Voltammetric monitoring of gold nanoparticle formation facilitated by glycyl-L-tyrosine : relation to electronic spectra and transmission electron microscopy images

Voltammetric techniques have been introduced to monitor the formation of gold nanoparticles produced via the reaction of the amino acid glycyl-L-tyrosine with Au(III) (bromoaurate) in 0.05 M KOH conditions. The alkaline conditions facilitate amino acid binding to Au(III), inhibit the rate of reduction to Au(0), and provide an excellent supporting electrolyte for voltammetric studies. Data obtained revealed that a range of time-dependent gold solution species are involved in gold nanoparticle formation and that the order in which reagents are mixed is critical to the outcome. Concomitantly with voltammetric measurements, the properties of gold nanoparticles formed are probed by examination of electronic spectra in order to understand how the solution environment present during nanoparticle growth affects the final distribution of the nanoparticles. Images obtained by the ex situ transmission electron microscopy (TEM) technique enable the physical properties of the nanoparticles isolated in the solid state to be assessed. Use of this combination of in situ and ex situ techniques provides a versatile framework for elucidating the details of nanoparticle formation.

A facile chemical screening method for the detection of stress corrosion cracking in 9 carat gold alloys

Stress corrosion cracking (SCC) is a well known form of environmental attack in low carat gold jewellery. It is desirable to have a quick, easy and cost effective way to detect SCC in alloys and prevent them from being used and later failing in their application. A facile chemical method to investigate SCC of 9 carat gold alloys is demonstrated. It involves a simple application of tensile stress to a wire sample in a corrosive environment such as 1–10 % FeCl3 which induces failure in less than 5 minutes. In this study three quaternary (Au, Ag, Cu and Zn) 9 carat gold alloy compositions were investigated for their resistance to SCC and the relationship between time to failure and processing conditions is studied. It is envisaged that the use of such a rapid and facile screening procedure at the production stage may readily identify alloy treatments that produce jewellery that will be susceptible to SCC in its lifetime.

The electrochemical corrosion behaviour of quaternary gold alloys when exposed to 3.5% NaCl solution

Lower carat gold alloys, specifically 9 carat gold alloys, containing less than 40 % gold, and alloying additions of silver, copper and zinc, are commonly used in many jewellery applications, to offset high costs and poor mechanical properties associated with pure gold. While gold is considered to be chemically inert, the presence of active alloying additions raises concerns about certain forms of corrosion, particularly selective dissolution of these alloys. The purpose of this study was to systematically study the corrosion behaviour of a series of quaternary gold–silver–copper–zinc alloys using dc potentiodynamic scanning in saline (3.5 % NaCl) environment. Full anodic/cathodic scans were conducted to determine the overall corrosion characteristics of the alloy, followed by selective anodic scans and subsequent morphological and compositional analysis of the alloy surface and corroding media to determine the extent of selective dissolution. Varying degrees of selective dissolution and associated corrosion rates were observed after anodic polarisation in 3.5 % NaCl, depending on the alloy composition. The corrosion behaviour of the alloys was determined by the extent of anodic reactions which induce (1) formation of oxide scales on the alloy surface and or (2) dissolution of Zn and Cu species. In general, the improved corrosion characteristics of alloy #3 was attributed to the composition of Zn/Cu in the alloy and thus favourable microstructure promoting the formation of protective oxide/chloride scales and reducing the extent of Cu and Zn dissolution.

Exploiting the facile oxidation of evaporated gold films to drive electroless silver deposition for the creation of bimetallic Au/Ag surfaces

Gold is often considered as an inert material but it has been unequivocally demonstrated that it possesses unique electronic, optical, catalytic and electrocatalytic properties when in a nanostructured form.[1] For the latter the electrochemical behaviour of gold in aqueous media has been widely studied on a plethora of gold samples, including bulk polycrystalline and single-crystal electrodes, nanoparticles, evaporated films as well as electrodeposited nanostructures, particles and thin films.[1b, 2] It is now well-established that the electrochemical behaviour of gold is not as simple as an extended double-layer charging region followed by a monolayer oxide-formation/-removal process. In fact the so-called double-layer region of gold is significantly more complicated and has been investigated with a variety of electrochemical and surface science techniques. Burke and others[3] have demonstrated that significant processes due to the oxidation of low lattice stabilised atoms or clusters of atoms occur in this region at thermally and electrochemically treated electrodes which were confirmed later by Bond[4] to be Faradaic in nature via large-amplitude Fourier transformed ac voltammetric experiments. Supporting evidence for the oxidation of gold in the double-layer region was provided by Bard,[5] who used a surface interrogation mode of scanning electrochemical microscopy to quantify the extent of this process that forms incipient oxides on the surface. These were estimated to be as high as 20% of a monolayer. This correlated with contact electrode resistance measurements,[6] capacitance measurements[7] and also electroreflection techniques...

