The encapsulation of gold nanoparticles using RAFT, ATRP and miniemulsion polymerisation techniques

The investigation into the encapsulation of gold nanoparticles (AuNPs) by poly(methyl methacrylate) (PMMA) was undertaken. This was performed by three polymerisation techniques including: grafting PMMA synthesised by reversible addition-fragmentation chain transfer (RAFT) polymerisation to AuNPs, grafting PMMA synthesised by atom transfer radical polymerisation (ATRP) from the surface of functionalised AuNPs and by encapsulation of AuNPs within PMMA latexes produced through photo-initiated oil-in-water (o/w) miniemulsion polymerisation. The grafting of RAFT PMMA to AuNPs was performed by the addition of the RAFT functionalised PMMA to citrate stabilised AuNPs. This was conducted with a range of PMMA of varying molecular weight distribution (MWD) as either the dithioester or thiol end-group functionalities. The RAFT PMMA polymers were characterised by gel permeation chromatography (GPC), ultraviolet-visible (UV-vis), Fourier transform infrared-attenuated total reflectance (FTIR-ATR), Fourier transform Raman (FT-Raman) and proton nuclear magnetic resonance (1H NMR) spectroscopies. The attachment of PMMA to AuNPs showed a tendency for AuNPs to associate with the PMMA structures formed, though significant aggregation occurred. Interestingly, thiol functionalised end-group PMMA showed very little aggregation of AuNPs. The spherical polymer-AuNP structures did not vary in size with variations in PMMA MWD. The PMMA-AuNP structures were characterised using scanning electron microscopy (SEM), transition electron microscopy (TEM), energy dispersive X-ray analysis (EDAX) and UV-vis spectroscopy. The surface confined ATRP grafting of PMMA from initiator functionalised AuNPs was polymerised in both homogeneous and heterogeneous media. 11,11’- dithiobis[1-(2-bromo-2-methylpropionyloxy)undecane] (DSBr) was used as the surface-confined initiator and was synthesised in a three step procedure from mercaptoundecanol (MUD). All compounds were characterised by 1H NMR, FTIR-ATR and Raman spectroscopies. The grafting in homogeneous media resulted in amorphous PMMA with significant AuNP aggregation. Individually grafted AuNPs were difficult to separate and characterise, though SEM, TEM, EDAX and UV-vis spectroscopy was used. The heterogeneous polymerisation did not produce grafted AuNPs as characterised by SEM and EDAX. The encapsulation of AuNPs within PMMA latexes through the process of photoinitiated miniemulsion polymerisation was successfully achieved. Initially, photoinitiated miniemulsion polymerisation was conducted as a viable low temperature method of miniemulsion initiation. This proved successful producing a stable PMMA with good conversion efficiency and narrow particle size distribution (PSD). This is the first report of such a system. The photo-initiated technique was further optimised and AuNPs were included into the miniemulsion. AuNP encapsulation was very effective, producing reproducible AuNP encapsulated PMMA latexes. Again, this is the first reported case of this. The latexes were characterised by TEM, SEM, GPC, gravimetric analysis and dynamic light scattering (DLS).

