A novel method for the synthesis of monodisperse gold-coated silica nanoparticles

Monodisperse silica nanoparticles were synthesised by the well-known Stober protocol, then dispersed in acetonitrile (ACN) and subsequently added to a bisacetonitrile gold(I) coordination complex ([Au(MeCN)2]?) in ACN. The silica hydroxyl groups were deprotonated in the presence of ACN, generating a formal negative charge on the siloxy groups. This allowed the [Au(MeCN)2]? complex to undergo ligand exchange with the silica nanoparticles and form a surface coordination complex with reduction to metallic gold (Au0) proceeding by an inner sphere mechanism. The residual [Au(MeCN)2]? complex was allowed to react with water, disproportionating into Au0 and Au(III), respectively, with the Au0 adding to the reduced gold already bound on the silica surface. The so-formed metallic gold seed surface was found to be suitable for the conventional reduction of Au(III) to Au0 by ascorbic acid (ASC). This process generated a thin and uniform gold coating on the silica nanoparticles. The silica NPs batches synthesised were in a size range from 45 to 460 nm. Of these silica NP batches, the size range from 400 to 480 nm were used for the gold-coating experiments.

Gold coating of silica and zinc oxide nanoparticles by the surface reduction of gold(I) chloride

The possibility of a surface inner sphere electron transfer mechanism leading to the coating of gold via the surface reduction of gold(I) chloride on metal and semi-metal oxide nanoparticles was investigated. Silica and zinc oxide nanoparticles are known to have very different surface chemistry, potentially leading to a new class of gold coated nanoparticles. Monodisperse silica nanoparticles were synthesised by the well known Stöber protocol in conjunction with sonication. The nanoparticle size was regulated solely by varying the amount of ammonia solution added. The presence of surface hydroxyl groups was investigated by liquid proton NMR. The resultant nanoparticle size was directly measured by the use of TEM. The synthesised silica nanoparticles were dispersed in acetonitrile (MeCN) and added to a bis acetonitrile gold(I) co-ordination complex [Au(MeCN)2]+ in MeCN. The silica hydroxyl groups were deprotonated in the presence of MeCN generating a formal negative charge on the siloxy groups. This allowed the [Au(MeCN)2]+ complex to undergo ligand exchange with the silica nanoparticles, which formed a surface co-ordination complex with reduction to gold(0), that proceeded by a surface inner sphere electron transfer mechanism. The residual [Au(MeCN)2]+ complex was allowed to react with water, disproportionating into gold(0) and gold(III) respectively, with gold(0) being added to the reduced gold already bound on the silica surface. The so-formed metallic gold seed surface was found to be suitable for the conventional reduction of gold(III) to gold(0) by ascorbic acid. This process generated a thin and uniform gold coating on the silica nanoparticles. This process was modified to include uniformly gold coated composite zinc oxide nanoparticles (Au@ZnO NPs) using surface co-ordination chemistry. AuCl dissolved in acetonitrile (MeCN) supplied chloride ions which were adsorbed onto ZnO NPs. The co-ordinated gold(I) was reduced on the ZnO surface to gold(0) by the inner sphere electron transfer mechanism. Addition of water disproportionated the remaining gold(I) to gold(0) and gold(III). Gold(0) bonded to gold(0) on the NP surface with gold(III) was reduced to gold(0) by ascorbic acid (ASC), which completed the gold coating process. This gold coating process of Au@ZnO NPs was modified to incorporate iodide instead of chloride. ZnO NPs were synthesised by the use of sodium oxide, zinc iodide and potassium iodide in refluxing basic ethanol with iodide controlling the presence of chemisorbed oxygen. These ZnO NPs were treated by the addition of gold(I) chloride dissolved in acetonitrile leaving chloride anions co-ordinated on the ZnO NP surface. This allowed acetonitrile ligands in the added [Au(MeCN)2]+ complex to surface exchange with adsorbed chloride from the dissolved AuCl on the ZnO NP surface. Gold(I) was then reduced by the surface inner sphere electron transfer mechanism. The presence of the reduced gold on the ZnO NPs allowed adsorption of iodide to generate a uniform deposition of gold onto the ZnO NP surface without the use of additional reducing agents or heat.

