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.

Using ontology for the representational analysis of process modelling techniques

Selecting an appropriate business process modelling technique forms an important task within the methodological challenges of a business process management project. While a plethora of available techniques has been developed over the last decades, there is an obvious shortage of well-accepted reference frameworks that can be used to evaluate and compare the capabilities of the different techniques. Academic progress has been made at least in the area of representational analyses that use ontology as a benchmark for such evaluations. This paper reflects on the comprehensive experiences with the application of a model based on the Bunge ontology in this context. A brief overview of the underlying research model characterizes the different steps in such a research project. A comparative summary of previous representational analyses of process modelling techniques over time gives insights into the relative maturity of selected process modelling techniques. Based on these experiences suggestions are made as to where ontology-based representational analyses could be further developed and what limitations are inherent to such analyses.

Fashion as consumer entrepreneurship : emergent risk culture, social network markets, and the launch of 'Vogue' in China

China has a reputation as an economy based on utility: the large-scale manufacture of low-priced goods. But useful values like functionality, fitness for purpose and efficiency are only part of the story. More important are what Veblen called ‘honorific’ values, arguably the driving force of development, change and value in any economy. To understand the Chinese economy therefore, it is not sufficient to point to its utilitarian aspect. Honorific status-competition is a more fundamental driver than utilitarian cost-competition. We argue that ‘social network markets’ are the expression of these honorific values, relationships and connections that structure and coordinate individual choices. This paper explores how such markets are developing in China in the area of fashion and fashion media. These, we argue, are an expression of ‘risk culture’ for high-end entrepreneurial consumers and producers alike, providing a stimulus to dynamic innovation in the arena of personal taste and comportment, as part of an international cultural system based on constant change. We examine the launch of Vogue China in 2005, and China’s reception as a fashion player among the international editions of Vogue, as an expression of a ‘decisive moment’ in the integration of China into an international social network market based on honorific values.

Consumer acceptance of m-services : Marketing implcations

Consumers' evolving relationships with their mobile devices and their desire to access mobile services (m-services) present new opportunities to marketers, yet little research has been conducted in the area of m-services. Using structural equation modelling, this paper examines the effect of hedonic and utilitarian value of mobile phones on product and purchase involvement. It also investigates the effect of involvement, innovativeness, and self-efficacy on use of m-services. Data were collected from a convenience sample of 250 respondents using an online survey and a modified snowball procedure. Findings are discussed, further implications for managers are suggested and directions for future research are proposed.

Examination of the influence of personal attributes on consumer use on m-services

The rapid uptake of mobile devices has created the capacity to provide services to consumers while they are on the move, and new mobile services (m-services) are constantly emerging. In past research, personal attributes have been found to be import ant in the adoption and use of information and communication technology. However, little research has been conducted in the area of m-services. To explore factors influencing the use of these services, this paper examines personal attributes in terms of motivational, attitudinal and demographic characteristics. Specifically, it investigates the influence of innovativeness, self- efficacy, involvement and impulsiveness, as well as age and gender on m-services use . Data were collected from a convenience sample of 250 respondents using an online survey and a modified snowball procedure. Age and gender were quite well balanced in the sample. The multiple regression model was significant and the hypotheses relating to the positive relationship between impulsiveness, involvement and gender and m-services were supported. Findings are discussed, further implications for managers are suggested and directions for future research are proposed.

