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.

Re-strengthening Brisbane City Hall : a case study of heritage engineering

Upgrading old buildings with the evolution of building requirements, this project investigates new approaches that can be applied to strengthen our own heritage buildings using historical and comparative analysis of heritage building restorations locally and abroad. Within the newly developing field of Heritage Engineering, it evaluates the innovative Concrete Overlay technique adapted to building restoration of the Brisbane City Hall. This study aims to extend the application of Concrete Overlay techniques and determine its compatibility specifically to heritage buildings. Concrete overlay involves drilling new reinforcement and placing concrete on top of the existing structure. It is akin to a bone transplant or bone grafting in the case of a human being and has been used by engineers to strengthen newer bridges.

Ovens : Talking fish - making connections with the rivers of the Murray-Darling Basin

The Ovens River rises in the Victorian Alps where it is linked to significant freshwater meadows and marshes. It flows past Harrietville, Bright, Myrtleford and Wangaratta where it is joined by the King River on its way to meet the Murray near the top of Lake Mulwala. These the traditional lands of the Bangerang people and their neighbours the Taungurung and Yorta Yorta peoples. They have fished the river and surrounding waterways and hunted the wetlands. The ebb and flow of water guided their travels and featured in their stories. The Bangerang, Taungurung and Yorta Yorta have seen their land and the river change...

A neutron diffraction investigation of residual stresses in rail ends after severe deformation of rail surfaces

Insulated rail joints (IRJs) are a primary component of the rail track safety and signalling systems. Rails are supported by two fishplates which are fastened by bolts and nuts and, with the support of sleepers and track ballast, form an integrated assembly. IRJ failure can result from progressive defects, the propagation of which is influenced by residual stresses in the rail. Residual stresses change significantly during service due to the complex deformation and damage effects associated with wheel rolling, sliding and impact. IRJ failures can occur when metal flows over the insulated rail gap (typically 6-8 mm width), breaks the electrically isolated section of track and results in malfunction of the track signalling system. In this investigation, residual stress measurements were obtained from rail-ends which had undergone controlled amounts of surface plastic deformation using a full scale wheel-on-track simulation test rig. Results were compared with those obtained from similar investigations performed on rail ends associated with ex-service IRJs. Residual stresses were measured by neutron diffraction at the Australian Nuclear Science and Technology Organisation (ANSTO). Measurements with constant gauge volume 3x3x3 mm3 were carried in the central vertical plane on 5mm thick sliced rail samples cut by an electric discharge machine (EDM). Stress evolution at the rail ends was found to exhibit characteristics similar to those of the ex-service rails, with a compressive zone of 5mm deep that is counterbalanced by a tension zone beneath, extending to a depth of around 15mm. However, in contrast to the ex-service rails, the type of stress distribution in the test-rig deformed samples was apparently different due to the localization of load under the particular test conditions. In the latter, in contrast with clear stress evolution, there was no obvious evolution of d0. Since d0 reflects rather long-term accumulation of crystal lattice damage and microstructural changes due to service load, the loading history of the test rig samples has not reached the same level as the ex-service rails. It is concluded that the wheel-on-rail simulation rig provides the potential capability for testing the wheel-rail rolling contact conditions in rails, rail ends and insulated rail joints.

ACE research briefing paper 007 : Ken Talbot - an entrepreneur's contribution to the growth of the Australian Mining Industry

Ken Talbot was one of Australian mining’s most successful entrepreneurs and rose to the top of his industry to become one of Australia’s wealthiest men. Although the nation’s resources industry is synonymous with global names such as Xstrata, BHP Billiton and Rio Tinto, Ken was an individual who made a big impact on the development and growth of the sector. This case study examines Ken’s achievements, his transition from employee to entrepreneur, and the qualities that enabled him to succeed at such a high level. In particular, it focuses on his Jellinbah and Coppabella mining developments that directly led to the creation of Macarthur Coal and the Talbot Group. By the time of his premature death in an African plane crash in 2010, Ken had amassed a fortune estimated at almost $1 billion and was aged just 59. The last publically available Talbot Group annual report for calendar year 2009 showed that the investment portfolio of the group returned 113 per cent that year. Even throughout the global financial crisis the portfolio made a positive return on investment of no less than 10 per cent. Ken’s sense of mateship and his tremendous people skills were keys to his success in the mining industry and the wider community. In addition to excelling in business, he is also remembered for his philanthropy and leaving 30 per cent of his estate to charity through the Talbot Family Foundation.