Coupling of energy from quantum emitters to the plasmonic mode of V groove waveguides: A numerical study

This work is a theoretical investigation into the coupling of a single excited quantum emitter to the plasmon mode of a V groove waveguide. The V groove waveguide consists of a triangular channel milled in gold and the emitter is modeled as a dipole emitter, and could represent a quantum dot, nitrogen vacancy in diamond, or similar. In this work the dependence of coupling efficiency of emitter to plasmon mode is determined for various geometrical parameters of the emitter-waveguide system. Using the finite element method, the effect on coupling efficiency of the emitter position and orientation, groove angle, groove depth, and tip radius, is studied in detail. We demonstrate that all parameters, with the exception of groove depth, have a significant impact on the attainable coupling efficiency. Understanding the effect of various geometrical parameters on the coupling between emitters and the plasmonic mode of the waveguide is essential for the design and optimization of quantum dot–V groove devices.

Experimental and theoretical investigation of ligand effects on the synthesis of ZnO nanoparticles

ZnO nanoparticles with highly controllable particle sizes(less than 10 nm) were synthesized using organic capping ligands in Zn(Ac)2 ethanolic solution. The molecular structure of the ligands was found to have significant influence on the particle size. The multi-functional molecule tris(hydroxymethyl)-aminomethane (THMA) favoured smaller particle distributions compared with ligands possessing long hydrocarbon chains that are more frequently employed. The adsorption of capping ligands on ZnnOn crystal nuclei (where n = 4 or 18 molecular clusters of(0001) ZnO surfaces) was modelled by ab initio methods at the density functional theory (DFT) level. For the molecules examined, chemisorption proceeded via the formation of Zn...O, Zn...N, or Zn...S chemical bonds between the ligands and active Zn2+ sites on ZnO surfaces. The DFT results indicated that THMA binds more strongly to the ZnO surface than other ligands, suggesting that this molecule is very effective at stabilizing ZnO nanoparticle surfaces. This study, therefore, provides new insight into the correlation between the molecular structure of capping ligands and the morphology of metal oxide nanostructures formed in their presence.

Nanoparticles in European cities and associated health impacts

Atmospheric nanoparticles are one of those pollutants currently unregulated through ambient air quality standards. The aim of this chapter is to assess the environmental and health impacts of atmospheric nanoparticles in European environments. The chapter begins with the conventional information on the origin of atmospheric nanoparticles, followed by their physical and chemical characteristics. A brief overview of recently published review articles on this topic is then presented to guide those readers interested in exploring any specific aspect of nanoparticles in greater detail. A further section reports a summary of recently published studies on atmospheric nanoparticles in European cities. This covers a total of about 45 sampling locations in 30 different cities within 15 European countries for quantifying levels of roadside and urban background particle number concentrations (PNCs). Average PNCs at roadside and urban background sites were found to be 3.82±3.25 ×104 cm–3 and 1.63±0.82 ×104 cm–3, respectively, giving a roadside to background PNC ratio of ~2.4. Engineered nanoparticles are one of the key emerging categories of airborne nanoparticles, especially for the indoor environments. Their ambient concentrations may increase in future due to widespread use of nanotechnology integrated products. Evaluation of their sources and probable impacts on air quality and human health are briefly discussed in the following section. Respiratory deposition doses received by the public exposed to roadside PNCs in numerous European locations are then estimated. These were found to be in the 1.17–7.56 1010 h–1 range over the studied roadside European locations. The following section discusses the potential framework for airborne nanoparticle regulations in Europe and, in addition, the existing control measures to limit nanoparticle emissions at source. The chapter finally concludes with a synthesis of the topic areas covered and highlights important areas for further work.

