The synthesis and application of novel profluorescent nitroxides as probes for polymer degradation

This PhD project has expanded the knowledge in the area of profluorescent nitroxides with regard to the synthesis and characterisations of novel profluorescent nitroxide probes as well as physical characterisation of the probe molecules in various polymer/physical environments. The synthesis of the first example of an azaphenalene-based fused aromatic nitroxide TMAO, [1,1,3,3-tetramethyl-2,3-dihydro-2-azaphenalen-2-yloxyl, was described. This novel nitroxide possesses some of the structural rigidity of the isoindoline class of nitroxides, as well as some properties akin to TEMPO nitroxides. Additionally, the integral aromatic ring imparts fluorescence that is switched on by radical scavenging reactions of the nitroxide, which makes it a sensitive probe for polymer degradation. In addition to the parent TMAO, 5 other azaphenalene derivatives were successfully synthesised. This new class of nitroxide was expected to have interesting redox properties when the structure was investigated by high-level ab initio molecular orbitals theory. This was expected to have implications with biological relevance as the calculated redox potentials for the azaphenalene ring class would make them potent antioxidant compounds. The redox potentials of 25 cyclic nitroxides from four different structural classes (pyrroline, piperidine, isoindoline and azaphenalene) were determined by cyclic voltammetry in acetonitrile. It was shown that potentials related to the one electron processes of the nitroxide were influenced by the type of ring system, ring substituents or groups surrounding the moiety. Favourable comparisons were found between theoretical and experimental potentials for pyrroline, piperidine and isoindoline ring classes. Substitution of these ring classes, were correctly calculated to have a small yet predictable effect on the potentials. The redox potentials of the azaphenalene ring class were underestimated by the calculations in all cases by at least a factor of two. This is believed to be due to another process influencing the redox potentials of the azaphenalene ring class which is not taken into account by the theoretical model. It was also possible to demonstrate the use of both azaphenalene and isoindoline nitroxides as additives for monitoring radical mediated damage that occurs in polypropylene as well as in more commercially relevant polyester resins. Polymer sample doped with nitroxide were exposed to both thermo-and photo-oxidative conditions with all nitroxides showing a protective effect. It was found that isoindoline nitroxides were able to indicate radical formation in polypropylene aged at elevated temperatures via fluorescence build-up. The azaphenalene nitroxide TMAO showed no such build-up of fluorescence. This was believed to be due to the more labile bond between the nitroxide and macromolecule and the protection may occur through a classical Denisov cycle, as is expected for commercially available HAS units. Finally, A new profluorescent dinitroxide, BTMIOA (9,10-bis(1,1,3,3- tetramethylisoindolin-2-yloxyl-5-yl)anthracene), was synthesised and shown to be a powerful probe for detecting changes during the initial stages of thermo-oxidative degradation of polypropylene. This probe, which contains a 9,10-diphenylanthracene core linked to two nitroxides, possesses strongly suppressed fluorescence due to quenching by the two nitroxide groups. This molecule also showed the greatest protective effect on thermo-oxidativly aged polypropylene. Most importantly, BTMIOA was found to be a valuable tool for imaging and mapping free-radical generation in polypropylene using fluorescence microscopy.