A review of LCADesign

Objective The review addresses two distinct sets of issues: 1. specific functionality, interface, and calculation problems that presumably can be fixed or improved; and 2. the more fundamental question of whether the system is close to being ready for ‘commercial prime time’ in the North American market. Findings Many of our comments relate to the first set of issues, especially sections B and C. Sections D and E deal with the second set. Overall, we feel that LCADesign represents a very impressive step forward in the ongoing quest to link CAD with LCA tools and, more importantly, to link the world of architectural practice and that of environmental research. From that perspective, it deserves continued financial support as a research project. However, if the decision is whether or not to continue the development program from a purely commercial perspective, we are less bullish. In terms of the North American market, there are no regulatory or other drivers to press design teams to use a tool of this nature. There is certainly interest in this area, but the tools must be very easy to use with little or no training. Understanding the results is as important in this regard as knowing how to apply the tool. Our comments are fairly negative when it comes to that aspect. Our opinion might change to some degree when the ‘fixes’ are made and the functionality improved. However, as discussed in more detail in the following sections, we feel that the multi-step process — CAD to IFC to LCADesign — could pose a serious problem in terms of market acceptance. The CAD to IFC part is impossible for us to judge with the information provided, and we can’t even begin to answer the question about the ease of using the software to import designs, but it appears cumbersome from what we do know. There does appear to be a developing North American market for 3D CAD, with a recent survey indicating that about 50% of the firms use some form of 3D modeling for about 75% of their projects. However, this does not mean that full 3D CAD is always being used. Our information suggests that AutoDesk accounts for about 75 to 80% of the 3D CAD market, and they are very cautious about any links that do not serve a latent demand. Finally, other system that link CAD to energy simulation are using XML data transfer protocols rather than IFC files, and it is our understanding that the market served by AutoDesk tends in that direction right now. This is a subject that is outside our area of expertise, so please take these comments as suggestions for more intensive market research rather than as definitive findings.

The Impact of Experiential Learning in Enhancing Palliative Care Knowledge and Skills among Nurses

Nurses working in community settings are increasingly required to care for people with chronic, life limiting conditions. Innovative educational programs are required to ensure nurses are equipped to deal with this challenging area of practice. The Program of Experience in the Palliative Approach (PEPA) started in 2003 as an initiative of the Australian Government, Department of Health and Ageing. The overall aim of PEPA is to improve the quality, availability and access to palliative care for people who are dying, and their families, by improving the skills and expertise of health practitioners, and enhancing collaboration between primary and specialist palliative care services. PEPA provides nurses with an opportunity to develop knowledge and skills in the palliative approach to care through funded clinical workforce placements or workshops.

Citizen journalism and everyday life : A case study of Germany’s myHeimat.de

Much recent research into citizen journalism has focussed on its role in political debate and deliberation. Such research examines important questions about citizen participation in democratic processes – however, it perhaps places undue focus on only one area of journalistic coverage, and presents a challenge which only a small number of citizen journalism projects can realistically hope to meet. A greater opportunity for broad-based citizen involvement in journalistic activities may lie outside of politics, in the coverage of everyday community life. A leading exponent of this approach is the German-based citizen journalism Website myHeimat.de, which provides a nationwide platform for participants to contribute reports about events in their community. myHeimat takes a hyperlocal approach but also allows for content aggregation on specific topics across multiple local communities; Hannover-based newspaper publishing house Madsack has recently acquired a stake in the project. Drawing on extensive interviews with myHeimat CEO Martin Huber and Madsack newspaper editors Peter Taubald and Clemens Wlokas during October 2008, this paper analyses the myHeimat project and examines its applicability beyond rural and regional areas in Germany; it investigates the question of what role citizen journalism may play beyond the political realm.

Contemporary consumer law : the role and effectiveness of regulation in consumer protection

This issue of the Griffith Law Review focuses on consumer law, and the pervasive nature of this area of law. We are all consumers, but do not necessarily identify as such, nor are we a homogeneous group. The boundaries of

Addressing the needs of struggling literacy learners

Think back to your teaching experiences over the past four years. Were there a number of children or adolescents in your classes who seemed to have learning difficulties? What area of their learning seemed to be of greatest concern for these students? Did most of these struggling learners have difficulty with reading? Was expressing their thoughts in writing also a challenge? Did some of these students also have difficulty in listening to and following directions? And did some of these students seem hesitant when asked to speak to the class?