Synthesis and modifications of metal oxide nanostructures and their applications

Transition metal oxides are functional materials that have advanced applications in many areas, because of their diverse properties (optical, electrical, magnetic, etc.), hardness, thermal stability and chemical resistance. Novel applications of the nanostructures of these oxides are attracting significant interest as new synthesis methods are developed and new structures are reported. Hydrothermal synthesis is an effective process to prepare various delicate structures of metal oxides on the scales from a few to tens of nanometres, specifically, the highly dispersed intermediate structures which are hardly obtained through pyro-synthesis. In this thesis, a range of new metal oxide (stable and metastable titanate, niobate) nanostructures, namely nanotubes and nanofibres, were synthesised via a hydrothermal process. Further structure modifications were conducted and potential applications in catalysis, photocatalysis, adsorption and construction of ceramic membrane were studied. The morphology evolution during the hydrothermal reaction between Nb2O5 particles and concentrated NaOH was monitored. The study demonstrates that by optimising the reaction parameters (temperature, amount of reactants), one can obtain a variety of nanostructured solids, from intermediate phases niobate bars and fibres to the stable phase cubes. Trititanate (Na2Ti3O7) nanofibres and nanotubes were obtained by the hydrothermal reaction between TiO2 powders or a titanium compound (e.g. TiOSO4·xH2O) and concentrated NaOH solution by controlling the reaction temperature and NaOH concentration. The trititanate possesses a layered structure, and the Na ions that exist between the negative charged titanate layers are exchangeable with other metal ions or H+ ions. The ion-exchange has crucial influence on the phase transition of the exchanged products. The exchange of the sodium ions in the titanate with H+ ions yields protonated titanate (H-titanate) and subsequent phase transformation of the H-titanate enable various TiO2 structures with retained morphology. H-titanate, either nanofibres or tubes, can be converted to pure TiO2(B), pure anatase, mixed TiO2(B) and anatase phases by controlled calcination and by a two-step process of acid-treatment and subsequent calcination. While the controlled calcination of the sodium titanate yield new titanate structures (metastable titanate with formula Na1.5H0.5Ti3O7, with retained fibril morphology) that can be used for removal of radioactive ions and heavy metal ions from water. The structures and morphologies of the metal oxides were characterised by advanced techniques. Titania nanofibres of mixed anatase and TiO2(B) phases, pure anatase and pure TiO2(B) were obtained by calcining H-titanate nanofibres at different temperatures between 300 and 700 °C. The fibril morphology was retained after calcination, which is suitable for transmission electron microscopy (TEM) analysis. It has been found by TEM analysis that in mixed-phase structure the interfaces between anatase and TiO2(B) phases are not random contacts between the engaged crystals of the two phases, but form from the well matched lattice planes of the two phases. For instance, (101) planes in anatase and (101) planes of TiO2(B) are similar in d spaces (~0.18 nm), and they join together to form a stable interface. The interfaces between the two phases act as an one-way valve that permit the transfer of photogenerated charge from anatase to TiO2(B). This reduces the recombination of photogenerated electrons and holes in anatase, enhancing the activity for photocatalytic oxidation. Therefore, the mixed-phase nanofibres exhibited higher photocatalytic activity for degradation of sulforhodamine B (SRB) dye under ultraviolet (UV) light than the nanofibres of either pure phase alone, or the mechanical mixtures (which have no interfaces) of the two pure phase nanofibres with a similar phase composition. This verifies the theory that the difference between the conduction band edges of the two phases may result in charge transfer from one phase to the other, which results in effectively the photogenerated charge separation and thus facilitates the redox reaction involving these charges. Such an interface structure facilitates charge transfer crossing the interfaces. The knowledge acquired in this study is important not only for design of efficient TiO2 photocatalysts but also for understanding the photocatalysis process. Moreover, the fibril titania photocatalysts are of great advantage when they are separated from a liquid for reuse by filtration, sedimentation, or centrifugation, compared to nanoparticles of the same scale. The surface structure of TiO2 also plays a significant role in catalysis and photocatalysis. Four types of large surface area TiO2 nanotubes with different phase compositions (labelled as NTA, NTBA, NTMA and NTM) were synthesised from calcination and acid treatment of the H-titanate nanotubes. Using the in situ FTIR emission spectrescopy (IES), desorption and re-adsorption process of surface OH-groups on oxide surface can be trailed. In this work, the surface OH-group regeneration ability of the TiO2 nanotubes was investigated. The ability of the four samples distinctively different, having the order: NTA > NTBA > NTMA > NTM. The same order was observed for the catalytic when the samples served as photocatalysts for the decomposition of synthetic dye SRB under UV light, as the supports of gold (Au) catalysts (where gold particles were loaded by a colloid-based method) for photodecomposition of formaldehyde under visible light and for catalytic oxidation of CO at low temperatures. Therefore, the ability of TiO2 nanotubes to generate surface OH-groups is an indicator of the catalytic activity. The reason behind the correlation is that the oxygen vacancies at bridging O2- sites of TiO2 surface can generate surface OH-groups and these groups facilitate adsorption and activation of O2 molecules, which is the key step of the oxidation reactions. The structure of the oxygen vacancies at bridging O2- sites is proposed. Also a new mechanism for the photocatalytic formaldehyde decomposition with the Au-TiO2 catalysts is proposed: The visible light absorbed by the gold nanoparticles, due to surface plasmon resonance effect, induces transition of the 6sp electrons of gold to high energy levels. These energetic electrons can migrate to the conduction band of TiO2 and are seized by oxygen molecules. Meanwhile, the gold nanoparticles capture electrons from the formaldehyde molecules adsorbed on them because of gold’s high electronegativity. O2 adsorbed on the TiO2 supports surface are the major electron acceptor. The more O2 adsorbed, the higher the oxidation activity of the photocatalyst will exhibit. The last part of this thesis demonstrates two innovative applications of the titanate nanostructures. Firstly, trititanate and metastable titanate (Na1.5H0.5Ti3O7) nanofibres are used as intelligent absorbents for removal of radioactive cations and heavy metal ions, utilizing the properties of the ion exchange ability, deformable layered structure, and fibril morphology. Environmental contamination with radioactive ions and heavy metal ions can cause a serious threat to the health of a large part of the population. Treatment of the wastes is needed to produce a waste product suitable for long-term storage and disposal. The ion-exchange ability of layered titanate structure permitted adsorption of bivalence toxic cations (Sr2+, Ra2+, Pb2+) from aqueous solution. More importantly, the adsorption is irreversible, due to the deformation of the structure induced by the strong interaction between the adsorbed bivalent cations and negatively charged TiO6 octahedra, and results in permanent entrapment of the toxic bivalent cations in the fibres so that the toxic ions can be safely deposited. Compared to conventional clay and zeolite sorbents, the fibril absorbents are of great advantage as they can be readily dispersed into and separated from a liquid. Secondly, new generation membranes were constructed by using large titanate and small ã-alumina nanofibres as intermediate and top layers, respectively, on a porous alumina substrate via a spin-coating process. Compared to conventional ceramic membranes constructed by spherical particles, the ceramic membrane constructed by the fibres permits high flux because of the large porosity of their separation layers. The voids in the separation layer determine the selectivity and flux of a separation membrane. When the sizes of the voids are similar (which means a similar selectivity of the separation layer), the flux passing through the membrane increases with the volume of the voids which are filtration passages. For the ideal and simplest texture, a mesh constructed with the nanofibres 10 nm thick and having a uniform pore size of 60 nm, the porosity is greater than 73.5 %. In contrast, the porosity of the separation layer that possesses the same pore size but is constructed with metal oxide spherical particles, as in conventional ceramic membranes, is 36% or less. The membrane constructed by titanate nanofibres and a layer of randomly oriented alumina nanofibres was able to filter out 96.8% of latex spheres of 60 nm size, while maintaining a high flux rate between 600 and 900 Lm–2 h–1, more than 15 times higher than the conventional membrane reported in the most recent study.