Measurements of particle emissions from nanotechnology processes, with assessment of measuring techniques and workplace controls

The overall aim of this project was to contribute to existing knowledge regarding methods for measuring characteristics of airborne nanoparticles and controlling occupational exposure to airborne nanoparticles, and to gather data on nanoparticle emission and transport in various workplaces. The scope of this study involved investigating the characteristics and behaviour of particles arising from the operation of six nanotechnology processes, subdivided into nine processes for measurement purposes. It did not include the toxicological evaluation of the aerosol and therefore, no direct conclusion was made regarding the health effects of exposure to these particles. Our research included real-time measurement of sub, and supermicrometre particle number and mass concentration, count median diameter, and alveolar deposited surface area using condensation particle counters, an optical particle counter, DustTrak photometer, scanning mobility particle sizer, and nanoparticle surface area monitor, respectively. Off-line particle analysis included scanning and transmission electron microscopy, energy-dispersive x-ray spectrometry, and thermal optical analysis of elemental carbon. Sources of fibrous and non-fibrous particles were included.

Predicting the localized surface plasmon resonances of spherical nanoparticles on substrate : electrostatic eigenmode method

We present experimental results that demonstrate that the wavelength of the fundamental localised surface plasmon resonance for spherical gold nanoparticles on glass can be predicted using a simple, one line analytical formula derived from the electrostatic eigenmode method. This allows the role of the substrate in lifting mode degeneracies to be determined, and the role of local environment refractive indices on the plasmon resonance to be investigated. The effect of adding silica to the casting solution in minimizing nanopaticle agglomeration is also discussed.

Graphene nanocomposites

Graphene, one of the allotropes (diamond, carbon nanotube, and fullerene) of carbon, is a monolayer of honeycomb lattice of carbon atoms discovered in 2004. The Nobel Prize in Physics 2010 was awarded to Andre Geim and Konstantin Novoselov for their ground breaking experiments on the twodimensional graphene [1]. Since its discovery, the research communities have shown a lot of interest in this novel material owing to its unique properties. As shown in Figure 1, the number of publications on graphene has dramatically increased in recent years. It has been confirmed that graphene possesses very peculiar electrical properties such as anomalous quantum hall effect, and high electron mobility at room temperature (250000 cm2/Vs). Graphene is also one of the stiffest (modulus ~1 TPa) and strongest (strength ~100 GPa) materials. In addition, it has exceptional thermal conductivity (5000 Wm-1K-1). Based on these exceptional properties, graphene has found its applications in various fields such as field effect devices, sensors, electrodes, solar cells, energy storage devices and nanocomposites. Only adding 1 volume per cent graphene into polymer (e.g. polystyrene), the nanocomposite has a conductivity of ~0.1 Sm-1 [2], sufficient for many electrical applications. Significant improvement in strength, fracture toughness and fatigue strength has also been achieved in these nanocomposites [3-5]. Therefore, graphene-polymer nanocomposites have demonstrated a great potential to serve as next generation functional or structural materials.

Numerical Modelling of Mechanical Behaviour of Graphene

Graphene, one of the allotropes (diamond, carbon nanotube, and fullerene) of element carbon, is a monolayer of honeycomb lattice of carbon atoms, which was discovered in 2004. The Nobel Prize in Physics 2010 was awarded to Andre Geim and Konstantin Novoselov for their ground breaking work on the two-dimensional (2D) graphene [1]. Since its discovery, the research communities have shown a lot of interest in this novel material owing to its intriguing electrical, mechanical and thermal properties. It has been confirmed that grapheme possesses very peculiar electrical properties such as anomalous quantum hall effect, and high electron mobility at room temperature (250000 cm2/Vs). Graphene also has exceptional mechanical properties. It is one of the stiffest (modulus ~1 TPa) and strongest (strength ~100 GPa) materials. In addition, it has exceptional thermal conductivity (5000 Wm-1K-1). Due to these exceptional properties, graphene has demonstrated its potential for broad applications in micro and nano devices, various sensors, electrodes, solar cells and energy storage devices and nanocomposites. In particular, the excellent mechanical properties of graphene make it more attractive for development next generation nanocomposites and hybrid materials...

Computer experiment – a case study for modelling and simulation of manufacturing systems

Deterministic computer simulation of physical experiments is now a common technique in science and engineering. Often, physical experiments are too time consuming, expensive or impossible to conduct. Complex computer models or codes, rather than physical experiments lead to the study of computer experiments, which are used to investigate many scientific phenomena. A computer experiment consists of a number of runs of the computer code with different input choices. The Design and Analysis of Computer Experiments is a rapidly growing technique in statistical experimental design. This paper aims to discuss some practical issues when designing a computer simulation and/or experiments for manufacturing systems. A case study approach is reviewed and presented.

