Probing the effect of charge transfer enhancement in off resonance mode SERS via conjugation of the probe dye between silver nanoparticles and metal substrates

The charge transfer-mediated surface enhanced Raman scattering (SERS) of crystal violet (CV) molecules that were chemically conjugated between partially polarized silver nanoparticles and optically smooth gold and silver substrates has been studied under off-resonant conditions. Tyrosine molecules were used as a reducing agent to convert silver ions into silver nanoparticles where oxidised tyrosine caps the silver nanoparticle surface with its semiquinone group. This binding through the quinone group facilitates charge transfer and results in partially oxidised silver. This establishes a chemical link between the silver nanoparticles and the CV molecules, where the positively charged central carbon of CV molecules can bind to the terminal carboxylate anion of the oxidised tyrosine molecules. After drop casting Ag nanoparticles bound with CV molecules it was found that the free terminal amine groups tend to bind with the underlying substrates. Significantly, only those CV molecules that were chemically conjugated between the partially polarised silver nanoparticles and the underlying gold or silver substrates were found to show SERS under off-resonant conditions. The importance of partial charge transfer at the nanoparticle/capping agent interface and the resultant conjugation of CV molecules to off resonant SERS effects was confirmed by using gold nanoparticles prepared in a similar manner. In this case the capping agent binds to the nanoparticle through the amine group which does not facilitate charge transfer from the gold nanoparticle and under these conditions SERS enhancement in the sandwich configuration was not observed.

Plasmonic effect of gold nanoparticles in organic solar cells

Light trapping, due to the embedding of metallic nanoparticles, has been shown to be beneficial for a better photoabsorption in organic solar cells. Researchers in plasmonics and in the organic photovoltaics fields are working together to improve the absorption of sunlight and the photon–electron coupling to boost the performance of the devices. Recent advances in the field of plasmonics for organic solar cells focus on the incorporation of gold nanoparticles. This article reviews the different methods to produce and embed gold nanoparticles into organic solar cells. In particular, concentration, size and geometry of gold nanoparticles are key factors that directly influence the light absorption in the devices. It is shown that a careful choice of size, concentration and location of gold nanoparticles in the device result in an enhancement of the power conversion efficiencies when compared to standard organic solar cell devices. Our latest results on gold nanoparticles embedded in on organic solar cell devices are included. We demonstrate that embedded gold nanoparticles, created by depositing and annealing a gold film on transparent electrode, generate a plasmonic effect which can be exploited to increase the power conversion efficiency of a bulk heterojunction solar cell up to 10%.

Perdido ties together Shell digital oilfield technologies

Located in the Gulf of Mexico in nearly 8,000 ft of water, the Perdido project is the deepest spar application to date in the world and Shell’s first fully integrated application of its inhouse digital oilfield technology— called “Smart Field”—in the Western hemisphere. Developed by Shell on behalf of partners BP and Chevron, the spar and the subsea equipment connected to it will eventually capture about an order of magnitude more data than is collected from any other Shelldesigned and -managed development operating in the Gulf of Mexico. This article describes Shell’s digital oilfield design philosophy, briefly explains the five design elements that underpin “smartness” in Shell’s North and South American operations and sheds light on the process by which a highly customized digital oilfield development and management plan was put together for Perdido. Although Perdido is the first instance in North and South America in which these design elements and processes were applied in an integrated way, all of Shell’s future new developments in the Western hemisphere are expected to follow the same overarching design principles. Accordingly, this article uses Perdido as a real-world example to outline the high-level details of Shell’s digital oilfield design philosophy and processes.

Photocatalysis on supported gold and silver nanoparticles under ultraviolet and visible light irradiation

Studies of the optical properties and catalytic capabilities of noble metal nanoparticles (NPs), such as gold (Au) and silver (Ag), have formed the basis for the very recent fast expansion of the field of green photocatalysis: photocatalysis utilizing visible and ultraviolet light, a major part of the solar spectrum. The reason for this growth is the recognition that the localised surface plasmon resonance (LSPR) effect of Au NPs and Ag NPs can couple the light flux to the conduction electrons of metal NPs, and the excited electrons and enhanced electric fields in close proximity to the NPs can contribute to converting the solar energy to chemical energy by photon-driven photocatalytic reactions. Previously the LSPR effect of noble metal NPs was utilized almost exclusively to improve the performance of semiconductor photocatalysts (for example, TiO2 and Ag halides), but recently, a conceptual breakthrough was made: studies on light driven reactions catalysed by NPs of Au or Ag on photocatalytically inactive supports (insulating solids with a very wide band gap) have demonstrated that these materials are a class of efficient photocatalysts working by mechanisms distinct from those of semiconducting photocatalysts. There are several reasons for the significant photocatalytic activity of Au and Ag NPs. (1) The conduction electrons of the particles gain the irradiation energy, resulting in high energy electrons at the NP surface which is desirable for activating molecules on the particles for chemical reactions. (2) In such a photocatalysis system, both light harvesting and the catalysing reaction take place on the nanoparticle, and so charge transfer between the NPs and support is not a prerequisite. (3) The density of the conduction electrons at the NP surface is much higher than that at the surface of any semiconductor, and these electrons can drive the reactions on the catalysts. (4) The metal NPs have much better affinity than semiconductors to many reactants, especially organic molecules. Recent progress in photocatalysis using Au and Ag NPs on insulator supports is reviewed. We focus on the mechanism differences between insulator and semiconductor-supported Au and Ag NPs when applied in photocatalytic processes, and the influence of important factors, light intensity and wavelength, in particular estimations of light irradiation contribution, by calculating the apparent activation energies of photo reactions and thermal reactions.

