Visible light-driven cross-coupling reactions at lower temperatures using a photocatalyst of palladium and gold alloy nanoparticles

Palladium (Pd)-catalyzed cross-coupling reactions are among the most important methods in organic synthesis. We report the discovery of highly efficient and green photocatalytic processes by which cross-coupling reactions, including Sonogashira, Stille, Hiyama, Ullmann, and Buchwald–Hartwig reactions, can be driven with visible light at temperatures slightly above room temperature using alloy nanoparticles of gold and Pd on zirconium oxide, thus achieving high yields. The alloy nanoparticles absorb visible light, and their conduction electrons gain energy, which is available at the surface Pd sites. Results of the density functional theory calculations indicate that transfer of the light excited electrons from the nanoparticle surface to the reactant molecules adsorbed on the nanoparticle surface activates the reactants. When the light intensity was increased, a higher reaction rate was observed, because of the increased population of photoexcited electrons. The irradiation wavelength also has an important impact on the reaction rates. Ultraviolet irradiation can drive some reactions with the chlorobenzene substrate, while visible light irradiation failed to, and substantially improve the yields of the reactions with the bromobenzene substrate. The discovery reveals the possibility of using low-energy and -density sources such as sunlight to drive chemical transformations.

Direct photocatalytic conversion of aldehydes to esters using supported gold nanoparticles under visible light irradiation at room temperature

Visible light can drive esteri fi cation from aldehydes and alcohols using supported gold nanoparticles (Au/Al 2 O 3 ) as photo- catalysts at ambient temperatures. The gold nanoparticles (AuNPs) absorb visible light due to the localized surface plasmon resonance (LSPR) e ff ect, and the conduction electrons of the AuNPs gain the energy of the incident light. The energetic electrons, which concentrate at the NP surface, facilitate the activation of a range of aldehyde and alcohol substrates. The photocatalytic e ffi ciencies strongly depend on the Au loading, particle sizes of the AuNPs, irradiance, and wavelength of the light irradiation. Finally, a plausible reaction mechanism was proposed, and the Au/Al 2 O 3 catalysts can be reused several times without signi fi cantly losing activity. The knowledge acquired in this study may inspire further studies in new e ffi cient recyclable photocatalysts and a wide range of organic synthesis driven by sunlight.

SERS-barcoded colloidal gold NP assemblies as imaging agents for use in biodiagnostics

There is a growing need for new biodiagnostics that combine high throughput with enhanced spatial resolution and sensitivity. Gold nanoparticle (NP) assemblies with sub-10 nm particle spacing have the benefits of improving detection sensitivity via Surface enhanced Raman scattering (SERS) and being of potential use in biomedicine due to their colloidal stability. A promising and versatile approach to form solution-stable NP assemblies involves the use of multi-branched molecular linkers which allows tailoring of the assembly size, hot-spot density and interparticle distance. We have shown that linkers with multiple anchoring end-groups can be successfully employed as a linker to assemble gold NPs into dimers, linear NP chains and clustered NP assemblies. These NP assemblies with diameters of 30-120 nm are stable in solution and perform better as SERS substrates compared with single gold NPs, due to an increased hot-spot density. Thus, tailored gold NP assemblies are potential candidates for use as biomedical imaging agents. We observed that the hot-spot density and in-turn the SERS enhancement is a function of the linker polymer concentration and polymer architecture. New deep Raman techniques like Spatially Offset Raman Spectroscopy (SORS) have emerged that allow detection from beneath diffusely scattering opaque materials, including biological media such as animal tissue. We have been able to demonstrate that the gold NP assemblies could be detected from within both proteinaceous and high lipid containing animal tissue by employing a SORS technique with a backscattered geometry.