Photoelectron spectroscopic study of the oxyallyl diradical

The photoelectron spectrum of the oxyallyl (OXA) radical anion has been measured. The radical anion has been generated in the reaction of the atomic oxygen radical anion (O center dot-) with acetone. Three low-lying electronic states of OXA have been observed in the spectrum. Electronic structure calculations have been performed for the triplet states (B-3(2) and B-3(1)) of OXA and the ground doublet state ((2)A(2)) of the radical anion using density, functional theory (DFT). Spectral simulations have been carried out for the triplet statics based on the results of the DFT calculations. The simulation identifies a vibrational progression of the CCC bending mode of the B-3(2) state of OXA in the lower electron binding energy (eBE) portion of the spectrum. On top of the B-3(2) feature, however, the experimental spectrum exhibits additional photoelectron peaks whose angular distribution is distinct from that for the vibronic peaks of the B-3(2) state. Complete active space self-consistent field (CASSCF) method and second-order perturbation theory based on the CASSCF wave function (CASPT2) have been employed to study the lowest singlet state ((1)A(1)) of OXA. The simulation based on the results of these electronic structure calculations establishes that the overlapping peaks represent the vibrational ground level of the (1)A(1) state and its vibrational progression of the CO stretching mode. The A, state is the lowest electronic state of,OXA, and the electron affinity (EA) of OXA is 1.940 +/- 0.010 eV. The B-3(2) state is the first excited state with an electronic term energy of 55 +/- 2 meV. The widths of the vibronic peaks of the (X) over tilde (1)A(1) state are much broader than those of the (a) over tilde B-3(2) state, implying that the (1)A(1) state is indeed a transition state. The CASSCF and CASPT2 calculations suggest that the (1)A(1) state is at a potential maximum along the nuclear coordinate representing disrotatory motion of the two methylene groups, which leads to three-membered-ring formation, i.e., cydopropanone. The simulation of (b) over tilde B-3(1) OXA reproduces the higher eBE portion of the spectrum very well. The term energy of the B-3(1) state is 0.883 +/- 0.012 eV. Photoelectron spectroscopic measurements have also been conducted for the other ion products of the O center dot- reaction with acetone. The photoelectron imaging spectrum of the acetylcarbene (AC) radical anion exhibits a broad, structureless feature, which is assigned to the (X) over tilde (3)A '' state of AC. The ground ((2)A '') and first excited ((2)A') states of the 1-methylvinoxy (1-MVO) radical have been observed in the photoelectron spectrum of the 1-MVO ion, and their vibronic structure has been analyzed.

Chemotaxis and chemokinesis of human prostate tumor cell lines in response to human prostate stromal cell secretory proteins containing a nerve growth factor-like protein

The migration of three human prostate tumor epithelial cell lines (TSU-pr1, PC-3, DU-145) in response to secreted protein from a human prostate stromal cell line was investigated by using the modified blind-well Boyden chamber assay. Migrated cells were quantified by spectrophotometrically measuring the concentration of crystal violet stain extracted from their nuclei. Cell number was correlated linearly with the concentration of extracted crystal violet stain. All three tumor cell lines showed intrinsic migratory ability in the absence of chemoattractants, such that approximately 1-7% of plated cells migrated across the filter of the Boyden chambers during a 5-h incubation period. Prostate tumor cell migration was significantly enhanced (3-13-fold) in response to stromal cell secretory protein in a dose-dependent manner, whereas bovine serum albumin had no effect on stimulating tumor cell migration. Immunoprecipitation of the stromal cell secreted protein with a nerve growth factor antibody partially and significantly reduced its stimulatory activity for tumor cell migration. A Zigmond-Hirsch matrix assay of tumor cell migration in response to various concentration gradients of stromal cell secreted protein demonstrated both chemotaxis and chemokinesis by all three cell lines. These results are consistent with the stromal cell secretory protein stimulation of chemokinetic tumor cell migration through the capsule of the prostate. Outside of the prostate gland metastasis of tumor cells may occur by chemotaxis to preferential sites containing chemoattractants similar to or related to maintenance factors that can substitute for components of stromal cell secretory protein.