Lateral charge propagation effects during the galvanic replacement of electrodeposited MTCNQ (M= Cu, Ag) microstructures with gold and its influence on catalysed electron transfer reactions

The galvanic replacement of isolated electrodeposited semiconducting CuTCNQ microstructures on a glassy carbon (GC) substrate with gold is investigated. It is found that anisotropic metal nanoparticles are formed which are not solely confined to the redox active sites on the semiconducting materials but are also observed on the GC substrate which occurs via a lateral charge propagation mechanism. We also demonstrate that this galvanic replacement approach can be used for the formation of isolated AgTCNQ/Au microwire composites which occurs via an analogous mechanism. The resultant MTCNQ/Au (M = Cu, Ag) composite materials are characterized by Raman, spectroscopy, X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM) and investigated for their catalytic properties for the reduction of ferricyanide ions with thiosulphate ions in aqueous solution. Significantly it is demonstrated that gold loading, nanoparticle shape and in particular the MTCNQ–Au interface are important factors that influence the reaction rate. It is shown that there is a synergistic effect at the CuTCNQ/Au composite when compared to AgTCNQ/Au at similar gold loadings.

Creating gold nanoprisms directly on quartz crystal microbalance electrodes for mercury vapor sensing

A novel electrochemical route is used to form highly {111}-oriented and size-controlled Au nanoprisms directly onto the electrodes of quartz crystal microbalances (QCMs) which are subsequently used as mercury vapor sensors. The Au nanoprism loaded QCM sensors exhibited excellent response–concentration linearity with a response enhancement of up to ~ 800% over a non-modified sensor at an operating temperature of 28 °C. The increased surface area and atomic-scale features (step/defect sites) introduced during the growth of nanoprisms are thought to play a significant role in enhancing the sensing properties of the Au nanoprisms toward Hg vapor. The sensors are shown to have excellent Hg sensing capabilities in the concentration range of 0.123–1.27 ppmv (1.02–10.55 mg m − 3), with a detection limit of 2.4 ppbv (0.02 mg m − 3) toward Hg vapor when operating at 28 °C, and 17 ppbv (0.15 mg m − 3) at 89 °C, making them potentially useful for air monitoring applications or for monitoring the efficiency of Hg emission control systems in industries such as mining and waste incineration. The developed sensors exhibited excellent reversible behavior (sensor recovery) within 1 h periods, and crucially were also observed to have high selectivity toward Hg vapor in the presence of ethanol, ammonia and humidity, and excellent long-term stability over a 33 day operating period.

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%.

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.

Modelling the economic benefits of gold standard care for chronic wounds in a community setting

Chronic leg ulcers are costly to manage for health service providers. Although evidence-based care leads to improved healing rates and reduced costs, a significant evidence-practice gap is known to exist. Lack of access to specialist skills in wound care is one reason suggested for this gap. The aim of this study was to model the change to total costs and health outcomes under two versions of health services for patients with leg ulcers: routine health services for community-living patients; and care provided by specialist wound clinics. Mean weekly treatment and health services costs were estimated from participants’ data (n=70) for the twelve months prior to their entry to a study specialist wound clinic, and prospectively for 24 weeks after entry. For the retrospective phase mean weekly costs of care were $AU130.30 (SD $12.64) and these fell to $AU53.32 (SD $6.47) for the prospective phase. Analysis at a population level suggests if 10,000 individuals receive 12 weeks of specialist evidence-based care, the cost savings are likely to be AU$9,238,800. Significant savings could be made by the adoption of evidence-based care such as that provided by the community and outpatient specialist wound clinics in this study.

Culture makes you stronger : Aboriginal women’s voices from the South Coast of NSW

This paper will describe a community based research project examining the health and wellbeing of a sample of Aboriginal women in Australia, and present preliminary findings of a community needs analysis. The Shoalhaven Koori Women’s Study (SKWS) is being led by an Aboriginal woman based within Waminda, an Aboriginal women’s community controlled service located on the South Coast of NSW. The community needs analysis is the first stage of the SKWS, and aims to explore Aboriginal women’s perceptions and experiences of wellness and wellbeing, including issues related to their personal strengths, health and social priorities, support needs and that of their families. Thirty Aboriginal women were interviewed using a survey that included closed and open ended questions. Methods used to administer the survey included yarning and Dadirri (deep listening), two valid and culturally safe approaches for data collection with Aboriginal people. Adopting these approaches ensured Aboriginal protocols were maintained and upheld throughout the research process. This enabled scientific rigour while also ensuring activities were culturally safe. Key findings of the survey will be presented, and how Waminda is modifying service delivery to better respond to the health and social priorities of Aboriginal women in the Shoalhaven region will be discussed. Community feedback of survey results will occur to validate the analysis from the community perspective.

