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.

The genesis of 'the new geography and the new imperialism : 1870-1918', or 'how I came to Jamaica and joined the UWI Geography Department

In this article, Brian Hudson relates how he came to write the paper published in the journal Antipode, for which he gained recognition as a radical geographer in the late 1970's. It is a tale of a journey in which the loves of his life, geography, history, travel and his wife of over 40 years, came together through living in a number of different places: the United Kingdom, Ghana, Hong Kong, and Jamaica. After leaving UWI, Brian and his family settled in Brisbane, Australia where he taught at Queensland University of Technology until his retirement.

…Where did I lose you? Accessing the literacy demands of assessment

In this study we sought to find out how teachers could make assessment fairer for Indigenous students in learning mathematics, given the context of the high stakes of the National Assessment Program Literacy and Numeracy (NAPLAN). Today, teachers are experiencing the full range of demands from their own students who require individual attention, through to system level expectations of improved performances for all students. Many staff experience reform fatigue with limited time for critical reflection and a reduction in support for the use and the analysis of the overwhelming amount of data that has become available in recent years. Over the past three years we worked with teachers in seven schools to gradually refine our research focus to centre on how we might best support teachers in this demanding context with the important outcome of improved teaching and learning of mathematics with particular consideration of how to respond to the cultural needs of Indigenous (Aboriginal and Torres Strait Islander) students.

Sampling environmental acoustic recordings to determine species richness : I

Acoustic sensors provide an effective means of monitoring biodiversity at large spatial and temporal scales. They can continuously and passively record large volumes of data over extended periods, however these data must be analysed to detect the presence of vocal species. Automated analysis of acoustic data for large numbers of species is complex and can be subject to high levels of false positive and false negative results. Manual analysis by experienced users can produce accurate results, however the time and effort required to process even small volumes of data can make manual analysis prohibitive. Our research examined the use of sampling methods to reduce the cost of analysing large volumes of acoustic sensor data, while retaining high levels of species detection accuracy. Utilising five days of manually analysed acoustic sensor data from four sites, we examined a range of sampling rates and methods including random, stratified and biologically informed. Our findings indicate that randomly selecting 120, one-minute samples from the three hours immediately following dawn provided the most effective sampling method. This method detected, on average 62% of total species after 120 one-minute samples were analysed, compared to 34% of total species from traditional point counts. Our results demonstrate that targeted sampling methods can provide an effective means for analysing large volumes of acoustic sensor data efficiently and accurately.

Effect of outdoor site location on calculated I/O ratios

Motor vehicle emissions have been identified as one of the major contributors of fine and ultrafine particles (UFP) in urban areas. Schools located near major roads could potentially be exposed to high levels of UPFs and school classroom is an important microenvironment where significant exposure to UFPs is likely to occur. Most of the research conducted to date has investigated the relationship between indoor and outdoor particle number concentration (PNC) in schools based on one outdoor location, which may introduce a level of error when calculating the variation of total UPFs, and can result in the underestimation or overestimation of indoor to outdoor (I/O) ratio values.

Influence of filtration on I/O particle concentration ratios at urban office buildings

Epidemiological research has consistently shown an association between fine and ultrafine particle concentrations, and increases in both respiratory and cardiovascular morbidity and mortality. These particles, often found in vehicle emissions outside buildings, can penetrate inside via their envelopes and mechanically ventilated systems. Indoor activities such as printing, cooking and cleaning, as well as the movement of building occupants are also an additional source of these particles. In this context, the filtration systems of mechanically ventilated buildings can reduce indoor particle concentrations. Several studies have quantified the efficiency of dry-media and electrostatic filters, but they mainly focused on the particle size range > 300 nm. Some others studied ultrafine particles but their investigations were conducted in laboratories. At this point, there is still only limited information on in situ filter efficiency and an incomplete understanding of filtration influence on I/O ratios of particle concentrations. To help address these gaps in knowledge and provide new information for the selection of appropriate filter types in office building HVAC systems, we aimed to: (1) measure particle concentrations at up and down stream flows of filter devices, as well as outdoor and indoor office buildings; (2) quantify efficiency of different filter types at different buildings; and (3) assess the impact of these filters on I/O ratios at different indoor and outdoor source operation scenarios.