Investigating erythemal UV exposure and vitamin D production in the urban canyon

Exposure to ultraviolet radiation (UV) results in both damaging and beneficial health outcomes. Excessive UV exposure has been linked to many skin and eye problems, but moderate exposure induces vitamin D production. It has been reported that humans receive 90-95% of their vitamin D from production that starts after UV exposure. Although it is possible to acquire vitamin D through dietary supplementation, the average person receives very little in this manner. Therefore, since most people acquire their vitamin D from synthesis after exposure to UV from sunlight, it is very important to understand the different environments in which people encounter UV. This project measured UV radiation and in-vitro vitamin D production in the urban canyon and at a nearby suburban location. The urban canyon is an environment consisting of tall buildings and tropospheric air pollution, which have an attenuating effect on UV. Typically, UV measurements are collected in areas outside the urban canyon, meaning that at times studies and public recommendations do not accurately represent the amount of UV reaching street-level in highly urbanized areas. Understanding of UV exposure in urban canyons becomes increasingly important as the number of people working and living in large cities steadily increases worldwide. This study was conducted in the central business district (CBD) of Brisbane, Australia, which models the urban canyons of large cities around the world in that it boasts a great number of tall buildings, including many skyscrapers, meaning that most areas only see a small amount of direct sunlight each day. During the winter of 2007 measurements of UV radiation and in-vitro vitamin D production were collected in the CBD and at a suburban site approximately 2.5km outside the CBD. Air pollution data was obtained from a central CBD measurement site. Data analysis showed that urban canyon measurements of both UV radiation and in-vitro vitamin D production were significantly lower than those collected at the suburban site. These results will aid both future researchers and policy makers in better understanding human UV exposure in Brisbane’s CBD and other urban canyons around the world.

Ex vivo investigation of novel wound healing therapies and development of a 3-D human skin equivalent wound model

It has previously been found that complexes comprised of vitronectin and growth factors (VN:GF) enhance keratinocyte protein synthesis and migration. More specifically, these complexes have been shown to significantly enhance the migration of dermal keratinocytes derived from human skin. In view of this, it was thought that these complexes may hold potential as a novel therapy for healing chronic wounds. However, there was no evidence indicating that the VN:GF complexes would retain their effect on keratinocytes in the presence of chronic wound fluid. The studies in this thesis demonstrate for the first time that the VN:GF complexes not only stimulate proliferation and migration of keratinocytes, but also these effects are maintained in the presence of chronic wound fluid in a 2-dimensional (2-D) cell culture model. Whilst the 2-D culture system provided insights into how the cells might respond to the VN:GF complexes, this investigative approach is not ideal as skin is a 3-dimensional (3-D) tissue. In view of this, a 3-D human skin equivalent (HSE) model, which reflects more closely the in vivo environment, was used to test the VN:GF complexes on epidermopoiesis. These studies revealed that the VN:GF complexes enable keratinocytes to migrate, proliferate and differentiate on a de-epidermalised dermis (DED), ultimately forming a fully stratified epidermis. In addition, fibroblasts were seeded on DED and shown to migrate into the DED in the presence of the VN:GF complexes and hyaluronic acid, another important biological factor in the wound healing cascade. This HSE model was then further developed to enable studies examining the potential of the VN:GF complexes in epidermal wound healing. Specifically, a reproducible partial-thickness HSE wound model was created in fully-defined media and monitored as it healed. In this situation, the VN:GF complexes were shown to significantly enhance keratinocyte migration and proliferation, as well as differentiation. This model was also subsequently utilized to assess the wound healing potential of a synthetic fibrin-like gel that had previously been demonstrated to bind growth factors. Of note, keratinocyte re-epitheliasation was shown to be markedly improved in the presence of this 3-D matrix, highlighting its future potential for use as a delivery vehicle for the VN:GF complexes. Furthermore, this synthetic fibrin-like gel was injected into a 4 mm diameter full-thickness wound created in the HSE, both keratinocytes and fibroblasts were shown to migrate into this gel, as revealed by immunofluorescence. Interestingly, keratinocyte migration into this matrix was found to be dependent upon the presence of the fibroblasts. Taken together, these data indicate that reproducible wounds, as created in the HSEs, provide a relevant ex vivo tool to assess potential wound healing therapies. Moreover, the models will decrease our reliance on animals for scientific experimentation. Additionally, it is clear that these models will significantly assist in the development of novel treatments, such as the VN:GF complexes and the synthetic fibrin-like gel described herein, ultimately facilitating their clinical trial in the treatment of chronic wounds.