If teams are so good.. : science teachers' conceptions of teams and teamwork

The focus of this study is the phenomenon of teams and teamwork. Currently the Professional Standards of Queensland’s teachers state that teams are critical to teachers’ work. This study uses a phenomenographic approach to investigate science teachers’ conceptions of teams and teamwork in the science departments of fifteen Queensland State secondary schools. The research identifies eight conceptions of teams and teamwork. The research findings suggest that the team represents a collective of science teachers bounded by the Science Department and their current timetabled subject. Collaboration was found in the study to be an activity that occurred between teachers in the same social space. The research recognises a new category of relationship between teachers, designated as ‘ask-and-receive’. The research identifies a lack of teamwork within the science department and the school. There appears to be no teaming with other subject departments. The research findings highlight the non-supportive team and teamwork policies, procedures and structures in the schools and identify the lack of recognition of the specialised skills of science teachers. The implications for the schools and science teachers are considerable, as the current Professional Standards of Education Queensland and the Queensland College of Teachers provide benchmarks of knowledge and practice of teams and teamwork for teachers. The research suggests that the professional standards relating to teams and teamwork cannot be achieved in the present school environment.

A problem-posing intervention in the development of problem-solving competence of underachieving, middle-year students

This study reported on the issues surrounding the acquisition of problem-solving competence of middle-year students who had been ascertained as above average in intelligence, but underachieving in problem-solving competence. In particular, it looked at the possible links between problem-posing skills development and improvements in problem-solving competence. A cohort of Year 7 students at a private, non-denominational, co-educational school was chosen as participants for the study, as they undertook a series of problem-posing sessions each week throughout a school term. The lessons were facilitated by the researcher in the students’ school setting. Two criteria were chosen to identify participants for this study. Firstly, each participant scored above the 60th percentile in the standardized Middle Years Ability Test (MYAT) (Australian Council for Educational Research, 2005) and secondly, the participants all scored below the cohort average for Criterion B (Problem-solving Criterion) in their school mathematics tests during the first semester of Year 7. Two mutually exclusive groups of participants were investigated with one constituting the Comparison Group and the other constituting the Intervention Group. The Comparison Group was chosen from a Year 7 cohort for whom no problem-posing intervention had occurred, while the Intervention Group was chosen from the Year 7 cohort of the following year. This second group received the problem-posing intervention in the form of a teaching experiment. That is, the Comparison Group were only pre-tested and post-tested, while the Intervention Group was involved in the teaching experiment and received the pre-testing and post-testing at the same time of the year, but in the following year, when the Comparison Group have moved on to the secondary part of the school. The groups were chosen from consecutive Year 7 cohorts to avoid cross-contamination of the data. A constructionist framework was adopted for this study that allowed the researcher to gain an “authentic understanding” of the changes that occurred in the development of problem-solving competence of the participants in the context of a classroom setting (Richardson, 1999). Qualitative and quantitative data were collected through a combination of methods including researcher observation and journal writing, video taping, student workbooks, informal student interviews, student surveys, and pre-testing and post-testing. This combination of methods was required to increase the validity of the study’s findings through triangulation of the data. The study findings showed that participation in problem-posing activities can facilitate the re-engagement of disengaged, middle-year mathematics students. In addition, participation in these activities can result in improved problem-solving competence and associated developmental learning changes. Some of the changes that were evident as a result of this study included improvements in self-regulation, increased integration of prior knowledge with new knowledge and increased and contextualised socialisation.

Beyond charity : outlines of a jurisprudence for civil society

There is not a single, coherent, jurisprudence for civil society organisations. Pressure for a clearly enuciated body of law applying to the whole of this sector of society continues to increase. The rise of third sector scholarship, the retreat of the welfare state, the rediscovery of the concept of civil society and pressures to strengthen social capital have all contributed to an ongoing stream of inquiry into the laws that regulate and favour civil society organisations. There have been almost thirty inquiries over the last sixty years into the doctrine of charitable purpose in common law countries. Those inquiries have established that problems with the law applying to civil society organisations are rooted in the common law adopting a ‘technical’ definition of charitable purpose and the failure of this body of law to develop in response to societal changes. Even though it is now well recognised that problems with law reform stem from problems inherent in the doctrine of charitable purpose, statutory reforms have merely ‘bolted on’ additions to the flawed ‘technical’ definition. In this way the scope of operation of the law has been incrementally expanded to include a larger number of civil society organisations. This piecemeal approach continues the exclusion of most civil society organisations from the law of charities discourse, and fails to address the underlying jurisprudential problems. Comprehensive reform requires revisiting the foundational problems embedded in the doctrine of charitable purpose, being informed by recent scholarship, and a paradigm shift that extends the doctrine to include all civil society organisations. Scholarly inquiry into civil society organisations, particularly from within the discipline of neoclassical economics, has elucidated insights that can inform legal theory development. This theory development requires decoupling the two distinct functions performed by the doctrine of charitable purpose which are: setting the scope of regulation, and determining entitlement to favours, such as tax exemption. If the two different functions of the doctrine are considered separately in the light of theoretical insights from other disciplines, the architecture for a jurisprudence emerges that facilitates regulation, but does not necessarily favour all civil society organisations. Informed by that broader discourse it is argued that when determining the scope of regulation, civil society organisations are identified by reference to charitable purposes that are not technically defined. These charitable purposes are in essence purposes which are: Altruistic, for public Benefit, pursued without Coercion. These charitable puposes differentiate civil society organisations from organisations in the three other sectors namely; Business, which is manifest in lack of altruism; Government, which is characterised by coercion; and Family, which is characterised by benefits being private not public. When determining entitlement to favour, it is theorised that it is the extent or nature of the public benefit evident in the pursuit of a charitable purpose that justifies entitlement to favour. Entitlement to favour based on the extent of public benefit is the theoretically simpler – the greater the public benefit the greater the justification for favour. To be entitled to favour based on the nature of a purpose being charitable the purpose must fall within one of three categories developed from the first three heads of Pemsel’s case (the landmark categorisation case on taxation favour). The three categories proposed are: Dealing with Disadvantage, Encouraging Edification; and Facilitating Freedom. In this alternative paradigm a recast doctrine of charitable purpose underpins a jurisprudence for civil society in a way similar to the way contract underpins the jurisprudence for the business sector, the way that freedom from arbitrary coercion underpins the jurisprudence of the government sector and the way that equity within families underpins succession and family law jurisprudence for the family sector. This alternative architecture for the common law, developed from the doctrine of charitable purpose but inclusive of all civil society purposes, is argued to cover the field of the law applying to civil society organisations and warrants its own third space as a body of law between public law and private law in jurisprudence.