Electrochemical mechanism of eugenol at a Cu doped gold nanoparticles modified glassy carbon electrode and its analytical application in food samples

A simple one-step electrodeposition method was used to construct a glassy carbon electrode (GCE), which has been modified with Cu doped gold nanoparticles (GNPs), i.e. a Cu@AuNPs/GCE. This electrode was characterized with the use of scanning electron microscopy (SEM) and X-ray diffraction (XRD) techniques. The eugenol was electrocatalytically oxidized at the Cu@AuNPs/GCE. At this electrode, in comparison with the behavior at the GCE alone, the corresponding oxidation peak current was enhanced and the shift of the oxidation potentials to lower values was observed. Electrochemical behavior of eugenol at the Cu@AuNPs/GCE was investigated with the use of the cyclic voltammetry (CV) technique, and additionally, in order to confirm the electrochemical reaction mechanism for o-methoxy phenols, CVs for catechol, guaiacol and vanillin were investigated consecutively. Based on this work, an electrochemical reaction mechanism for o-methoxy phenols was suggested, and in addition, the above Cu@AuNPs/GCE was successfully employed for the analysis of eugenol in food samples.

Estimating the parameters of stochastic volatility models using option price data

This article describes a maximum likelihood method for estimating the parameters of the standard square-root stochastic volatility model and a variant of the model that includes jumps in equity prices. The model is fitted to data on the S&P 500 Index and the prices of vanilla options written on the index, for the period 1990 to 2011. The method is able to estimate both the parameters of the physical measure (associated with the index) and the parameters of the risk-neutral measure (associated with the options), including the volatility and jump risk premia. The estimation is implemented using a particle filter whose efficacy is demonstrated under simulation. The computational load of this estimation method, which previously has been prohibitive, is managed by the effective use of parallel computing using graphics processing units (GPUs). The empirical results indicate that the parameters of the models are reliably estimated and consistent with values reported in previous work. In particular, both the volatility risk premium and the jump risk premium are found to be significant.

Self-assembly of indole-2-carboxylic acid at graphite and gold surfaces

Model systems are critical to our understanding of self-assembly processes. As such, we have studied the surface self-assembly of a small and simple molecule, indole-2-carboxylic acid (I2CA). We combine density functional theory gas-phase (DFT) calculations with scanning tunneling microscopy to reveal details of I2CA assembly in two different solvents at the solution/solid interface, and on Au(111) in ultrahigh vacuum (UHV). In UHV and at the trichlorobenzene/highly oriented pyrolytic graphite (HOPG) interface, I2CA forms epitaxial lamellar structures based on cyclic OH⋯O carboxylic dimers. The structure formed at the heptanoic acid/HOPG interface is different and can be interpreted in a model where heptanoic acid molecules co-adsorb on the substrate with the I2CA, forming a bicomponent commensurate unit cell. DFT calculations of dimer energetics elucidate the basic building blocks of these structures, whereas calculations of periodic two-dimensional assemblies reveal the epitaxial effects introduced by the different substrates.

Remember or Revive: Alice Payne and the Gold Coast and Hinterland Historical Society

In this creative practice work, designer Alice Payne examines the history of twentieth century Queensland fashion icon Paula Stafford, and interprets her story into an illustrated narrative and textile print. Paula Stafford was a swimwear designer operating in the Gold Coast, Queensland Australia 1940s to 1980s, and is credited with bringing the bikini to Australia. This project was commissioned by The Fashion Archives as part of their series Remember or Revive, in which the curators partnered designers with museums to reinterpret historical costume for a contemporary fashion audience. To develop the project, Payne visited The Gold Coast and Hinterland Historical Society to view Paula Stafford’s swimwear, resortwear, photographs, newspaper articles, fabric swatches and other artefacts relating to Stafford’s practice. Through examining Stafford’s work and history, Payne developed a series of designs based on the story and the experience of viewing and handling the garments. Research statement Fashion history is often experienced via static museum displays of garments and photographs from the period, and this research examines other means through which the archive and the fashion museum collection may be reinterpreted and made fresh. It does this in two ways: first, the work interprets a story from fashion history for a contemporary audience. Second, the project illuminates the fashion design process by demonstrating how garments from the past may be reinterpreted to inspire contemporary textile prints. The Paula Stafford collection at The Gold Coast and Hinterland Historical Society has a number of garments and photographs on display, however these only show a partial picture of the richness of Stafford’s work and legacy. Undertaking a practice-led methodology, in the course of developing the work, Payne examined the archive in order to interpret Stafford’s contribution to Queensland fashion through photography, narrative, and illustration. The work contributes to research into historical fashion curation and interpretation. The work appeared in Issue 11, March 2014 of the The Fashion Archives, an online publication by fashion curators Nadia Buick and Madeline King. The Fashion Archives has received funding from Arts Queensland, State Library Queensland and Creative Partnerships Australia and has published over 200 articles and projects related to Queensland Style. The Fashion Archives is the first project to examine in depth Queensland fashion history. As Paula Stafford is one of Queensland’s most iconic designers, this project is significant in being the first to examine her legacy through creative practice. The Fashion Archives was established in 2013 and involvement is by invitation from the curators.