The city, self, and connections : transyouth and urban social networking in Seoul

The end of the Korean War in 1953 marked the beginning of Seoul’s transformation from the shattered capital city of South Korea to one of the most connected, populous, and fast-changing hubs of global economy. Seoul’s technosocial development has been celebrated nationally and internationally. To the outside, young Koreans’ swift and extensive adoption and adaptation to digital technologies has been a subject of exotification; to adults in Korea, it has been a subject of criticism (see Yoon in this volume). With the understanding that ‘the city is connections,’ it is crucial to study not only the macro-level design of the city as a network (through policy, for example), but also its micro-level construction at the intersection of people, place, and technology. Accordingly, this chapter explores this exact intersection to comprehensively portray the constant renewal of the city as imagined and experienced by young Koreans. The chapter is based on fieldwork conducted in Seoul, South Korea, from 2007 to 2008 as part of a research project on the mobile play culture of Seoul transyouth, the transitional demographic situated between youth and adulthood, and the pioneers of the Korean ‘broadband miracle’ (Hazlett, 2004). The study draws upon transdisciplinary research data including interviews, questionnaires, diaries, and Shared Visual Ethnography (SVE) to render the everyday urban social networking of young Seoulites with and through which they interact to constantly (re)create the city and the self.

Encounters and content sharing in an urban village : reading texts through an archaeological lens

Archaeology provides a framework of analysis and interpretation that is useful for disentangling the textual layers of a contemporary lived-in urban space. The producers and readers of texts may include those who planned and developed the site and those who now live, visit and work there. Some of the social encounters and content sharing between these people may be artificially produced or manufactured in the hope that certain social situations will occur. Others may be serendipitous. With archaeology’s original focus on places that are no longer inhabited it is often only the remaining artefacts and features of the built environment that form the basis for interpreting the social relationships of past people. Our analysis however, is framed within a contemporary notion of archaeological artefacts in an urban setting. Unlike an excavation, where the past is revealed through digging into the landscape, the application of landscape archaeology within a present day urban context is necessarily more experiential, visual and based on recording and analysing the physical traces of social encounters and relationships between residents and visitors. These physical traces are present within the creative content, and the built and natural elements of the environment. This chapter explores notions of social encounters and content sharing in an urban village by analysing three different types of texts: the design of the built environment; content produced by residents through a geospatial web application; and, print and online media produced in digital storytelling workshops.

Sleeper [for laptop computer and live performer]

Sleeper is an 18'00" musical work for live performer and laptop computer which exists as both a live performance work and a recorded work for audio CD. The work has been presented at a range of international performance events and survey exhibitions. These include the 2003 International Computer Music Conference (Singapore) where it was selected for CD publication, Variable Resistance (San Francisco Museum of Modern Art, USA), and i.audio, a survey of experimental sound at the Performance Space, Sydney. The source sound materials are drawn from field recordings made in acoustically resonant spaces in the Australian urban environment, amplified and acoustic instruments, radio signals, and sound synthesis procedures. The processing techniques blur the boundaries between, and exploit, the perceptual ambiguities of de-contextualised and processed sound. The work thus challenges the arbitrary distinctions between sound, noise and music and attempts to reveal the inherent musicality in so-called non-musical materials via digitally re-processed location audio. Thematically the work investigates Paul Virilio’s theory that technology ‘collapses space’ via the relationship of technology to speed. Technically this is explored through the design of a music composition process that draws upon spatially and temporally dispersed sound materials treated using digital audio processing technologies. One of the contributions to knowledge in this work is a demonstration of how disparate materials may be employed within a compositional process to produce music through the establishment of musically meaningful morphological, spectral and pitch relationships. This is achieved through the design of novel digital audio processing networks and a software performance interface. The work explores, tests and extends the music perception theories of ‘reduced listening’ (Schaeffer, 1967) and ‘surrogacy’ (Smalley, 1997), by demonstrating how, through specific audio processing techniques, sounds may shifted away from ‘causal’ listening contexts towards abstract aesthetic listening contexts. In doing so, it demonstrates how various time and frequency domain processing techniques may be used to achieve this shift.

