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.

Doing cultural heritage using the torque game engine: supporting indigenous storytelling in a 3D virtual environment

Digital Songlines (DSL) is an Australasian CRC for Interaction Design (ACID) project that is developing protocols, methodologies and toolkits to facilitate the collection, education and sharing of indigenous cultural heritage knowledge. This paper outlines the goals achieved over the last three years in the development of the Digital Songlines game engine (DSE) toolkit that is used for Australian Indigenous storytelling. The project explores the sharing of indigenous Australian Aboriginal storytelling in a sensitive manner using a game engine. The use of the game engine in the field of Cultural Heritage is expanding. They are an important tool for the recording and re-presentation of historically, culturally, and sociologically significant places, infrastructure, and artefacts, as well as the stories that are associated with them. The DSL implementation of a game engine to share storytelling provides an educational interface. Where the DSL implementation of a game engine in a CH application differs from others is in the nature of the game environment itself. It is modelled on the 'country' (the 'place' of their heritage which is so important to the clients' collective identity) and authentic fauna and flora that provides a highly contextualised setting for the stories to be told. This paper provides an overview on the development of the DSL game engine.

Discovering, applying and integrating: The process of learning in coaching

Professional coaching is a rapidly expanding field with interdisciplinary roots and broad application. However, despite abundant prescriptive literature, research into the process of coaching is minimal. Similarly, although learning is inherently recognised in the process of coaching, the process of learning in coaching is little understood and learning theory makes up only a small part of the evidence-based coaching literature. In this grounded theory study of coaches and their clients, the process of learning in coaching across a range of coaching models is examined and discussed. The findings demonstrate how learning in coaching emerged as a process of discovering, applying and integrating new knowledge, which culminated in a process of developing. This process occurred through eight key coaching processes shared between coaches and clients and combined a multitude of learning theories.

Improving the management of building life cycle : a data mining approach

The construction industry has adapted information technology in its processes in terms of computer aided design and drafting, construction documentation and maintenance. The data generated within the construction industry has become increasingly overwhelming. Data mining is a sophisticated data search capability that uses classification algorithms to discover patterns and correlations within a large volume of data. This paper presents the selection and application of data mining techniques on maintenance data of buildings. The results of applying such techniques and potential benefits of utilising their results to identify useful patterns of knowledge and correlations to support decision making of improving the management of building life cycle are presented and discussed.

Literature Review Value Alignment Process for Project Delivery

The objective of the project “Value Alignment Process for Project Delivery” is to provide a catalyst and tools for reform in the building and construction industry to transform business-as-usual performance into exceptional performance. The outcomes of this project will be beneficial to not only the construction industry, but to the community as a whole because a more sophisticated industry can deliver more effective use of assets, financing, operating and maintenance of facilities to suit the community’s needs. The research project consists of a study into best practice project delivery and the development of a suite of products, resources and services to guide project teams towards the best approach for a specific project. These resources will be focused on promoting the principles that underlie best practice project delivery, rather than on identifying a particular delivery system. The need for such tools and resources becomes more and more acute as the environment within which the construction industry operates becomes more and more complex, and as business and political imperatives shift to encompass or represent diverse stakeholder interests. To this end, this literature review looks at why it is essential to achieve transformation in the Australian construction industry in the context of its importance to the Australian economy. It seeks to investigate the concepts of ‘alignment’ and value’ as they pertain to construction industry processes and relationships. It comprehensively reviews drivers of project excellence and best practice project delivery principles and looks at how clients approach selection of project delivery systems. It critiques existing project delivery strategies and gives an overview of recent best practice initiatives. The literature review represents a milestone against the Project Agreement and forms a foundation document for this research project

Building procurement methods

A plethora of methods for procuring building projects are available to meet the needs of clients. Deciding what method to use for a given project is a difficult and challenging task as a client’s objectives and priorities need to marry with the selected method so as to improve the likelihood of the project being procured successfully. The decision as to what procurement system to use should be made as early as possible and underpinned by the client’s business case for the project. The risks and how they can potentially affect the client’s business should also be considered. In this report, the need for client’s to develop a procurement strategy, which outlines the key means by which the objectives of the project are to be achieved is emphasised. Once a client has established a business case for a project, appointed a principal advisor, determined their requirements and brief, then consideration as to which procurement method to be adopted should be made. An understanding of the characteristics of various procurement options is required before a recommendation can be made to a client. Procurement systems can be categorised as traditional, design and construct, management and collaborative. The characteristics of these systems along with the procurement methods commonly used are described. The main advantages and disadvantages, and circumstances under which a system could be considered applicable for a given project are also identified.

BRITE report 2004

This document reports on an innovation survey of the Australian construction industry undertaken by the BRITE Project of the CRC for Construction Innovation in 2004. The survey sample was drawn from 3,500 businesses in the road/bridge and commercial building sectors in NSW, Vic and Qld, covering main contractors, trade contractors, consultants, suppliers and clients. One-third of this population was sampled and a response rate of 30% was achieved. The survey investigates innovation determinants in the industry, comprising various aspects of business strategy and business environment.