Probing the surface oxidation of chemically synthesised gold nanospheres and nanorods

In this study, the electrochemical behaviour of commercially available gold spheres and rods stabilised by carboxylic acid and cetyl trimethyl ammonium bromide (CTAB) moieties, respectively, are investigated. The cyclic voltammetric behaviour in acidic electrolyte is distinctly different with the nanorods exhibiting unusual oxidative behaviour due to an electrodissolution process. The nanospheres exhibited responses typical of a highly defective surface which significantly impacted on electrocatalytic activity. A repetitive potential cycling cleaning procedure was also investigated which did not improve the activity of the nanorods and resulted in deactivating the gold spheres due to decreasing the level of surface defects.

Hyperbranched polymer-gold nanoparticle assemblies : role of polymer architecture in hybrid assembly formation and SERS activity

Plasmonic gold nano-assemblies that self-assemble with the aid of linking molecules or polymers have the potential to yield controlled hierarchies of morphologies and consequently result in materials with tailored optical (e.g. localized surface plasmon resonances (LSPR)) and spectroscopic properties (e.g. surface enhanced Raman scattering (SERS)). Molecular linkers that are structurally well-defined are promising for forming hybrid nano-assemblies which are stable in aqueous solution and are increasingly finding application in nanomedicine. Despite much ongoing research in this field, the precise role of molecular linkers in governing the morphology and properties of the hybrid nano-assemblies remains unclear. Previously we have demonstrated that branched linkers, such as hyperbranched polymers, with specific anchoring end groups can be successfully employed to form assemblies of gold NPs demonstrating near-infrared SPRs and intense SERS scattering. We herein introduce a tailored polymer as a versatile molecular linker, capable of manipulating nano-assembly morphologies and hot-spot density. In addition, this report explores the role of the polymeric linker architecture, specifically the degree of branching of the tailored polymer in determining the formation, morphology and properties of the hybrid nano-assemblies. The degree of branching of the linker polymer, in addition to the concentration and number of anchoring groups, is observed to strongly influence the self-assembly process. The assembly morphology shifts primarily from 1D-like chains to 2D plates and finally to 3D-like globular structures, with increase in degree of branching. Insights have been gained into how the morphology influences the SERS performance of these nano-assemblies with respect to hot-spot density. These findings supplement the understanding of the morphology determining nano-assembly formation and pave the way for the possible application of these nano-assemblies as SERS bio-sensors for medical diagnostics.

Analysis of the needs of the East Coast cluster regional natural resource management bodies in relation to planning for climate change adaptation