The oral health of critically ill children

Introduction. In adults, oral health has been shown to worsen during critical illness as well as influence systemic health. There is a paucity of paediatric critical care research in the area of oral health; hence the purpose of the Critically ill Children’s Oral Health (CCOH) study is to describe the status of oral health of critically ill children over time spent in the paediatric intensive care unit (PICU). The study will also examine the relationship between poor oral health and a variety of patient characteristics and PICU therapies and explore the relationship between dysfunctional oral health and PICU related Healthcare-Associated Infections (HAI). Method. An observational study was undertaken at a single tertiary-referral PICU. Oral health was measured using the Oral Assessment Scale (OAS) and culturing oropharyngeal flora. Information was also collected surrounding the use of supportive therapies, clinical characteristics of the children and the occurrence of PICU related HAI. Results. Forty-six participants were consecutively recruited to the CCOH study. Of the participants 63% (n=32) had oral dysfunction while 41% (n=19) demonstrated pathogenic oropharyngeal colonisation during their critical illness. The potential systemic pathogens isolated from the oropharynx and included Candida sp., Staphylococcus aureus, Haemophilus influenzae, Enterococcus sp. and Pseudomonas aeruginosa. The severity of critical illness had a significant positive relationship (p=0.046) with pathogenic and absent colonisation of the oropharynx. Sixty-three percent of PICU-related HAI involved the preceding or simultaneous colonisation of the oropharynx by the causative pathogen. Conclusion. Given the prevalence of poor oral health during childhood critical illness and the subsequent potential systemic consequences, evidence based oral hygiene practices should be developed and validated to guide clinicians when nursing critically ill children.

Investigation of highly regulated promoters for the production of recombinant proteins in plants