Sample size considerations and augmentation of computer experiments

Computer Experiments, consisting of a number of runs of a computer model with different inputs, are now common-place in scientific research. Using a simple fire model for illustration some guidelines are given for the size of a computer experiment. A graph is provided relating the error of prediction to the sample size which should be of use when designing computer experiments. Methods for augmenting computer experiments with extra runs are also described and illustrated. The simplest method involves adding one point at a time choosing that point with the maximum prediction variance. Another method that appears to work well is to choose points from a candidate set with maximum determinant of the variance covariance matrix of predictions.

Understanding the enhancement in photoelectrochemical properties of photocatalytically prepared TiO2-reduced graphene oxide composite

Solution-phase photocatalytic reduction of graphene oxide to reduced graphene oxide (RGO) by titanium dioxide (TiO2) nanoparticles produces an RGO-TiO2 composite that possesses enhanced charge transport properties beyond those of pure TiO2 nanoparticle films. These composite films exhibit electron lifetimes up to four times longer than that of intrinsic TiO2 films due to RGO acting as a highly conducting intraparticle charge transport network within the film. The intrinsic UV-active charge generation (photocurrent) of pure TiO2 was enhanced by a factor of 10 by incorporating RGO; we attribute this to both the highly conductive nature of the RGO and to improved charge collection facilitated by the intimate contact between RGO and the TiO2, uniquely afforded by the solution-phase photocatalytic reduction method. Integrating RGO into nanoparticle films using this technique should improve the performance of photovoltaic devices that utilize nanoparticle films, such as dye-sensitized and quantum-dot-sensitized solar cells.

Investigation of ultra trace detection in functionalised-surface enhanced Raman spectroscopy (SERS)

We have developed an explanation for ultra trace detection found when using Au/Ag SERS nanoparticles linked to biochemical affinity tags, e.g. antibodies. The nanoparticle structure is not as usually assumed and the aggregated nanoparticles constitute hot spots that are indispensable for these very low levels of analyte detection, even more so when using a direct detection method.

Excursion guidance criteria to guide control of peak emission and exposure to airborne engineered particles

The overall aim of our research was to characterize airborne particles from selected nanotechnology processes and to utilize the data to develop and test quantitative particle concentration-based criteria that can be used to trigger an assessment of particle emission controls. We investigated particle number concentration (PNC), particle mass (PM) concentration, count median diameter (CMD), alveolar deposited surface area, elemental composition, and morphology from sampling of aerosols arising from six nanotechnology processes. These included fibrous and non-fibrous particles, including carbon nanotubes (CNTs). We adopted standard occupational hygiene principles in relation to controlling peak emission and exposures, as outlined by both Safe Work Australia, (1) and the American Conference of Governmental Industrial Hygienists (ACGIH®). (2) The results from the study were used to analyses peak and 30-minute averaged particle number and mass concentration values measured during the operation of the nanotechnology processes. Analysis of peak (highest value recorded) and 30-minute averaged particle number and mass concentration values revealed: Peak PNC20–1000 nm emitted from the nanotechnology processes were up to three orders of magnitude greater than the local background particle concentration (LBPC). Peak PNC300–3000 nm was up to an order of magnitude greater, and PM2.5 concentrations up to four orders of magnitude greater. For three of these nanotechnology processes, the 30-minute average particle number and mass concentrations were also significantly different from the LBPC (p-value < 0.001). We propose emission or exposure controls may need to be implemented or modified, or further assessment of the controls be undertaken, if concentrations exceed three times the LBPC, which is also used as the local particle reference value, for more than a total of 30 minutes during a workday, and/or if a single short-term measurement exceeds five times the local particle reference value. The use of these quantitative criteria, which we are terming the universal excursion guidance criteria, will account for the typical variation in LBPC and inaccuracy of instruments, while precautionary enough to highlight peaks in particle concentration likely to be associated with particle emission from the nanotechnology process. Recommendations on when to utilize local excursion guidance criteria are also provided.