Designing interaction for local communications : an urban screen study

This paper discusses the ongoing design and use of a digital community noticeboard situated in a suburban hub. The design intention is to engage residents, collect and display local information and communications, and spark discussion. A key contribution is an understanding of Situated Display navigation that aids retrieval from a long-term collection created by and for suburban community, and engaging qualities of this collection.

A national building products inventory

Australia has no nationally accepted building products life cycle inventory (LCI) database for use in building Ecologically Sustainable Development (ESD) assessment (BEA) tools. More information about the sustainability of the supply chain is limited by industry’s lack of real capacity to deliver objective information on process and product environmental impact. Recognition of these deficits emerged during compilation of a National LCI database to inform LCADesign, a prototype 3 dimensional object oriented computer aided design (3-D CAD) commercial building design tool. Development of this Australian LCI represents 24 staff years of effort here since 1995. Further development of LCADesign extensions is proposed as being essential to support key applications demanded from a more holistic theoretical framework calling for modules of new building and construction industry tools. A proposed tool, conceptually called LCADetails, is to serve the building product industries own needs as well as that of commercial building design amongst other industries’ prospective needs. In this paper, a proposition is examined that the existing national LCI database should be further expanded to serve Australian building product industries’ needs as well as to provide details for its client-base from a web based portal containing a module of practical supply and procurement applications. Along with improved supply chain assessment services, this proposed portal is envisaged to facilitate industry environmental life cycle improvement assessment and support decision-making to provide accredited data for operational reporting capabilities, load-based reasoning as well as BEA applications. This paper provides an overview of developments to date, including a novel 3-D CAD information and communications technology (ICT) platform for more holistic integration of existing tools for true cost assessment. Further conceptualisation of future prospects, based on a new holistic life cycle assessment framework LCADevelop, considering stakeholder relationships and their need for a range of complementary tools leveraging automated function off such ICT platforms to inform dimensionally defined operations for such as automotive, civil, transport and industrial applications are also explored.

Development of a particle number and particle mass vehicle emissions inventory for an urban fleet

Motor vehicles are major emitters of gaseous and particulate pollution in urban areas, and exposure to particulate pollution can have serious health effects, ranging from respiratory and cardiovascular disease to mortality. Motor vehicle tailpipe particle emissions span a broad size range from 0.003-10µm, and are measured as different subsets of particle mass concentrations or particle number count. However, no comprehensive inventories currently exist in the international published literature covering this wide size range. This paper presents the first published comprehensive inventory of motor vehicle tailpipe particle emissions covering the full size range of particles emitted. The inventory was developed for urban South-East Queensland by combining two techniques from distinctly different disciplines, from aerosol science and transport modelling. A comprehensive set of particle emission factors were combined with traffic modelling, and tailpipe particle emissions were quantified for particle number (ultrafine particles), PM1, PM2.5 and PM10 for light and heavy duty vehicles and buses. A second aim of the paper involved using the data derived in this inventory for scenario analyses, to model the particle emission implications of different proportions of passengers travelling in light duty vehicles and buses in the study region, and to derive an estimate of fleet particle emissions in 2026. It was found that heavy duty vehicles (HDVs) in the study region were major emitters of particulate matter pollution, and although they contributed only around 6% of total regional vehicle kilometres travelled, they contributed more than 50% of the region’s particle number (ultrafine particles) and PM1 emissions. With the freight task in the region predicted to double over the next 20 years, this suggests that HDVs need to be a major focus of mitigation efforts. HDVs dominated particle number (ultrafine particles) and PM1 emissions; and LDV PM2.5 and PM10 emissions. Buses contributed approximately 1-2% of regional particle emissions.