Plasma heating effects in catalyzed growth of carbon nanofibres

A theoretical model describing the plasma-assisted growth of carbon nanofibres (CNFs) that accounts for the nanostructure heating by ion and etching gas fluxes from the plasma is developed. Using the model, it is shown that fluxes from the plasma environment can substantially increase the temperature of the catalyst nanoparticle located on the top of the CNF with respect to the substrate temperature. The difference between the catalyst and the substrate temperatures depends on the substrate width, the length of the CNF, the neutral gas density and temperature as well as the densities of the ions and atoms of the etching gas. In addition to the heating of the nanostructure, the ions and etching gas atoms from the ionized gas environment also strongly affect the CNF growth rates. Due to ion bombardment, the CNF growth rates in plasma enhanced chemical vapour deposition may be much higher than the rates in similar neutral gas-based thermal processes. The CNF growth model, which accounts for the nanostructure heating by the plasma-generated species, provides the growth rates that are in better agreement with the available experimental data on CNF growth than the models in which the heating effects are ignored.

Plasma-controlled nanocrystallinity and phase composition of TiO2 : a smart way to enhance biomimetic response

This contribution sheds light on the role of crystal size and phase composition in inducing biomimetic apatite growth on the surface of nanostructured titania films synthesized by reactive magnetron sputtering of Ti targets in Ar+O2 plasmas. Unlike most existing techniques, this method enables one to deposit highly crystalline titania films with a wide range of phase composition and nanocrystal size, without any substrate heating or postannealing. Moreover, by using this dry plasma-based method one can avoid surface hydroxylation at the deposition stage, almost inevitable in wet chemical processes. Results of this work show that high phase purity and optimum crystal size appear to be the essential requirement for efficient apatite formation on magnetron plasma-fabricated bioactive titania coatings. © 2006 Wiley Periodicals, Inc.

Effect of plasma environment on synthesis of vertically aligned carbon nanofibers in plasma-enhanced chemical vapor deposition

We present a theoretical model describing a plasma-assisted growth of carbon nanofibers (CNFs), which involves two competing channels of carbon incorporation into stacked graphene sheets: via surface diffusion and through the bulk of the catalyst particle (on the top of the nanofiber), accounting for a range of ion- and radical-assisted processes on the catalyst surface. Using this model, it is found that at low surface temperatures, Ts, the CNF growth is indeed controlled by surface diffusion, thus quantifying the semiempirical conclusions of earlier experiments. On the other hand, both the surface and bulk diffusion channels provide a comparable supply of carbon atoms to the stacked graphene sheets at elevated synthesis temperatures. It is also shown that at low Ts, insufficient for effective catalytic precursor decomposition, the plasma ions play a key role in the production of carbon atoms on the catalyst surface. The model is used to compute the growth rates for the two extreme cases of thermal and plasma-enhanced chemical vapor deposition of CNFs. More importantly, these results quantify and explain a number of observations and semiempirical conclusions of earlier experiments.

Mathematical modelling and experimental validation of solar assisted heat pump system

Singapore is located at the equator, with abundant supply of solar radiation, relatively high ambient temperature and relative humidity throughout the year. The meteorological conditions of Singapore are favourable for efficient operation of solar energy based systems. Solar assisted heat pump systems are built on the roof-top of National University of Singapore’s Faculty of Engineering. The objectives of this study include the design and performance evaluation of a solar assisted heat-pump system for water desalination, water heating and drying of clothes. Using MATLAB programming language, a 2-dimensional simulation model has been developed to conduct parametric studies on the system. The system shows good prospect to be implemented in both industrial and residential applications and would give new opportunities in replacing conventional energy sources with green renewable energy.