Plants have been identified as promising expression systems for the commercial production of recombinant proteins. Plant-based protein production or “biofarming” offers a number of advantages over traditional expression systems in terms of scale of production, the capacity for post-translation processing, providing a product free of contaminants and cost effectiveness. A number of pharmaceutically important and commercially valuable proteins, such as antibodies, biopharmaceuticals and industrial enzymes are currently being produced in plant expression systems. However, several challenges still remain to improve recombinant protein yield with no ill effect on the host plant. The ability for transgenic plants to produce foreign proteins at commercially viable levels can be directly related to the level and cell specificity of the selected promoter driving the transgene. The accumulation of recombinant proteins may be controlled by a tissue-specific, developmentally-regulated or chemically-inducible promoter such that expression of recombinant proteins can be spatially- or temporally- controlled. The strict control of gene expression is particularly useful for proteins that are considered toxic and whose expression is likely to have a detrimental effect on plant growth. To date, the most commonly used promoter in plant biotechnology is the cauliflower mosaic virus (CaMV) 35S promoter which is used to drive strong, constitutive transgene expression in most organs of transgenic plants. Of particular interest to researchers in the Centre for Tropical Crops and Biocommodities at QUT are tissue-specific promoters for the accumulation of foreign proteins in the roots, seeds and fruit of various plant species, including tobacco, banana and sugarcane. Therefore this Masters project aimed to isolate and characterise root- and seed-specific promoters for the control of genes encoding recombinant proteins in plant-based expression systems. Additionally, the effects of matching cognate terminators with their respective gene promoters were assessed. The Arabidopsis root promoters ARSK1 and EIR1 were selected from the literature based on their reported limited root expression profiles. Both promoters were analysed using the PlantCARE database to identify putative motifs or cis-acting elements that may be associated with this activity. A number of motifs were identified in the ARSK1 promoter region including, WUN (wound-inducible), MBS (MYB binding site), Skn-1, and a RY core element (seed-specific) and in the EIR1 promoter region including, Skn-1 (seed-specific), Box-W1 (fungal elicitor), Aux-RR core (auxin response) and ABRE (ABA response). However, no previously reported root-specific cis-acting elements were observed in either promoter region. To confirm root specificity, both promoters, and truncated versions, were fused to the GUS reporter gene and the expression cassette introduced into Arabidopsis via Agrobacterium-mediated transformation. Despite the reported tissue-specific nature of these promoters, both upstream regulatory regions directed constitutive GUS expression in all transgenic plants. Further, similar levels of GUS expression from the ARSK1 promoter were directed by the control CaMV 35S promoter. The truncated version of the EIR1 promoter (1.2 Kb) showed some differences in the level of GUS expression compared to the 2.2 Kb promoter. Therefore, this suggests an enhancer element is contained in the 2.2 Kb upstream region that increases transgene expression. The Arabidopsis seed-specific genes ATS1 and ATS3 were selected from the literature based on their seed-specific expression profiles and gene expression confirmed in this study as seed-specific by RT-PCR analysis. The selected promoter regions were analysed using the PlantCARE database in order to identify any putative cis elements. The seed-specific motifs GCN4 and Skn-1 were identified in both promoter regions that are associated with elevated expression levels in the endosperm. Additionaly, the seed-specific RY element and the ABRE were located in the ATS1 promoter. Both promoters were fused to the GUS reporter gene and used to transform Arabidopsis plants. GUS expression from the putative promoters was consitutive in all transgenic Arabidopsis tissue tested. Importantly, the positive control FAE1 seed-specific promoter also directed constitutive GUS expression throughout transgenic Arabidopsis plants. The constitutive nature seen in all of the promoters used in this study was not anticipated. While variations in promoter activity can be caused by a number of influencing factors, the variation in promoter activity observed here would imply a major contributing factor common to all plant expression cassettes tested. All promoter constructs generated in this study were based on the binary vector pCAMBIA2300. This vector contains the plant selection gene (NPTII) under the transcriptional control of the duplicated CaMV 35S promoter. This CaMV 35S promoter contains two enhancer domains that confer strong, constitutive expression of the selection gene and is located immediately upstream of the promoter-GUS fusion. During the course of this project, Yoo et al. (2005) reported that transgene expression is significantly affected when the expression cassette is located on the same T-DNA as the 35S enhancer. It was concluded, the trans-acting effects of the enhancer activate and control transgene expression causing irregular expression patterns. This phenomenon seems the most plausible reason for the constitutive expression profiles observed with the root- and seed-specific promoters assessed in this study. The expression from some promoters can be influenced by their cognate terminator sequences. Therefore, the Arabidopsis ARSK1, EIR1, ATS1 and ATS3 terminator sequences were isolated and incorporated into expression cassettes containing the GUS reporter gene under the control of their cognate promoters. Again, unrestricted GUS activity was displayed throughout transgenic plants transformed with these reporter gene fusions. As previously discussed constitutive GUS expression was most likely due to the trans-acting effect of the upstream CaMV 35S promoter in the selection cassette located on the same T-DNA. The results obtained in this study make it impossible to assess the influence matching terminators with their cognate promoters have on transgene expression profiles. The obvious future direction of research continuing from this study would be to transform pBIN-based promoter-GUS fusions (ie. constructs containing no CaMV 35S promoter driving the plant selection gene) into Arabidopsis in order to determine the true tissue specificity of these promoters and evaluate the effects of their cognate 3’ terminator sequences. Further, promoter truncations based around the cis-elements identified here may assist in determining whether these motifs are in fact involved in the overall activity of the promoter.

Dynamics of transformation and fragmentation of composite liquid nano-particles

Recent research on particle size distributions and particle concentrations near a busy road cannot be explained by the conventional mechanisms for particle evolution of combustion aerosols. Specifically they appear to be inadequate to explain the experimental observations of particle transformation and the evolution of the total number concentration. This resulted in the development of a new mechanism based on their thermal fragmentation, for the evolution of combustion aerosol nano-particles. A complex and comprehensive pattern of evolution of combustion aerosols, involving particle fragmentation, was then proposed and justified. In that model it was suggested that thermal fragmentation occurs in aggregates of primary particles each of which contains a solid graphite/carbon core surrounded by volatile molecules bonded to the core by strong covalent bonds. Due to the presence of strong covalent bonds between the core and the volatile (frill) molecules, such primary composite particles can be regarded as solid, despite the presence of significant (possibly, dominant) volatile component. Fragmentation occurs when weak van der Waals forces between such primary particles are overcome by their thermal (Brownian) motion. In this work, the accepted concept of thermal fragmentation is advanced to determine whether fragmentation is likely in liquid composite nano-particles. It has been demonstrated that at least at some stages of evolution, combustion aerosols contain a large number of composite liquid particles containing presumably several components such as water, oil, volatile compounds, and minerals. It is possible that such composite liquid particles may also experience thermal fragmentation and thus contribute to, for example, the evolution of the total number concentration as a function of distance from the source. Therefore, the aim of this project is to examine theoretically the possibility of thermal fragmentation of composite liquid nano-particles consisting of immiscible liquid v components. The specific focus is on ternary systems which include two immiscible liquid droplets surrounded by another medium (e.g., air). The analysis shows that three different structures are possible, the complete encapsulation of one liquid by the other, partial encapsulation of the two liquids in a composite particle, and the two droplets separated from each other. The probability of thermal fragmentation of two coagulated liquid droplets is discussed and examined for different volumes of the immiscible fluids in a composite liquid particle and their surface and interfacial tensions through the determination of the Gibbs free energy difference between the coagulated and fragmented states, and comparison of this energy difference with the typical thermal energy kT. The analysis reveals that fragmentation was found to be much more likely for a partially encapsulated particle than a completely encapsulated particle. In particular, it was found that thermal fragmentation was much more likely when the volume ratio of the two liquid droplets that constitute the composite particle are very different. Conversely, when the two liquid droplets are of similar volumes, the probability of thermal fragmentation is small. It is also demonstrated that the Gibbs free energy difference between the coagulated and fragmented states is not the only important factor determining the probability of thermal fragmentation of composite liquid particles. The second essential factor is the actual structure of the composite particle. It is shown that the probability of thermal fragmentation is also strongly dependent on the distance that each of the liquid droplets should travel to reach the fragmented state. In particular, if this distance is larger than the mean free path for the considered droplets in the air, the probability of thermal fragmentation should be negligible. In particular, it follows form here that fragmentation of the composite particle in the state with complete encapsulation is highly unlikely because of the larger distance that the two droplets must travel in order to separate. The analysis of composite liquid particles with the interfacial parameters that are expected in combustion aerosols demonstrates that thermal fragmentation of these vi particles may occur, and this mechanism may play a role in the evolution of combustion aerosols. Conditions for thermal fragmentation to play a significant role (for aerosol particles other than those from motor vehicle exhaust) are determined and examined theoretically. Conditions for spontaneous transformation between the states of composite particles with complete and partial encapsulation are also examined, demonstrating the possibility of such transformation in combustion aerosols. Indeed it was shown that for some typical components found in aerosols that transformation could take place on time scales less than 20 s. The analysis showed that factors that influenced surface and interfacial tension played an important role in this transformation process. It is suggested that such transformation may, for example, result in a delayed evaporation of composite particles with significant water component, leading to observable effects in evolution of combustion aerosols (including possible local humidity maximums near a source, such as a busy road). The obtained results will be important for further development and understanding of aerosol physics and technologies, including combustion aerosols and their evolution near a source.