Brite innovation survey : executive summary

This report summarises the fi ndings of an innovation survey of the Australian construction industry undertaken by the BRITE Project of the CRC for Construction Innovation in 2004. The BRITE Innovation Survey can be viewed in full at www.brite.crcci.info.The objective of the BRITE project is to improve the incidence and quality of innovation in the Australian construction industry. Many stakeholders in the industry are sceptical about the potential for innovation and its likely benefi ts. Many also lack the linkages and capabilities required for successful innovation. The BRITE Project is redressing this situation through demonstration and benchmarking activities. The term ‘innovation’ is defi ned as a new or signifi cantly improved technology or advanced business practice. Innovation may be technological or organisational, and it may be new to the world, or just new to the industry or business concerned. The defi nition includes the adoption of existing advancements developed outside a particular business. The survey sample was drawn from 3,500 businesses in the road/bridge and commercial building sectors in New South Wales, Victoria and Queensland, covering main contractors, trade contractors, consultants, suppliers and clients. Onethird of this population was sampled and a response rate of almost 30% was achieved. The survey collected information about respondents’ perceptions of innovation determinants in the industry, comprising various aspects of business strategy and business environment.

Ethical behaviour in the construction procurement process

In construction, inter-organisational relationships are of the highest importance. Ethical practice and behaviour is a means for improving inter-organisational relationships by providing a clear understanding of the rights and obligations of all parties, improving productivity, affecting long-term business dealings, and influencing quality, time and costs. Therefore, the ability to build sustainable relationships grounded in ethical practice is important to the construction industry. Establishing ethical standards at the beginning of the procurement process provides an ethical platform for the project life cycle and the relationship between procurers and contractors. Therefore it is important to determine what the ethical issues are in the Australian construction industry from members of the industry themselves; including clients. This “bottom up” approach is not a particularly new concept. Ever since the Gyles Royal Commission in 1992 there has been a considerable effort by government agencies to develop policies to improve the ethical behaviour of the industry.

Assessing the structure of learning outcomes from counselling using the SOLO taxonomy: an exploratory study

Thirty-five clients who had received counselling completed a letter to a friend describing in as much detail as possible what they had learned from counselling. The participants' written responses were analysed and classified using the Structure of Learning Outcomes (SOLO) taxonomy. The results suggested that an expanded SOLO offers a promising and exciting way to view the outcomes of counselling within a learning framework. If the SOLO taxonomy is found to be stable in subsequent research, and clients are easily able to be classified using the taxonomy, then this approach may have implications for the process of counselling. To maximise the learning outcomes, counsellors could use strategies and techniques to enhance their clients' learning.

Health professional partnerships and their impact on Aboriginal health : an occupational therapist's and Aboriginal health worker's perspective

Objective: To describe the extent and nature of demonstrated professional partnerships between occupational therapists and Aboriginal health workers in rural and remote communities of North Queensland. The study identifies ways in which professional partnerships improve client services and enhance occupational therapy outcomes through exploring the aspects of communication, collaboration and bridging cultural boundaries.---------- Design: Data collected via in-depth, semistructured telephone interviews. ---------- Setting: Aboriginal and mainstream health and human service organisations in rural and remote North Queensland. Rural and remote areas were identified using the Accessibility and Remoteness Index of Australia codes. ---------- Participants: Seven participants working in rural and remote areas of North Queensland, comprising four occupational therapists and three Aboriginal health workers. All participants were female. ---------- Results: Participants identified five core themes when describing the extent and nature of professional partnerships between occupational therapists and Aboriginal health workers. Themes include: professional interaction; perception of professional roles; benefits to the client; professional interdependence; and significance of Aboriginal culture. According to participants, when partnerships between occupational therapists and Aboriginal health workers were formed, clients received a more culturally appropriate service, were more comfortable in the presence of the occupational therapist, obtained a greater understanding of occupational therapy assessment and intervention, and felt valued in the health care process. ---------- Conclusions: This study substantiates the necessity for the formation of professional partnerships between occupational therapists and Aboriginal health workers. The findings suggest that participation in professional partnerships has positive implications for occupational therapists working with Aboriginal clients and Aboriginal health workers in rural and remote regions of North Queensland.

Procurement selection in the public sector : a tale of two states.

The decision as to which procurement system to adopt is a complex and challenging task for clients of construction projects. Despite a plethora of tools and techniques available for selecting a procurement method, clients are still uncertain about what method to adopt for a given construction project to achieve success. This paper examines ‘how and why’ procurement methods are selected by public sector clients in Queensland (QLD) and Western Australia (WA). Findings from workshops with senior managers in procurement selection revealed that traditional lump sum methods (TLS) are preferred even though alternative forms could be better suited for a given project. Participants of the workshops agreed that alternative procurement forms should be considered for projects but an embedded culture of uncertainty avoidance meant the selection of TLS methods. It was perceived that only a limited number of contractors operating in the marketplace have the resources and experience to deliver projects using the non-traditional methods.

Evaluation of distress mechanisms in bridges exposed to aggressive environments.

There are about 2500 bridges in Queensland, Australia. Majority of these structures require significant repairs around the halfway mark of their design life with probably 1% or less reaching a 100 year design life. (Carse, 2005). This is due to the fact that bridges constructed in aggressive environments such as the coastal regions experience accelerated deterioration. As a result, maintaining the service delivery of these assets has become one of the important issues for the Queensland Department of Main Roads (QDMR).

Benchmarks for recycling practices in commercial office building refurbishment : data collection challenges

In recent years considerable effort has gone into quantifying the reuse and recycling potential of waste generated by residential construction. Unfortunately less information is available for the commercial refurbishment sector. It is hypothesised that significant economic and environmental benefit can be derived from closer monitoring of the commercial construction waste stream. With the aim of assessing these benefits, the authors are involved in ongoing case studies to record both current standard practice and the most effective means of improving the eco-efficiency of materials use in office building refurbishments. This paper focuses on the issues involved in developing methods for obtaining the necessary information on better waste management practices and establishing benchmark indicators. The need to create databases to establish benchmarks of waste minimisation best practice in commercial construction is stressed. Further research will monitor the delivery of case study projects and the levels of reuse and recycling achieved in directly quantifiable ways