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.

Understanding the physical processes of pollutant build-up and wash-off on roof surfaces

Pollutants originating with roof runoff can have a significant impact to urban stormwater quality. This signifies the importance of understanding pollutant processes on roof surfaces. Additionally, knowledge of pollutant processes on roof surfaces is important as roofs are used as the primary catchment surface for domestic rainwater harvesting. In recent years, rainwater harvesting has become one of the primary sustainable water management techniques to counteract the growing demand for potable water. Similar to all impervious services, pollutants associated with roof runoff undergo two primary processes: build-up and wash-off. The knowledge relating to these processes is limited. This paper presents outcomes of an in-depth research study into pollutant build-up and wash-off for roof surfaces. The knowledge will be important in order to develop appropriate strategies to safeguard rainwater users from possible health risks.

Equal employment opportunity and diversity management : can either live up to the promise of achieving gender equity?

This paper examines the extent to which women movement into management positions. Like many other countries, this progress in Australia is slow. The paper includes discussion of the theoretical explanations for this and the extent to which these are borne out in Australia. We are aware this group represents only a minority of Australian women workers, and there are many other groups of women workers for whom constraints to women’s access to senior management may not be the most pressing issue. We have, however, chosen to focus on women in management in this paper, as while there was considerable research and public policy attention directed towards this group in the 1980s and early 1990s, over the past decade there seems to have been a reluctance to continue to address this group, despite the numerical evidence that women continue to be disproportionately represented in senior management positions. We believe it’s timely to refocus on women in management.

Infrared and infrared emission spectroscopy of gallium oxide α-GaO(OH) nanostructures

Infrared spectroscopy has been used to study nano to micro sized gallium oxyhydroxide α-GaO(OH), prepared using a low temperature hydrothermal route. Rod-like α-GaO(OH) crystals with average length of ~2.5 μm and width of 1.5 μm were prepared when the initial molar ratio of Ga to OH was 1:3. β-Ga2O3 nano and micro-rods were prepared through the calcination of α-GaO(OH) The initial morphology of α-GaO(OH) is retained in the β-Ga2O3 nanorods. The combination of infrared and infrared emission spectroscopy complimented with dynamic thermal analysis were used to characterise the α-GaO(OH) nanotubes and the formation of β-Ga2O3 nanorods. Bands at around 2903 and 2836 cm-1 are assigned to the -OH stretching vibration of α-GaO(OH) nanorods. Infrared bands at around 952 and 1026 cm-1 are assigned to the Ga-OH deformation modes of α-GaO(OH). A significant number of bands are observed in the 620 to 725 cm-1 region and are assigned to GaO stretching vibrations.

Catching up with consumer realities: the need for legislation prohibiting unfair terms in consumer contracts

In the policy debate about the need for legislation to prohibit the use of unfair terms in consumer contracts, substantive unfairness is often distinguished from procedural unfairness. Current consumer protection laws appear to offer the potential for relief on substantive unfairness grounds alone. However, a review of cases involving credit contracts shows this potential is rarely realised. This reluctance to provide relief for substantive injustice reflects a preoccupation with freedom and certainty of contract, the notions underpinning classical contract theories. As a class, consumers are vulnerable in the marketplace, and they do need protection from substantively unfair terms. A new framework for regulating consumer contracts is needed, one that relies less on classical contract theories and takes the reality of consumer contracting and consumer behavior as its starting point. Unfair contract terms legislation will be a step on the path towards this new framework.

The cost-effectiveness of routine follow-up after primary total hip arthroplasty

Routine postsurgery assessment of primary total hip arthroplasty (THA) is recommended in many countries. Whether the benefits of this activity are justified by the costs is not known. We used a decision-analytic Markov model to compare the costs and health outcomes of 3 different follow-up strategies after primary THA. If there is no routine follow-up of patients for 7 years after primary THA, there would be cost savings between AU$6.5 and $11.9 million and gains of between 1.8 and 8.8 quality-adjusted life years. Policy makers should investigate less resource-intensive alternatives to common routine postsurgical assessment.

Tricking up the suburb

The following article arises from the projects submitted for the 2004 Awards fo the Western Australian Chapter of the Australian Institute of Landscape Architects, for which we were judges, together with Craig Burton of CAB Consulting and Natalie palleros of Tierra Design. This article is an attempt to understand some dominant trends that emerged from viewing a range of new suburban developments. Suburban developments dominated the awards and seemed to characterise much of the work being done by landscape architects in the west. It is easy to be critical of contemporary landscape architecture in Perth, as the projects presented were mostly the same in that their scope of design activity was restricted to the decorative rather than the structural. However, as critics, we feel it is important to initate a conversation about what has been presented as the best of the profession, in order to begin to understand the current state of the profession.

"Okay girl, it's up to you": a case study of the use of a seizure alert dog to improve the wellbeing of a student with epilepsy

The relationship between student well-being and the other vital outcomes of school is unequivocal. Improved outcomes in all aspects of student well-being are positively associated with improved outcomes in all other aspects of schooling. This educational imperative only serves to strengthen and support the moral imperative for schools and schooling to be inclusive, supportive and nurturing in order to maintain and support student well-being. (Fraillon 2005, p. 12)

8-Ammonionaphthalene-2-sulfonate monohydrate : the zwitterionic hydrate of 1,7-Cleve's acid

The structure of 8-amino-2-naphthalenesulfonic acid monohydrate (1,7-Cleve's acid hydrate), C10H9NO3S.H2O, shows the presence of a sulfonate-aminium group zwitterion, both groups and the water molecule of solvation giving cyclic R3/3(8) intermolecular hydrogen-bonding interactions forming chains which extend down a axis of the unit cell. Additional peripheral associations, including weak aromatic ring pi-pi interactions [centroid-centroid distance 3.6299(15)A], result in a two-dimensional sheet structure.

4-Chloroanilinium 2-carboxy-4,5-dichlorobenzoate

The structure of the 1:1 proton-transfer compound of 4-chloroaniline with 4,5-dichlorophthalic acid (DCPA), viz. C6H7ClN+ C8H3Cl2O4-, has been determined at 130 K. The non-planar hydrogen phthalate anions and the 4-chloroanilinium cations form two-dimensional O-H...O and N-H...O hydrogen-bonded substructures which have no peripheral extension. Between the sheets there are weak \p--\p associations between alternating cation--anion aromatic ring systems [shortest centroid separation, 3.735(4)A].