A near Optimal Cane Rail Scheduler under Limited and Unlimited Capacity Constraints

Australia is the world’s third largest exporter of raw sugar after Brazil and Thailand, with around $2.0 billion in export earnings. Transport systems play a vital role in the raw sugar production process by transporting the sugarcane crop between farms and mills. In 2013, 87 per cent of sugarcane was transported to mills by cane railway. The total cost of sugarcane transport operations is very high. Over 35% of the total cost of sugarcane production in Australia is incurred in cane transport. A cane railway network mainly involves single track sections and multiple track sections used as passing loops or sidings. The cane railway system performs two main tasks: delivering empty bins from the mill to the sidings for filling by harvesters; and collecting the full bins of cane from the sidings and transporting them to the mill. A typical locomotive run involves an empty train (locomotive and empty bins) departing from the mill, traversing some track sections and delivering bins at specified sidings. The locomotive then, returns to the mill, traversing the same track sections in reverse order, collecting full bins along the way. In practice, a single track section can be occupied by only one train at a time, while more than one train can use a passing loop (parallel sections) at a time. The sugarcane transport system is a complex system that includes a large number of variables and elements. These elements work together to achieve the main system objectives of satisfying both mill and harvester requirements and improving the efficiency of the system in terms of low overall costs. These costs include delay, congestion, operating and maintenance costs. An effective cane rail scheduler will assist the traffic officers at the mill to keep a continuous supply of empty bins to harvesters and full bins to the mill with a minimum cost. This paper addresses the cane rail scheduling problem under rail siding capacity constraints where limited and unlimited siding capacities were investigated with different numbers of trains and different train speeds. The total operating time as a function of the number of trains, train shifts and a limited number of cane bins have been calculated for the different siding capacity constraints. A mathematical programming approach has been used to develop a new scheduler for the cane rail transport system under limited and unlimited constraints. The new scheduler aims to reduce the total costs associated with the cane rail transport system that are a function of the number of bins and total operating costs. The proposed metaheuristic techniques have been used to find near optimal solutions of the cane rail scheduling problem and provide different possible solutions to avoid being stuck in local optima. A numerical investigation and sensitivity analysis study is presented to demonstrate that high quality solutions for large scale cane rail scheduling problems are obtainable in a reasonable time. Keywords: Cane railway, mathematical programming, capacity, metaheuristics

Rapid isolation and detection of erythropoietin in blood plasma by magnetic core gold nanoparticles and portable Raman spectroscopy

Isolating, purifying, and identifying proteins in complex biological matrices is often difficult, time consuming, and unreliable. Herein we describe a rapid screening technique for proteins in biological matrices that combines selective protein isolation with direct surface enhanced Raman spectroscopy (SERS) detection. Magnetic core gold nanoparticles were synthesised, characterised, and subsequently functionalized with recombinant human erythropoietin (rHuEPO)-specific antibody. The functionalized nanoparticles were used to capture rHuEPO from horse blood plasma within 15 minutes. The selective binding between the protein and the functionalized nanoparticles was monitored by SERS. The purified protein was then released from the nanoparticles’ surface and directly spectroscopically identified on a commercial nanopillar SERS substrate. ELISA independently confirmed the SERS identification and quantified the released rHuEPO. Finally, the direct SERS detection of the extracted protein was successfully demonstrated for in-field screening by a handheld Raman spectrometer within 1 minute sample measurement time.

