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.

Cultural selection and its influence on perceptions of reputation within organisations

The capacity to identify, interpret, and prioritise environmental issues is critical in the management of corporate reputation. In spite of the significance of these abilities for corporate reputation management, there has been little effort to document and describe internal organizational influences on these capacities. Contrary to this state of affairs in the discipline of public relations, a long history of ethnographic research in cultural anthropology documents how sets of shared environmental perceptions can influence and moderate environmental factors in cultural populations (see for example, Durham, 1991 ). This study explores how cultural “frames of reference” derived from shared values and assumptions among organizational members influence organizational perceptions, and consequently, organizational actions. Specifically, this study explores how a central attribute of organizational culture--the property of cultural selection-- influences perceptions of organizational reputation held by organizational members. Perceptions of reputation among organizational members are obvious drivers to both the nature of and rationale for organizational communication strategies and responses. These perceptions are the result of collective processes that synthesise (with varying degrees of consensus) member conceptualisations, interpretations, and representations of the environmental realities in which their organization operate. To explore how cultural selection influences member perceptions of organizational reputation, this study employs ethnographic research including 20 depth interviews and six months of organizational observation in the focal organization. We argue that while external indicators of organizational reputation are acknowledged by members as significant, the internal action of cultural selection is a far stronger influence on organizational action.

Empowerment games : empathic design probes for user participation in community housing

This paper documents the empowering process of a group of public housing residents through different design probing exercises. These exercises worked along with existing social processes without any involvement of designers. This paper shows how a design researcher devised a series of probing tools called "empowerment games" with a group of active users. These games are self-learning tools for making the abstract language of design legible to users. The main purpose of this intitiative was to change the preconception of govenmental bodies and professional designers of the passivity of the users with regard to their designed environment. This was the first case of the application of a participatory design process in Hong Kong subsidized housing. Design empathy is a central skill when working with users throughout the whole design research project.

Firm social, cultural and intellectual capital : strategic indicators of international client satisfaction

Despite the increasing significance of the construction industry as an emerging sector of the Australian economy, there is inadequate research performed on construction design firms in terms of theoretical and empirical foundations. Although past research has identified the barriers and success factors for firm market entry, evidence suggests that to date no research has explicitly explored the sustainability of construction design firms in international markets. SMEs and their approach to firm internationalisation differ significantly from large manufacturing firms and a vast majority of construction design firms operate as SMEs. This paper develops a sustainable business model for construction design SMEs, which rely upon the development of clear Client Following (CF) versus Market Seeking (MS) strategies to support internal firm strategic and operational management. The understanding of these strategies is vital as the application of either will shape the design management approach of firms, which would in turn impact on the sustainability of these firms in foreign markets. Long-term sustainability of firms in international markets relies heavily upon client satisfaction. Client and project team participants’ communication during various design processes has often been problematic and the added difficulty of communicating across international boundaries further compounds the problem of capturing and maintaining client’s requirements. Therefore this paper develops a model for economic sustainability of Australian construction design firms working in international markets by exploring factors that affect client satisfaction across international boundaries, through the development of business performance indicators. These include not only the critical financial capital but also other ‘softer’ indicators, namely: social, cultural and intellectual capital. These act as a firm’s measure of success and the acquisition of this type of capital will provide significant advantages to firms’ success, hence sustainability in international markets.

An investigation of cross-cultural differences in binge-drinking perceptions and behaviours

This paper examines the variance in binge-drinking attitudes and behaviours between university student cohorts from Western and Eastern countries who reside in Australia. In particular, we investigate the impact of social influence on these consumer responses. An online survey resulted in 190 useable responses from university students at three different Australian universities. The results show that students from Western countries consume alcohol at higher levels and demonstrate more ‘approach’ behaviours towards binge-drinking, whereas students from Eastern countries demonstrate more ‘avoid’ behaviours. Social distancing from drunk or story-telling people is evident as students from Eastern countries while students from Western countries were more likely to indulge in story-telling and either ignored or encouraged surrounding people who were drunk.

Cross-cultural differences in self-reported decision-making style and confidence

The Melbourne Decision Making Questionnaire (Mann, Burnett, Radford, & Ford, 1997) measures selfreported decision-making coping patterns. The questionnaire was administered to samples of University students in the US (N = 475), Australia (N = 262), New Zealand (N = 260), Japan (N = 359), Hong Kong (N = 281), and Taiwan (N = 414). As predicted, students from the three Western, individualistic cultures (US, Australia, and New Zealand) were more con® dent of their decision-making ability than students from the three East Asian, group-oriented cultures (Japan, Hong Kong, Taiwan). No cross-cultural differences were found in scores on decision vigilance (a careful decision-making style). However, compared with Western students, the Asian students tended to score higher on buck-passing and procrastination (avoidant styles of decision making) as well as hypervigilance (a panicky style of decision making). Japanese students scored lowest on decision self-esteem and highest on procrastination and hypervigilance. It was argued that the con¯ ict model and its attendant coping patterns is relevant for describing and comparing decision making in both Western and Asian cultures.

Getting skilled for education, training and employment : Indigenous Cultural Knowledges and mainstream knowledges of mathematics

This abstract is a preliminary discussion of the importance of blending of Indigenous cultural knowledges with mainstream knowledges of mathematics for supporting Indigenous young people. This import is emphasised in the documents Preparing the Ground for Partnership (Priest, 2005), The Indigenous Education Strategic Directions 2008–2011 (Department of Education, Training and the Arts, 2007) and the National Goals for Indigenous Education (Department of Education, Employment and Work Relations, 2008). These documents highlight the contextualising of literacy and numeracy to students’ community and culture (see Priest, 2005). Here, Community describes “a culture that is oriented primarily towards the needs of the group. Martin Nakata (2007) describes contextualising to culture as about that which already exists, that is, Torres Strait Islander community, cultural context and home languages (Nakata, 2007, p. 2). Continuing, Ezeife (2002) cites Hollins (1996) in stating that Indigenous people belong to “high-context culture groups” (p. 185). That is, “high-context cultures are characterized by a holistic (top-down) approach to information processing in which meaning is “extracted” from the environment and the situation. Low-context cultures use a linear, sequential building block (bottom-up) approach to information processing in which meaning is constructed” (p.185). In this regard, students who use holistic thought processing are more likely to be disadvantaged in mainstream mathematics classrooms. This is because Westernised mathematics is presented as broken into parts with limited connections made between concepts and with the students’ culture. It potentially conflicts with how they learn. If this is to change the curriculum needs to be made more culture-sensitive and community orientated so that students know and understand what they are learning and for what purposes.

Remediating vernacular creativity : photography and cultural citizenship in the Flickr photosharing network

Read through a focus on the remediation of personal photography in the Flickr photosharing website, in this essay I treat vernacular creativity as a field of cultural practice; one that that does not operate inside the institutions or cultural value systems of high culture or the commercial popular media, and yet draws on and is periodically appropriated by these other systems in dynamic and productive ways. Because of its porosity to commercial culture and art practice, this conceptual model of ‘vernacular creativity’ implies a historicised account of ‘ordinary’ or everyday creative practice that accounts for both continuity and change and avoids creating a nostalgic desire for the recuperation of an authentic folk culture. Moving beyond individual creative practice, the essay concludes by considering the unintended consequences of vernacular creativity practiced in online social networks: in particular, the idea of cultural citizenship.