The Climate Change Adaptation for Natural Resource Management (NRM) in East Coast Australia Project aims to foster and support an effective “community of practice” for climate change adaptation within the East Coast Cluster NRM regions that will increase the capacity for adaptation to climate change through enhancements in knowledge and skills and through the establishment of long‐term collaborations. It is being delivered by six consortium research partners: * The University of Queensland (project lead) * Griffith University * University of the Sunshine Coast * CSIRO * New South Wales Office of Environment and Heritage * Queensland Department of Science, IT, Innovation and the Arts (Queensland Herbarium). The project relates to the East Coast Cluster, comprising the six coastal NRM regions and regional bodies between Rockhampton and Sydney: * Fitzroy Basin Association (FBA) * Burnett‐Mary Regional Group (BMRG) * SEQ Catchments (SEQC) * Northern Rivers Catchment Management Authority (CMA) (NRCMA) * Hunter‐Central Rivers CMA (HCRCMA) * Hawkesbury Nepean CMA (HNCMA). The aims of this report are to summarise the needs of the regional bodies in relation to NRM planning for climate change adaptation, and provide a basis for developing the detailed work plan for the research consortium. Two primary methods were used to identify the needs of the regional bodies: (1) document analysis of the existing NRM/ Catchment Action Plans (CAPs) and applications by the regional bodies for funding under Stream 1 of the Regional NRM Planning for Climate Change Fund, and; (2) a needs analysis workshop, held in May 2013 involving representatives from the research consortium partners and the regional bodies. The East Coast Cluster includes five of the ten largest significant urban areas in Australia, world heritage listed natural environments, significant agriculture, mining and extensive grazing. The three NSW CMAs have recently completed strategic level CAPs, with implementation plans to be finalised in 2014/2015. SEQC and FBA are beginning a review of their existing NRM Plans, to be completed in 2014 and 2015 respectively; while BMRG is aiming to produce a NRM and Climate Variability Action Strategy. The regional bodies will receive funding from the Australian Government through the Regional NRM Planning for Climate Change Fund (NRM Fund) to improve regional planning for climate change and help guide the location of carbon and biodiversity activities, including wildlife corridors. The bulk of the funding will be available for activities in 2013/2014, with smaller amounts available in subsequent years. Most regional bodies aim to have a large proportion of the planning work complete by the end of 2014. In addition, NSW CMAs are undergoing major structural change and will be incorporated into semi‐autonomous statutory Local Land Services bodies from 2014. Boundaries will align with local government boundaries and there will be significant change in staff and structures. The regional bodies in the cluster have a varying degree of climate knowledge. All plans recognise climate change as a key driver of change, but there are few specific actions or targets addressing climate change. Regional bodies also have varying capacity to analyse large volumes of spatial or modelling data. Due to the complex nature of natural resource management, all regional bodies work with key stakeholders (e.g. local government, industry groups, and community groups) to deliver NRM outcomes. Regional bodies therefore require project outputs that can be used directly in stakeholder engagement activities, and are likely to require some form of capacity building associated with each of the outputs to maximise uptake. Some of the immediate needs of the regional bodies are a summary of information or tools that are able to be used immediately; and a summary of the key outputs and milestone dates for the project, to facilitate alignment of planning activities with research outputs. A project framework is useful to show the linkages between research elements and the relevance of the research to the adaptive management cycle for NRM planning in which the regional bodies are engaged. A draft framework is proposed to stimulate and promote discussion on research elements and linkages; this will be refined during and following the development of the detailed project work plan. The regional bodies strongly emphasised the need to incorporate a shift to a systems based resilience approach to NRM planning, and that approach is included in the framework. The regional bodies identified that information on climate projections would be most useful at regional and subregional scale, to feed into scenario planning and impact analysis. Outputs should be ‘engagement ready’ and there is a need for capacity building to enable regional bodies to understand and use the projections in stakeholder engagement. There was interest in understanding the impacts of climate change projections on ecosystems (e.g. ecosystem shift), and the consequent impacts on the production of ecosystem services. It was emphasised that any modelling should be able to be used by the regional bodies with their stakeholders to allow for community input (i.e. no black box models). The online regrowth benefits tool was of great interest to the regional bodies, as spatial mapping of carbon farming opportunities would be relevant to their funding requirements. The NSW CMAs identified an interest in development of the tool for NSW vegetation types. Needs relating to socio‐economic information included understanding the socio‐economic determinants of carbon farming uptake and managing community expectations. A need was also identified to understand the vulnerability of industry groups as well as community to climate change impacts, and in particular understanding how changes in the flow of ecosystem services would interact with the vulnerability of these groups to impact on the linked ecologicalsocio‐economic system. Responses to disasters (particularly flooding and storm surge) and recovery responses were also identified as being of interest. An ecosystem services framework was highlighted as a useful approach to synthesising biophysical and socioeconomic information in the context of a systems based, resilience approach to NRM planning. A need was identified to develop processes to move towards such an approach to NRM planning from the current asset management approach. Examples of best practice in incorporating climate science into planning, using scenarios for stakeholder engagement in planning and processes for institutionalising learning were also identified as cross‐cutting needs. The over‐arching theme identified was the need for capacity building for the NRM bodies to best use the information available at any point in time. To this end a planners working group has been established to support the building of a network of informed and articulate NRM agents with knowledge of current climate science and capacity to use current tools to engage stakeholders in NRM planning for climate change adaptation. The planners working group would form the core group of the community of practice, with the broader group of stakeholders participating when activities aligned with their interests. In this way, it is anticipated that the Project will contribute to building capacity within the wider community to effectively plan for climate change adaptation.

Partial rectification of the plasmon-induced electrical tunnel current in discontinuous thin gold film at optical frequency

The effect of plasmonoscillations, induced by pulsed laserirradiation, on the DC tunnel current between islands in a discontinuous thin goldfilm is studied. The tunnel current is found to be strongly enhanced by partial rectification of the plasmon-induced AC tunnel currents flowing between adjacent gold islands. The DC tunnel current enhancement is found to increase approximately linearly with the laser intensity and the applied DC bias voltage. The experimental data can be well described by an electron tunnelling model which takes the plasmon-induced AC voltage into account. Thermal heating seems not to contribute to the tunnel current enhancement.