Being and Living in an Australian Urban Community

There is a limited evidence base which highlights the plight of Australian Aboriginal and Torres Strait Islander populations living in urban areas and the issues that impact on Indigenous achievements in education, health status, housing needs, rates of incarceration and the struggle for cultural recognition. This is despite over 70 % of all Aboriginal and Torres Strait Islander people in Australia now living in urban or regional urban areas (ABS 2008). The statistics demonstrate that living in urban centres is as much part of reality for Australian Aboriginal and Torres Strait Islander people as living in a remote discrete community. Using the capital city of Brisbane, Queensland as a case study, this paper will explore some of the issues that Aboriginal and Torres Strait Islander peoples face against a backdrop of the statistics and some of the current literature. It will additionally explore why there has been limited research with Aboriginal and Torres Strait Islander populations in urban areas and highlight some of the innovative research taking place which will begin to redress this gap. The research issues presented within this paper will resonate with some of the Native American and Indigenous movement patterns and associated issues additionally occurring in the United States of America, Canada and New Zealand.

The big brother : monitoring urban growth and change for sustainable infrastructure provision

Monitoring urban growth and land-use change is an important issue for sustainable infrastructure planning. Rapid urban development, sprawl and increasing population pressure, particularly in developing nations, are resulting in deterioration of infrastructure facilities, loss of productive agricultural lands and open spaces, pollution, health hazards and micro-climatic changes. In addressing these issues effectively, it is crucial to collect up-to-date and accurate data and monitor the changing environment at regular intervals. This chapter discusses the role of geospatial technologies for mapping and monitoring the changing environment and urban structure, where such technologies are highly useful for sustainable infrastructure planning and provision.

Chlamydial infection and spatial ascension of the female genital tract : a novel hybrid cellular automata and continuum mathematical model

Sexually transmitted chlamydial infection initially establishes in the endocervix in females, but if the infection ascends the genital tract, significant disease, including infertility, can result. Many of the mechanisms associated with chlamydial infection kinetics and disease ascension are unknown. We attempt to elucidate some of these processes by developing a novel mathematical model, using a cellular automata–partial differential equation model. We matched our model outputs to experimental data of chlamydial infection of the guinea-pig cervix and carried out sensitivity analyses to determine the relative influence of model parameters. We found that the rate of recruitment and action of innate immune cells to clear extracellular chlamydial particles and the rate of passive movement of chlamydial particles are the dominant factors in determining the early course of infection, magnitude of the peak chlamydial time course and the time of the peak. The rate of passive movement was found to be the most important factor in determining whether infection would ascend to the upper genital tract. This study highlights the importance of early innate immunity in the control of chlamydial infection and the significance of motility-diffusive properties and the adaptive immune response in the magnitude of infection and in its ascension.

Anti-metabolic effects of Galanthus nivalis agglutinin and wheat germ agglutinin on nymphal stages of the common brown leafhopper using a novel artificial diet system

The common brown leafhopper, Orosius orientalis (Matsumura) (Homoptera: Cicadellidae), previously described as Orosius argentatus (Evans), is an important vector of several viruses and phytoplasmas worldwide. In Australia, phytoplasmas vectored by O. orientalis cause a range of economically important diseases, including legume little leaf (Hutton & Grylls, 1956), tomato big bud (Osmelak, 1986), lucerne witches broom (Helson, 1951), potato purple top wilt (Harding & Teakle, 1985), and Australian lucerne yellows (Pilkington et al., 2004). Orosius orientalis also transmits Tobacco yellow dwarf virus (TYDV; genus Mastrevirus, family Geminiviridae) to beans, causing bean summer death disease (Ballantyne, 1968), and to tobacco, causing tobacco yellow dwarf disease (Hill, 1937, 1941). TYDV has only been recorded in Australia to date. Both diseases result in significant production and quality losses (Ballantyne, 1968; Thomas, 1979; Moran & Rodoni, 1999). Although direct damage caused by leafhopper feeding has been observed, it is relatively minor compared to the losses resulting from disease (P Tr E bicki, unpubl.).