indicate that the morphological transformation in the composite microstructures depends significantly on the capping agent of the nanoparticles. Differential scanning calorimetry (DSC) showed that gel formation from sol occurred at a lower temperature upon incorporation of AuNPs having capping ligands that were able to align and noncovalently interact with the gel fibers. Rheological studies indicate that the gel-nanoparticle composites exhibit significantly greater viscoelasticity compared to the native gel alone when the capping ligands are able to interact through interdigitation into the gelator assembly. Thus, it was possible to define a clear relationship between the materials and the molecular-level properties by means of manipulation of the information inscribed on the NP surface.

Synthesis of wurtzite-phase ZnS nanocrystal and its optical properties

The wurtzite phase of ZnS nanocrystal has been prepared by annealing in 200-600 degrees C temperature range, its cubic phase of 2-3 nm size. prepared through soft chemical method. Results of isochronal experiments of 2 h at different temperatures indicate that visible transformation to wurtzite from cubic ZnS appears at a temperature of 400 degrees C, which is about three times smaller than that of bulk ZnS phase transition temperature. The phases, nanostructures, and optical absorption characteristics are obtained through X-ray diffraction. transmission electron microscopy, and UV-visible absorption spectroscopy. A stable and green photoluminescence emission peaked at 518 nm is observed from the 600 degrees C annealed samples, under ultraviolet light excitation.

Occupational release of engineered nanoparticles: A review

Characterising the release of different types of Engineered Nanoparticles (ENPs) from various processes is of critical importance for the assessment of human exposure, as well as understanding the possible health effects of these particles. Therefore, the main aim of this chapter is to present a comprehensive review of studies which report on the release of airborne ENPs in different nanotechnology workplaces. The chapter will cover topics of relevance to the occupational characterisation of ENP emissions, ranging from the identification of different particle release sources and scenarios, to measurement methods and working towards a more uniform approach to characterisation. Furthermore, a brief review of ENP exposure control strategies, together with the application of mathematical modelling as an effective tool for the characterisation of emissions at nanotechnology workplaces is included.

A green protocol for room temperature synthesis of silver nanoparticles in seconds

We describe here a rapid, energy-efficient, green and economically scalable room temperature protocol for the synthesis of silver nanoparticles. Tannic acid, a polyphenolic compound derived from plant extracts is used as the reducing agent. Silver nanoparticles of mean size ranging from 3.3 to 22.1 nm were synthesized at room temperature by the addition of silver nitrate to tannic acid solution maintained at an alkaline pH. The mean size was tuned by varying the molar ratio of tannic acid to silver nitrate. We also present proof of concept results demonstrating its suitability for room temperature continuous flow processing.

Phthalocyanine macrocycle as stabilizer for gold and silver nanoparticles

A one-step process was used for the preparation of gold and silver nanoparticles stabilized by an aminophthalocyanine macrocycle. The resultant nanoparticles were characterized by absorption spectra, infrared spectroscopy, scanning electron microscopy and transmission electron microscopy. The nanoparticles were found to possess relatively narrow size distribution. The gold nanoparticles have an average diameter of similar to 2 nm, while silver particles have 4-5 nm. Preliminary studies on fluorescence and surface enhanced Raman spectroscopy were carried out using these nanoparticles. Fluorescence studies indicate that gold nanoparticles do not quench the fluorescence, while silver nanoparticles do. The stabilized nanoparticles showed enhancement of the Raman signals, thus revealing that they are good substrates for surface enhanced Raman scattering studies.

Fabrication and Phase Transformation in Crystalline Nanoparticles of PbZrO3 Derived By Sol-Gel

In this research fabrication of crystalline PbZrO3 (PZ) nanoparticles and their phase transformation behavior is investigated. A novel sol-gel method was used for the synthesis of air-stable and precipitate-free diol-based sol of PZ, which was dried at 150 degrees C and then calcined at 300-700 degrees C for 1 h. The morphology, crystallinity and phase formation of as synthesized nanoparticles were studied by the selected-area electron diffraction (SAED), X-ray diffraction (XRD), thermal gravimetric analysis/differential scanning calorimetry (TGA-DSC), and high resolution transmission electron microscope (HRTEM). The XRD, SAED, and TGA-DSC analyses confirmed the tetragonal lead rich zirconia phase (t-Z phase) and monoclinic zirconia phase (m-Z phase) as the intermediate phases during the calcinations process followed by crystallization of single orthorhombic PZ phase at about 700 degrees C. The average PZ particle size was observed about 20 nm as confirmed by TEM study. Energy-dispersive X-ray spectroscopy (EDX) analysis demonstrated that stoichiometric PbZrO3 was formed.