Synthesis and characterisation of metal oxyhydroxide and oxide nanomaterials

In this work, a range of nanomaterials have been synthesised based on metal oxyhydroxides MO(OH), where M=Al, Co, Cr, etc. Through a self-assembly hydrothermal route, metal oxyhydroxide nanomaterials with various morphologies were successfully synthesised: one dimensional boehmite (AlO(OH)) nanofibres, zero dimensional indium hydroxide (In(OH)3) nanocubes and chromium oxyhydroxide (CrO(OH)) nanoparticles, as well as two dimensional cobalt hydroxide and oxyhydroxide (Co(OH)2 & CoO(OH)) nanodiscs. In order to control the synthetic nanomaterial morphology and growth, several factors were investigated including cation concentration, temperature, hydrothermal treatment time, and pH. Metal ion doping is a promising technique to modify and control the properties of materials by intentionally introducing impurities or defects into the material. Chromium was successfully applied as a dopant for fabricating doped boehmite nanofibres. The thermal stability of the boehmite nanofibres was enhanced by chromium doping, and the photoluminescence property was introduced to the chromium doped alumina nanofibres. Doping proved to be an efficient method to modify and functionalize nanomaterials. The synthesised nanomaterials were fully characterised by X-ray diffraction (XRD), transmission electron microscopy (TEM) combined with selected area electron diffraction (SAED), scanning electron microscopy (SEM), BET specific surface area analysis, X-ray photoelectron spectroscopy (XPS) and thermo gravimetric analysis (TGA). Hot-stage Raman and infrared emission spectroscopy were applied to study the chemical reactions during dehydration and dehydroxylation. The advantage of these techniques is that the changes in molecular structure can be followed in situ and at the elevated temperatures.

The structure of the mineral leogangite Cu10(OH)6(SO4)(AsO4)4•8H2O–implications for arsenic accumulation and removal

The objective of this research is to determine the molecular structure of the mineral leogangite. The formation of the types of arsenosulphate minerals offers a mechanism for arsenate removal from soils and mine dumps. Raman and infrared spectroscopy have been used to characterise the mineral. Observed bands are assigned to the stretching and bending vibrations of (SO4)2- and (AsO4)3- units, stretching and bending vibrations of hydrogen bonded (OH)- ions and Cu2+-(O,OH) units. The approximate range of O-H...O hydrogen bond lengths is inferred from the Raman spectra. Raman spectra of leogangite from different origins differ in that some spectra are more complex, where bands are sharp and the degenerate bands of (SO4)2- and (AsO4)3- are split and more intense. Lower wavenumbers of  H2O bending vibration in the spectrum may indicate the presence of weaker hydrogen bonds compared with those in a different leogangite samples. The formation of leogangite offers a mechanism for the removal of arsenic from the environment.

Assessment of retinal structure and visual function in association with diabetic peripheral neuropathy

Diabetes is an increasingly prevalent disease worldwide. Providing early management of the complications can prevent morbidity and mortality in this population. Peripheral neuropathy, a significant complication of diabetes, is the major cause of foot ulceration and amputation in diabetes. Delay in attending to complication of the disease contributes to significant medical expenses for diabetic patients and the community. Early structural changes to the neural components of the retina have been demonstrated to occur prior to the clinically visible retinal vasculature complication of diabetic retinopathy. Additionally visual functionloss has been shown to exist before the ophthalmoscopic manifestations of vasculature damage. The purpose of this thesis was to evaluate the relationship between diabetic peripheral neuropathy and both retinal structure and visual function. The key question was whether diabetic peripheral neuropathy is the potential underlying factor responsible for retinal anatomical change and visual functional loss in people with diabetes. This study was conducted on a cohort with type 2 diabetes. Retinal nerve fibre layer thickness was assessed by means of Optical Coherence Tomography (OCT). Visual function was assessed using two different methods; Standard Automated Perimetry (SAP) and flicker perimetry were performed within the central 30 degrees of fixation. The level of diabetic peripheral neuropathy (DPN) was assessed using two techniques - Quantitative Sensory Testing and Neuropathy Disability Score (NDS). These techniques are known to be capable of detecting DPN at very early stages. NDS has also been shown as a gold standard for detecting 'risk of foot ulceration'. Findings reported in this thesis showed that RNFL thickness, particularly in the inferior quadrant, has a significant association with severity of DPN when the condition has been assessed using NDS. More specifically it was observed that inferior RNFL thickness has the ability to differentiate individuals who are at higher risk of foot ulceration from those who are at lower risk, indicating that RNFL thickness can predict late-staged DPN. Investigating the association between RNFL and QST did not show any meaningful interaction, which indicates that RNFL thickness for this cohort was not as predictive of neuropathy status as NDS. In both of these studies, control participants did not have different results from the type 2 cohort who did not DPN suggesting that RNFL thickness is not a marker for diagnosing DPN at early stages. The latter finding also indicated that diabetes per se, is unlikely to affect the RNFL thickness. Visual function as measured by SAP and flicker perimetry was found to be associated with severity of peripheral neuropathy as measured by NDS. These findings were also capable of differentiating individuals at higher risk of foot ulceration; however, visual function also proved not to be a maker for early diagnosis of DPN. It was found that neither SAP, nor flicker sensitivity have meaningful associations with DPN when neuropathy status was measured using QST. Importantly diabetic retinopathy did not explain any of the findings in these experiments. The work described here is valuable as no other research to date has investigated the association between diabetic peripheral neuropathy and either retinal structure or visual function.