Plasmonic photocatalysts of supported gold nanoparticles for organic conversions

This thesis is a comprehensive study of plasmonic gold photocatalysts for organic conversions. It presents the advantages of plasmonic gold photocatalysts in the selective oxidation, reduction, and acetalisation. It is discovered that plasmonic gold photocatalysts exhibit better catalytic performance (higher selectivity or activity) in these organic conversions. The study in this thesis highlights the capacity of plasmonic gold photocatalysts in harvesting solar energy for converting organic raw materials to value-added chemicals, and the great potential of gold photocatalysts in chemical production.

Hydrogels containing silver nanoparticles for burn wounds show antimicrobial activity without cytotoxicity

This research introduces a novel dressing for burn wounds, containing silver nanoparticles in hydrogels for infected burn care. The 2-acrylamido-2-methylpropane sulfonic acid sodium salt hydrogels containing silver nanoparticles have been prepared via ultraviolet radiation. The formation of silver nanoparticles was monitored by surface plasmon bands and transmission electron microscopy. The concentration of silver nitrate loaded in the solutions slightly affected the physical properties and mechanical properties of the neat hydrogel. An indirect cytotoxicity study found that none of the hydrogels were toxic to tested cell lines. The measurement of cumulative release of silver indicated that 70%–82% of silver was released within 72 hr. The antibacterial activities of the hydrogels against common burn pathogens were studied and the results showed that 5 mM silver hydrogel had the greatest inhibitory activity. The results support its use as a potential burn wound dressing.

Effects of joint thickness, adhesion and web shells to the face shell bedded concrete masonry loaded in compression

The Australian masonry standard allows either prism tests or correction factors based on the block height and mortar thickness to evaluate masonry compressive strength. The correction factor helps the taller units with conventional 10 mm mortar being not disadvantaged due to size effect. In recent times, 2-4 mm thick, high-adhesive mortars and H blocks with only the mid-web shell are used in masonry construction. H blocks and thinner and higher adhesive mortars have renewed interest of the compression behaviour of hollow concrete masonry and hence is revisited in this paper. This paper presents an experimental study carried out to examine the effects of the thickness of mortar joints, the type of mortar adhesives and the presence of web shells in the hollow concrete masonry prisms under axial compression. A non-contact digital image correlation technique was used to measure the deformation of the prisms and was found adequate for the determination of strain fi eld of the loaded face shells subjected to axial compression. It is found that the absence of end web shells lowers the compressive strength and stiffness of the prisms and the thinner and higher adhesive mortars increase the compressive strength and stiffness, while lowering the Poisson's ratio. © Institution of Engineers Australia, 2013.

Optical coupling of Au nanoparticles on vertical graphenes to maximize SERS response

Gold particle interaction with few-layer graphenes is of interest for the development of numerous optical nanodevices. The results of numerical studies of the coupling of gold nanoparticles with few-layer vertical graphene sheets are presented. The field strengths are computed and the optimum nanoparticle configurations for the formation of SERS hotpots are obtained. The nanoparticles are modeled as 8 nm diameter spheres atop 1.5 nm (5 layers) graphene sheet. The vertical orientation is of particular interest as it is possible to use both sides of the graphene structure and potentially double the number of particles in the system. Our results show that with the addition of an opposing particle a much stronger signal can be obtained as well as the particle separation can be controlled by the number of atomic carbon layers. These results provide further insights and contribute to the development of next-generation plasmonic devices based on nanostructures with hybrid dimensionality.

Mechanochemical synthesis of aluminium nanoparticles and their deuterium sorption properties to 2 kbar

A mechanochemical synthesis process has been used to synthesise aluminium nanoparticles. The aluminium is synthesised via a solid state chemical reaction which is initiated inside a ball mill at room temperature between either lithium (Li) or sodium (Na) metal which act as reducing agents with unreduced aluminium chloride (AlCl3). The reaction product formed consists of aluminium nanoparticles embedded within a by-product salt phase (LiCl or NaCl, respectively). The LiCl is washed with a suitable solvent resulting in aluminium (Al) nanoparticles which are not oxidised and are separated from the byproduct phase. Synthesis and washing was confirmed using X-ray diffraction (XRD). Nanoparticles were found to be ∼25–100nm from transmission electron microscopy (TEM) and an average size of 55nm was determined fromsmall angle X-ray scattering (SAXS) measurements. As synthesised Al/NaCl composites, washed Al nanoparticles, and purchased Al nanoparticles were deuterium (D2) absorption tested up to 2 kbar at a variety of temperatures, with no absorption detected within system resolution.