Vision-based topological mapping and localisation

Competent navigation in an environment is a major requirement for an autonomous mobile robot to accomplish its mission. Nowadays, many successful systems for navigating a mobile robot use an internal map which represents the environment in a detailed geometric manner. However, building, maintaining and using such environment maps for navigation is difficult because of perceptual aliasing and measurement noise. Moreover, geometric maps require the processing of huge amounts of data which is computationally expensive. This thesis addresses the problem of vision-based topological mapping and localisation for mobile robot navigation. Topological maps are concise and graphical representations of environments that are scalable and amenable to symbolic manipulation. Thus, they are well-suited for basic robot navigation applications, and also provide a representational basis for the procedural and semantic information needed for higher-level robotic tasks. In order to make vision-based topological navigation suitable for inexpensive mobile robots for the mass market we propose to characterise key places of the environment based on their visual appearance through colour histograms. The approach for representing places using visual appearance is based on the fact that colour histograms change slowly as the field of vision sweeps the scene when a robot moves through an environment. Hence, a place represents a region of the environment rather than a single position. We demonstrate in experiments using an indoor data set, that a topological map in which places are characterised using visual appearance augmented with metric clues provides sufficient information to perform continuous metric localisation which is robust to the kidnapped robot problem. Many topological mapping methods build a topological map by clustering visual observations to places. However, due to perceptual aliasing observations from different places may be mapped to the same place representative in the topological map. A main contribution of this thesis is a novel approach for dealing with the perceptual aliasing problem in topological mapping. We propose to incorporate neighbourhood relations for disambiguating places which otherwise are indistinguishable. We present a constraint based stochastic local search method which integrates the approach for place disambiguation in order to induce a topological map. Experiments show that the proposed method is capable of mapping environments with a high degree of perceptual aliasing, and that a small map is found quickly. Moreover, the method of using neighbourhood information for place disambiguation is integrated into a framework for topological off-line simultaneous localisation and mapping which does not require an initial categorisation of visual observations. Experiments on an indoor data set demonstrate the suitability of our method to reliably localise the robot while building a topological map.

The application of the Park & Ride and TOD concepts to develop a new framework that can maximise public transport patronage

With growing concern over the use of the car in our urbanized society, there have emerged a number of lobby groups and professional bodies promoting a return to public transport, walking and cycling, with the urban village as the key driving land use, as a means of making our cities’ transportation systems more sustainable. This research has aimed at developing a framework applicable to the Australian setting that can facilitate increased passenger patronage of rail based urban transport systems from adjacent or associated land uses. The framework specifically tested the application of the Park & Ride and Transit Oriented Development (TOD) concepts and their applicability within the cultural, institutional, political and transit operational characteristics of Australian society. The researcher found that, although the application of the TOD concept had been limited to small pockets of town houses and mixed use developments around stations, the development industry and emerging groups within the community are posed to embrace the concept and bring with it increased rail patronage. The lack of a clear commitment to infrastructure and supporting land uses is a major barrier to the implementation of TODs. The research findings demonstrated significant scope for the size of a TOD to expand to a much greater radius of activity from the public transport interchange, than the commonly quoted 400 to 600 meters, thus incorporating many more residents and potential patrons. The provision of Park & Rides, and associated support facilities like Kiss & Rides, have followed worldwide trends of high patronage demands from the middle and outer car dependent suburbs of our cities. The data collection and analysis gathered by the researcher demonstrated that in many cases Park & Rides should form part of a TOD to ensure ease of access to rail stations by all modes and patron types. The question, however, remains how best to plan the incorporation of a Park & Ride within a TOD and still maintain those features that attract and promote TODs as a living entity.

The experience of emotional expression in the context of social relations for people diagnosed with schizophrenia : a phenomenological explication

The experience of emotional expression in the context of social relations is not well understood for people diagnosed with schizophrenia. Early phenomenological research on the experience of people diagnosed with schizophrenia traditionally focussed on self experience in isolation from others, with later research explicating isolated aspects of self experience in relation to others. The current research aimed to focus on the progressive experience of emotional expression of people diagnosed with schizophrenia in relation to others over 12 months, in order to gain a broad spectrum of experience. This study involved unstructured interviews with 7 participants, an average of 4 times each, over a period of 12 months. Due to the unstructured nature of the interviews, a great breadth of experience was explicated. From the interviews there emerged 6 themes grouped together as a transition into, and 5 themes grouped together as a recovery from, symptoms associated with a diagnosis of schizophrenia. Special significance was given to the theme of relational confusion as an experience that provides an understanding of the relationship between social stressors and personal characteristics with responses that are associated with a diagnosis of schizophrenia. It was suggested that participants experienced themselves, including their distancing and isolating responses, as a part of a social system. The breadth of experiences that emerged afforded a framework of experiences within which prior phenomenological research findings on static moments of experience have been located. A more meaningful understanding of the transitioning into and recovery from the experiences associated with a diagnosis of schizophrenia will afford advances in mental health practice.