E-government policies for broadband adoption : the case of the UK Government

Broadband technology has been introduced to the business community and the public as a fast and easy way of exploiting the Internet. The benefits of its use (fast reliable connections, always on) have been widely realised and broadband diffusion is one of the items at the top of the agenda for technology related polices of governments worldwide. Broadband diffusion and capacity development are central to debates in many countries concerning the role of the government in developing efficient broadband policies particularly in terms of the usage of public money. In this paper we examine the impact of government polices to broadband adoption in the case of the UK government, a country that is striving to have the most extensive and competitive broadband market in the G7 by 2005. We analyse specific institutional actions related to IT diffusion as pursued by the government with the view to identify best practices in government intervention. We believe that are our analysis is useful for broadband strategies in particular and technology in general when applied elsewhere.

Effect of chute level on mill capacity

IN MANY FACTORIES, the feed chute of the first mill is operated with a high chute level for the purpose of maximising the cane rate through the mill. There is a trend towards trying to control chute level within a small control range near the top of a chute that can result in rapid changes in cane feeding rate to maintain the chute level set point. This paper reviews the theory that predicts higher cane rate with higher chute level and discusses the main weakness in the theory that it does not consider the beneficial effect on capacity of cane falling from the top of the chute to the top surface of the cane mat. An extension to the chute theory model is described that predicts higher capacity with lower chute level because of the effect of the falling cane. The original model and this extended model are believed to be the upper and lower limits to the true effect. The paper reports an experiment that measured the real effect of chute level on capacity and finds that increasing chute level does lead to higher capacity but that the trend is only about one-third as strong as the original theory predicted. The paper questions whether the benefits of slightly greater capacity outweigh the costs of operating with the small control range near the top of the chute.

Regulating supply-chains to address the occupational health and safety problems associated with precarious employment: The case of home-based clothing workers in Australia

Over the past 20 years the labour market, workforce and work organisation of most if not all industrialised countries have been significantly refashioned by the increased use of more flexible work arrangements, variously labelled as precarious employment or contingent work. There is now a substantial and growing body of international evidence that many of these arrangements are associated with a significant deterioration in occupational health and safety (OHS), using a range of measures such as injury rates, disease, hazard exposures and work-related stress. Moreover, there is an emerging body of evidence that these arrangements pose particular problems for conventional regulatory regimes. Recognition of these problems has aroused the concern of policy makers - especially in Europe, North America and Australia - and a number of responses have been adopted in terms of modifying legislation, producing new guidance material and codes of practice and revised enforcement practices. This article describes one such in itiative in Australia with regard to home-based clothing workers. The regulatory strategy developed in one Australian jurisdiction (and now being ‘exported’ into others) seeks to counter this process via contractual tracking mechanisms to follow the work, tie in liability and shift overarching legal responsibility to the top of the supply chain. The process also entails the integration of minimum standards relating to wages, hours and working conditions; OHS and access to workers’ compensation. While home-based clothing manufacture represents a very old type of ‘flexible’ work arrangement, it is one that regulators have found especially difficult to address. Further, the elaborate multi-tiered subcont racting and diffuse work locations found in this industry are also characteristic of newer forms of contingent work in other industries (such as some telework) and the regulatory challenges they pose (such as the tendency of elaborate supply chains to attenuate and fracture statutory responsibilities, at least in terms of the attitudes and behaviour of those involved).

Supply chain regulation to protect the occupational health and safety of vulnerable workers

The last two decades have witnessed a fragmentation of previously integrated systems of production and service delivery with the advent of boundary-less, networked and porous organisational forms. This trend has been associated with the growth of outsourcing and increased use of contingent workers. One consequence of these changes is the development of production/service delivery systems based on complex national and international networks of multi-tiered subcontracting increasingly labelled as supply chains. A growing body of research indicates that subcontracting and contingent work arrangements affect design and decision-making processes in ways that can seriously undermine occupational health and safety (OHS). Elaborate supply chains also present a regulatory challenge because legal responsibility for OHS is diffused amongst a wider array of parties, targeting key decision-makers is more difficult, and government agencies encounter greater logistical difficulties trying to safeguard contingent workers. In a number of industries these problems have prompted new forms of regulatory intervention, including mechanisms for sheeting legal responsibility to the top of supply chains, contractual tracking devices and increasing industry, union and community involvement in enforcement. After describing the problems just alluded to this paper examines recent efforts to regulate supply chains to safeguard OHS in the United Kingdom and Australia.