Encapsulation of nanoparticles into single-crystal ZnO nanorods and microrods

One-dimensional single crystal incorporating functional nanoparticles of other materials could be an interesting platform for various applications. We studied the encapsulation of nanoparticles into single-crystal ZnO nanorods by exploiting the crystal growth of ZnO in aqueous solution. Two types of nanodiamonds with mean diameters of 10 nm and 40 nm, respectively, and polymer nanobeads with size of 200 nm have been used to study the encapsulation process. It was found that by regrowing these ZnO nanorods with nanoparticles attached to their surfaces, a full encapsulation of nanoparticles into nanorods can be achieved. We demonstrate that our low-temperature aqueous solution growth of ZnO nanorods do not affect or cause degradation of the nanoparticles of either inorganic or organic materials. This new growth method opens the way to a plethora of applications combining the properties of single crystal host and encapsulated nanoparticles. We perform micro-photoluminescence measurement on a single ZnO nanorod containing luminescent nanodiamonds and the spectrum has a different shape from that of naked nanodiamonds, revealing the cavity effect of ZnO nanorod.

Numerical investigation into the buckling behavior of advanced grid stiffened composite cylindrical shell

Advanced grid stiffened composite cylindrical shell is widely adopted in advanced structures due to its exceptional mechanical properties. Buckling is a main failure mode of advanced grid stiffened structures in engineering, which calls for increasing attention. In this paper, the buckling response of advanced grid stiffened structure is investigated by three different means including equivalent stiffness model, finite element model and a hybrid model (H-model) that combines equivalent stiffness model with finite element model. Buckling experiment is carried out on an advanced grid stiffened structure to validate the efficiency of different modeling methods. Based on the comparison, the characteristics of different methods are independently evaluated. It is arguable that, by considering the defects of material, finite element model is a suitable numerical tool for the buckling analysis of advanced grid stiffened structures.

Ultra sensitive label free surface enhanced Raman spectroscopy method for the detection of biomolecules

We present a proof of concept for a novel nanosensor for the detection of ultra-trace amounts of bio-active molecules in complex matrices. The nanosensor is comprised of gold nanoparticles with an ultra-thin silica shell and antibody surface attachment, which allows for the immobilization and direct detection of bio-active molecules by surface enhanced Raman spectroscopy (SERS) without requiring a Raman label. The ultra-thin passive layer (~1.3 nm thickness) prevents competing molecules from binding non-selectively to the gold surface without compromising the signal enhancement. The antibodies attached on the surface of the nanoparticles selectively bind to the target molecule with high affinity. The interaction between the nanosensor and the target analyte result in conformational rearrangements of the antibody binding sites, leading to significant changes in the surface enhanced Raman spectra of the nanoparticles when compared to the spectra of the un-reacted nanoparticles. Nanosensors of this design targeting the bio-active compounds erythropoietin and caffeine were able to detect ultra-trace amounts the analyte to the lower quantification limits of 3.5×10−13 M and 1×10−9 M, respectively.

Electromagnetic propulsion and separation by chirality of nanoparticles in liquids

We introduce a new mechanism for the propulsion and separation by chirality of small ferromagnetic particles suspended in a liquid. Under the action of a uniform dc magnetic field H and an ac electric field E isomers with opposite chirality move in opposite directions. Such a mechanism could have a significant impact on a wide range of emerging technologies. The component of the chiral velocity that is odd in H is found to be proportional to the intrinsic orbital and spin angular momentum of the magnetized electrons. This effect arises because a ferromagnetic particle responds to the applied torque as a small gyroscope. © 2012 American Physical Society.

Microplasma-chemical synthesis and tunable real-time plasmonic responses of alloyed Aux Ag1−x nanoparticles

Tunable synthesis of bimetallic AuxAg1-x alloyed nanoparticles and in situ monitoring of their plasmonic responses is presented. This is a new conceptual approach based on green and energy efficient, reactive, and highly-non-equilibrium microplasma chemistry.

Plasma polymer-coated on nanoparticles to improve dielectric and electrical insulation properties of nanocomposites

Polymeric nanocomposites have been shown to possess superior electrical insulation properties compared to traditional filled-resins. However, poor dispersion uniformity and insufficient filler-matrix interaction can adversely affect insulation properties of nanocomposites. In this study, the use of plasma polymerization is proposed to coat poly(ethylene oxide) polymer layers on silica nanoparticles. It is shown that better dispersion is achieved and C-O bonds are created between the surface functional groups of the nanoparticles and the host epoxy polymer. Electrical insulation tests demonstrate that the nanocomposites with plasma polymerized silica nanoparticles feature better resistance against electrical treeing, lower dielectric constant, and also mitigated space charge built-up. Therefore, plasma polymerization offers a promising fabrication technique to further improve the synthesis of nanocomposite dielectrics with superior electrical insulation properties.