Addressing issues in sparseness, ecological bias and formulation of the adjacency matrix in Bayesian spatio-temporal analysis of disease counts

The main objective of this PhD was to further develop Bayesian spatio-temporal models (specifically the Conditional Autoregressive (CAR) class of models), for the analysis of sparse disease outcomes such as birth defects. The motivation for the thesis arose from problems encountered when analyzing a large birth defect registry in New South Wales. The specific components and related research objectives of the thesis were developed from gaps in the literature on current formulations of the CAR model, and health service planning requirements. Data from a large probabilistically-linked database from 1990 to 2004, consisting of fields from two separate registries: the Birth Defect Registry (BDR) and Midwives Data Collection (MDC) were used in the analyses in this thesis. The main objective was split into smaller goals. The first goal was to determine how the specification of the neighbourhood weight matrix will affect the smoothing properties of the CAR model, and this is the focus of chapter 6. Secondly, I hoped to evaluate the usefulness of incorporating a zero-inflated Poisson (ZIP) component as well as a shared-component model in terms of modeling a sparse outcome, and this is carried out in chapter 7. The third goal was to identify optimal sampling and sample size schemes designed to select individual level data for a hybrid ecological spatial model, and this is done in chapter 8. Finally, I wanted to put together the earlier improvements to the CAR model, and along with demographic projections, provide forecasts for birth defects at the SLA level. Chapter 9 describes how this is done. For the first objective, I examined a series of neighbourhood weight matrices, and showed how smoothing the relative risk estimates according to similarity by an important covariate (i.e. maternal age) helped improve the model’s ability to recover the underlying risk, as compared to the traditional adjacency (specifically the Queen) method of applying weights. Next, to address the sparseness and excess zeros commonly encountered in the analysis of rare outcomes such as birth defects, I compared a few models, including an extension of the usual Poisson model to encompass excess zeros in the data. This was achieved via a mixture model, which also encompassed the shared component model to improve on the estimation of sparse counts through borrowing strength across a shared component (e.g. latent risk factor/s) with the referent outcome (caesarean section was used in this example). Using the Deviance Information Criteria (DIC), I showed how the proposed model performed better than the usual models, but only when both outcomes shared a strong spatial correlation. The next objective involved identifying the optimal sampling and sample size strategy for incorporating individual-level data with areal covariates in a hybrid study design. I performed extensive simulation studies, evaluating thirteen different sampling schemes along with variations in sample size. This was done in the context of an ecological regression model that incorporated spatial correlation in the outcomes, as well as accommodating both individual and areal measures of covariates. Using the Average Mean Squared Error (AMSE), I showed how a simple random sample of 20% of the SLAs, followed by selecting all cases in the SLAs chosen, along with an equal number of controls, provided the lowest AMSE. The final objective involved combining the improved spatio-temporal CAR model with population (i.e. women) forecasts, to provide 30-year annual estimates of birth defects at the Statistical Local Area (SLA) level in New South Wales, Australia. The projections were illustrated using sixteen different SLAs, representing the various areal measures of socio-economic status and remoteness. A sensitivity analysis of the assumptions used in the projection was also undertaken. By the end of the thesis, I will show how challenges in the spatial analysis of rare diseases such as birth defects can be addressed, by specifically formulating the neighbourhood weight matrix to smooth according to a key covariate (i.e. maternal age), incorporating a ZIP component to model excess zeros in outcomes and borrowing strength from a referent outcome (i.e. caesarean counts). An efficient strategy to sample individual-level data and sample size considerations for rare disease will also be presented. Finally, projections in birth defect categories at the SLA level will be made.

Theoretical investigation of mechanisms of formation and interaction of nanoparticles