Planning the unplanned City: The story of the gold coast

One of the distinctive features of Gold Coast urbanisation is its historically ad hoc approach to development with little or no strategic planning to guide it. Many have commented on the lack of planning on the Gold Coast calling it ‘an experiment in freedom’ or ‘free enterprise city’. Following a major restructuring of the Queensland’s local councils, the 1990s witnessed a shift from ad hoc decision making to more systematic planning on the Gold Coast. Understanding the past is important for shaping the future. This paper reviews the history of regulatory planning on the Gold Coast, encompassing decisions affecting the form and development of its earliest settlements through to its periods of greatest construction and most streamlined decision–making. It focuses mainly on past planning processes, the problems identified in each planning exercise and the interventions introduced, asking whether these were implemented or not and why. The paper positions the Gold Coast as a physical embodiment of this history of decision making, assessing the effects on the city as a whole of specific measures either affording freedoms or insisting on accountability to various levels of regulation. It examines how the absence of some planning measures influenced the form of the city and its internal arrangements and considers how the shift from ad hoc decision making towards more systematic planning efforts affected the city’s urbanisation. The lessons that the Gold Coast example provides will resonate with places elsewhere in Australia and the world, if not always in scale definitely in substance.

Direct electrochemical formation of nanostructured amorphous Co(OH)2 on gold electrodes with enhanced activity for the oxygen evolution reaction.

The oxides of cobalt have recently been shown to be highly effective electrocatalysts for the oxygen evolution reaction (OER) under alkaline conditions. In general species such as Co3O4 and CoOOH have been investigated that often require an elevated temperature step during their synthesis to create crystalline materials. In this work we investigate the rapid and direct electrochemical formation of amorphous nanostructured Co(OH)2 on gold electrodes under room temperture conditions which is a highly active precursor for the OER. During the OER some conversion to crystalline Co3O4 occurs at the surface, but the bulk of the material remains amorphous. It is found that the underlying gold electrode is crucial to the materials enhanced performance and provides higher current density than can be achieved using carbon, palladium or copper support electrodes. This catalyst exhibits excellent activity with a current density of 10 mA cm-2 at an overpotential of 360 mV with a high turnover frequency of 2.1 s-1 in 1 M NaOH. A Tafel slope of 56 mV dec-1 at low overpotentials and a slope of 122 mV dec-1 at high overpotentials is consistent with the dual barrier model for the electrocatalytic evolution of oxygen. Significantly, the catalyst maintains excellent activity for up to 24 hr of continuous operation and this approach offers a facile way to create a highly effective and stable material.

Crude oil and agricultural futures: An analysis of correlation dynamics

Correlations between oil and agricultural commodities have varied over previous decades, impacted by renewable fuels policy and turbulent economic conditions. We estimate smooth transition conditional correlation models for 12 agricultural commodities and WTI crude oil. While a structural change in correlations occurred concurrently with the introduction of biofuel policy, oil and food price levels are also key influences. High correlation between biofuel feedstocks and oil is more likely to occur when food and oil price levels are high. Correlation with oil returns is strong for biofuel feedstocks, unlike with other agricultural futures, suggesting limited contagion from energy to food markets.

Get ready for a fruit fight: the fallout from Coles' price war on produce

Amid tough trading conditions and intense competition, Coles has fired the latest salvo in its ongoing supermarket war with Woolworths, announcing it will reduce the price of some fruit and vegetables by 50%. The move is the latest in a battle between the supermarket giants to wrest market share and follows previous cuts to staples such as milk and bread, beer and chicken. However, Australia’s peak industry body of vegetable growers, Ausveg, is concerned about the impact the price decision will have on growers' livelihoods.

Predicting the last brand standing in the supermarket price wars

On January 26, 2011, grocery retailer Coles fired the first salvo in what would soon be dubbed the “supermarket price wars” by reducing the price of its own-brand milk to A$1 per litre. Woolworths immediately responded. In the three years since, grocery prices have been tumbling, with 85 cent bread being the latest “sacrificial lamb”. This period of intense competition has brought about not just lower grocery prices, but a senate enquiry, and increasing media and analyst interest.

Food price and affordability update

This presentation outlines recent achievements in development of tools, protocols and methods to monitoring and benchmark food prices and affordability globally under International Network for Food and Obesity/non-communicable diseases Research, Monitoring and Action Support(INFORMAS)