The efficacy of waste management plans in Australian commercial construction refurbishment projects

Renovation and refurbishment of the existing commercial building stock is a growing area of total construction activity and a significant generator of waste sent to landfill in Australia. A written waste management plan (WMP) is a widespread regulatory requirement for commercial office redevelopment projects. There is little evidence, however, that WMPs actually increase the quantity of waste that is ultimately diverted from landfill. Some reports indicate an absence of any formal verification or monitoring process by regulators to assess the efficacy of the plans. In order to gauge the extent of the problem a survey was conducted of twenty four consultants and practitioners involved in commercial office building refurbishment projects to determine the state of current practice with regard to WMPs and to elicit suggestions with regard to ways of making the process more effective. Considerable variation in commitment to recycling policies was encountered indicating a need to revisit waste minimisation practices if the environmental performance of refurbishment projects is to be improved.

Exploring product placement in video games : an investigation of recall effects

Despite its growth and prominence, product placement is generally under-researched and this is even more apparent in the area of placement in video gaming. This paper presents exploratory focus group research into this practice. Findings indicate that the introductory footage to a game provides placement opportunities with the highest level of recall, while peripheral non-action is the worst. Interestingly, recall also appears to be higher for individual brands as opposed to manufacturer brands.

A longitudinal study of motivation and competence in children with Down syndrome : early childhood to early adolescence

Background Motivation has been identified as an area of difficulty for children with Down syndrome. Although individual differences in mastery motivation are presumed to have implications for subsequent competence, few longitudinal studies have addressed the stability of motivation and the predictive validity of early measures for later academic achievement, especially in atypical populations. Method The participants were 25 children with Down syndrome. Mastery motivation, operationalised as persistence, was measured in early childhood and adolescence using tasks and parent report. At the older age, preference for challenge, another aspect of mastery motivation, was also measured and the children completed assessments of academic competence. Results There were significant concurrent correlations among measures of persistence at both ages, and early task persistence was associated with later persistence. Persistence in early childhood was related to academic competence in adolescence, even when the effects of cognitive ability at the younger age were controlled. Conclusions For children with Down syndrome, persistence appears to be an individual characteristic that is relatively stable from early childhood to early adolescence. The finding that early mastery motivation is significant for later achievement has important implications for the focus of early interventions.

Termination of a minor’s pregnancy : critical issues for consent and the criminal law

The recent Supreme Court decision of Queensland v B [2008] 2 Qd R 562 has significant implications for the law that governs consent and abortions. The judgment purports to extend the ratio of Secretary, Department of Health and Community Services (NT) v JWB and SMB (1991) 175 CLR 218 (Marion’s Case) and impose a requirement of court approval for terminations of pregnancy for minors who are not Gillick-competent. This article argues against the imposition of this requirement on the ground that such an approach is an unjustifiable extension of the reasoning in Marion’s Case. The decision, which is the first judicial consideration in Queensland of the position of medical terminations, also reveals systemic problems with the criminal law in that State. In concluding that the traditional legal excuse for abortions will not apply to those which are performed medically, Queensland v B provides further support for calls to reform this area of law.

Major depressive disorder and nutritional medicine : a review of monotherapies and adjuvant treatments

A literature review was conducted to examine the evidence for nutritional interventions in depression. It revealed a number of significant conclusions. Interestingly, more positive clinical trials were found to support adjuvant, rather than monotherapeutic, use of nutrients to treat depression. Much evidence exists in the area of adjuvant application of folic acid, S-adenosyl-methionine, omega-3, and L-tryptophan with antidepressants. Current evidence does not support omega-3 as an effective monotherapy to treat depression. However, this may be due, at least in part, to olive oil being used as the control intervention, some studies using docosahexaenoic acid alone or a higher docosahexaenoic acid to eicosapentaenoic acid ratio, and significant heterogeneity regarding depressive populations. Nevertheless, adjunctive prescription of omega-3 with antidepressants, or in people with dietary deficiency, may be beneficial. Inositol lacks evidence as an effective antidepressant and cannot be currently recommended. Evidence on the use of L-trytophan for depression is inconclusive and additional studies utilizing a more robust methodology are required.