In this thesis an investigation into theoretical models for formation and interaction of nanoparticles is presented. The work presented includes a literature review of current models followed by a series of five chapters of original research. This thesis has been submitted in partial fulfilment of the requirements for the degree of doctor of philosophy by publication and therefore each of the five chapters consist of a peer-reviewed journal article. The thesis is then concluded with a discussion of what has been achieved during the PhD candidature, the potential applications for this research and ways in which the research could be extended in the future. In this thesis we explore stochastic models pertaining to the interaction and evolution mechanisms of nanoparticles. In particular, we explore in depth the stochastic evaporation of molecules due to thermal activation and its ultimate effect on nanoparticles sizes and concentrations. Secondly, we analyse the thermal vibrations of nanoparticles suspended in a fluid and subject to standing oscillating drag forces (as would occur in a standing sound wave) and finally on lattice surfaces in the presence of high heat gradients. We have described in this thesis a number of new models for the description of multicompartment networks joined by a multiple, stochastically evaporating, links. The primary motivation for this work is in the description of thermal fragmentation in which multiple molecules holding parts of a carbonaceous nanoparticle may evaporate. Ultimately, these models predict the rate at which the network or aggregate fragments into smaller networks/aggregates and with what aggregate size distribution. The models are highly analytic and describe the fragmentation of a link holding multiple bonds using Markov processes that best describe different physical situations and these processes have been analysed using a number of mathematical methods. The fragmentation of the network/aggregate is then predicted using combinatorial arguments. Whilst there is some scepticism in the scientific community pertaining to the proposed mechanism of thermal fragmentation,we have presented compelling evidence in this thesis supporting the currently proposed mechanism and shown that our models can accurately match experimental results. This was achieved using a realistic simulation of the fragmentation of the fractal carbonaceous aggregate structure using our models. Furthermore, in this thesis a method of manipulation using acoustic standing waves is investigated. In our investigation we analysed the effect of frequency and particle size on the ability for the particle to be manipulated by means of a standing acoustic wave. In our results, we report the existence of a critical frequency for a particular particle size. This frequency is inversely proportional to the Stokes time of the particle in the fluid. We also find that for large frequencies the subtle Brownian motion of even larger particles plays a significant role in the efficacy of the manipulation. This is due to the decreasing size of the boundary layer between acoustic nodes. Our model utilises a multiple time scale approach to calculating the long term effects of the standing acoustic field on the particles that are interacting with the sound. These effects are then combined with the effects of Brownian motion in order to obtain a complete mathematical description of the particle dynamics in such acoustic fields. Finally, in this thesis, we develop a numerical routine for the description of "thermal tweezers". Currently, the technique of thermal tweezers is predominantly theoretical however there has been a handful of successful experiments which demonstrate the effect it practise. Thermal tweezers is the name given to the way in which particles can be easily manipulated on a lattice surface by careful selection of a heat distribution over the surface. Typically, the theoretical simulations of the effect can be rather time consuming with supercomputer facilities processing data over days or even weeks. Our alternative numerical method for the simulation of particle distributions pertaining to the thermal tweezers effect use the Fokker-Planck equation to derive a quick numerical method for the calculation of the effective diffusion constant as a result of the lattice and the temperature. We then use this diffusion constant and solve the diffusion equation numerically using the finite volume method. This saves the algorithm from calculating many individual particle trajectories since it is describes the flow of the probability distribution of particles in a continuous manner. The alternative method that is outlined in this thesis can produce a larger quantity of accurate results on a household PC in a matter of hours which is much better than was previously achieveable.

The experience of China-educated nurses working in Australia : a symbolic interactionist perspective

Transnational nurse migration is a growing phenomenon. However, relatively little is known about the experiences of immigrant nurses and particularly about non-English speaking background nurses who work in more economically developed countries. Informed by a symbolic interactionist framework, this research explored the experience of China-educated nurses working in the Australian health care system. Using a modified constructivist grounded theory method, the main source of data were 46 face to face in-depth interviews with 28 China-educated nurses in two major cities in Australia. The key findings of this research are fourfold. First, the core category developed in this study is reconciling different realities, which inserts a theoretical understanding beyond the concepts of acculturation, assimilation, and integration. Second, in contrast to the dominant discourse which reduces the experience of immigrant nurses to language and culture, this research concludes that it was not just about language and nor was it simply about culture. Third, rather than focus on the negative aspects of difference as in the immigration literature and in the practice of nursing, this research points to the importance of recognising the social value of difference. Finally, the prevailing view that the experience of immigrant nurses is largely negative belies its complexities. This research concludes that it is naïve to define the experience as either good or bad. Rather, ambivalence was the essential feature of the experience and a more appropriate theoretical concept. This research produced a theoretical understanding of the experience of China-educated nurses working in Australia. The findings may not only inform Chinese nurses who wish to immigrate but also contribute to the implementation of more effective support services for immigrant nurses in Australian health care organisations.

Adaptive dual control of topic-based information retrieval

Information Retrieval is an important albeit imperfect component of information technologies. A problem of insufficient diversity of retrieved documents is one of the primary issues studied in this research. This study shows that this problem leads to a decrease of precision and recall, traditional measures of information retrieval effectiveness. This thesis presents an adaptive IR system based on the theory of adaptive dual control. The aim of the approach is the optimization of retrieval precision after all feedback has been issued. This is done by increasing the diversity of retrieved documents. This study shows that the value of recall reflects this diversity. The Probability Ranking Principle is viewed in the literature as the “bedrock” of current probabilistic Information Retrieval theory. Neither the proposed approach nor other methods of diversification of retrieved documents from the literature conform to this principle. This study shows by counterexample that the Probability Ranking Principle does not in general lead to optimal precision in a search session with feedback (for which it may not have been designed but is actively used). Retrieval precision of the search session should be optimized with a multistage stochastic programming model to accomplish the aim. However, such models are computationally intractable. Therefore, approximate linear multistage stochastic programming models are derived in this study, where the multistage improvement of the probability distribution is modelled using the proposed feedback correctness method. The proposed optimization models are based on several assumptions, starting with the assumption that Information Retrieval is conducted in units of topics. The use of clusters is the primary reasons why a new method of probability estimation is proposed. The adaptive dual control of topic-based IR system was evaluated in a series of experiments conducted on the Reuters, Wikipedia and TREC collections of documents. The Wikipedia experiment revealed that the dual control feedback mechanism improves precision and S-recall when all the underlying assumptions are satisfied. In the TREC experiment, this feedback mechanism was compared to a state-of-the-art adaptive IR system based on BM-25 term weighting and the Rocchio relevance feedback algorithm. The baseline system exhibited better effectiveness than the cluster-based optimization model of ADTIR. The main reason for this was insufficient quality of the generated clusters in the TREC collection that violated the underlying assumption.