The molecular structure of the mineral sarmientite Fe2(AsO4,SO4)2(OH)6•5H2O : implications for arsenic accumulation and removal

Sarmientite is an environmental mineral; its formation in soils enables the entrapment and immobilisation of arsenic. The mineral sarmientite is often amorphous making the application of X-ray diffraction difficult. Vibrational spectroscopy has been applied to the study of sarmientite. Bands are attributed to the vibrational units of arsenate, sulphate, hydroxyl and water. Raman bands at 794, 814 and 831 cm−1 are assigned to the ν3 (AsO4)3− antisymmetric stretching modes and the ν1 symmetric stretching mode is observed at 891 cm−1. Raman bands at 1003 and 1106 cm−1 are attributed to vibrations. The Raman band at 484 cm−1 is assigned to the triply degenerate (AsO4)3− bending vibration. The high intensity Raman band observed at 355 cm−1 (both lower and upper) is considered to be due to the (AsO4)3−ν2 bending vibration. Bands attributed to water and OH stretching vibrations are observed.

Boundary weaving : the social structure and processes of organizational boundaries

Boundaries are an important field of study because they mediate almost every aspect of organizational life. They are becoming increasingly more important as organizations change more frequently and yet, despite the endemic use of the boundary metaphor in common organizational parlance, they are poorly understood. Organizational boundaries are under-theorized and researchers in related fields often simply assume their existence, without defining them. The literature on organizational boundaries is fragmented with no unifying theoretical basis. As a result, when it is recognized that an organizational boundary is "dysfunctional". there is little recourse to models on which to base remediating action. This research sets out to develop just such a theoretical model and is guided by the general question: "What is the nature of organizational boundaries?" It is argued that organizational boundaries can be conceptualised through elements of both social structure and of social process. Elements of structure include objects, coupling, properties and identity. Social processes include objectification, identification, interaction and emergence. All of these elements are integrated by a core category, or basic social process, called boundary weaving. An organizational boundary is a complex system of objects and emergent properties that are woven together by people as they interact together, objectifying the world around them, identifying with these objects and creating couplings of varying strength and polarity as well as their own fragmented identity. Organizational boundaries are characterised by the multiplicity of interconnections, a particular domain of objects, varying levels of embodiment and patterns of interaction. The theory developed in this research emerged from an exploratory, qualitative research design employing grounded theory methodology. The field data was collected from the training headquarters of the New Zealand Army using semi-structured interviews and follow up observations. The unit of analysis is an organizational boundary. Only one research context was used because of the richness and multiplicity of organizational boundaries that were present. The model arose, grounded in the data collected, through a process of theoretical memoing and constant comparative analysis. Academic literature was used as a source of data to aid theory development and the saturation of some central categories. The final theory is classified as middle range, being substantive rather than formal, and is generalizable across medium to large organizations in low-context societies. The main limitation of the research arose from the breadth of the research with multiple lines of inquiry spanning several academic disciplines, with some relevant areas such as the role of identity and complexity being addressed at a necessarily high level. The organizational boundary theory developed by this research replaces the typology approaches, typical of previous theory on organizational boundaries and reconceptualises the nature of groups in organizations as well as the role of "boundary spanners". It also has implications for any theory that relies on the concept of boundaries, such as general systems theory. The main contribution of this research is the development of a holistic model of organizational boundaries including an explanation of the multiplicity of boundaries . no organization has a single definable boundary. A significant aspect of this contribution is the integration of aspects of complexity theory and identity theory to explain the emergence of higher-order properties of organizational boundaries and of organizational identity. The core category of "boundary weaving". is a powerful new metaphor that significantly reconceptualises the way organizational boundaries may be understood in organizations. It invokes secondary metaphors such as the weaving of an organization's "boundary fabric". and provides managers with other metaphorical perspectives, such as the management of boundary friction, boundary tension, boundary permeability and boundary stability. Opportunities for future research reside in formalising and testing the theory as well as developing analytical tools that would enable managers in organizations to apply the theory in practice.

Caregiving experience and its influencing factors : rural versus urban adult-child caregivers caring for parents with dementia in China

Background: It is predicted that China will have the largest number of cases of dementia in the world by 2025 (Ferri et al., 2005). Research has demonstrated that caring for family members with dementia can be a long-term, burdensome activity resulting in physical and emotional distress and impairment (Pinquart & Sorensen, 2003b). The establishment of family caregiver supportive services in China can be considered urgent; and the knowledge of the caregiving experience and related influencing factors is necessary to inform such services. Nevertheless, in the context of rapid demographic and socioeconomic change, the impact of caregiving for rural and urban Chinese adult-child caregivers may be different, and different needs in supportive services may therefore be expected. Objectives: The aims of this research were 1) to examine the potential differences existing in the caregiving experience between rural and urban adult-child caregivers caring for parents with dementia in China; and 2) to examine the potential differences existing in the influencing factors of the caregiving experience for rural as compared with urban adult-child caregivers caring for parents with dementia in China. Based on the literature review and Kramer.s (1997) caregiver adaptation model, six concepts and their relationships of caregiving experience were studied: severity of the care receivers. dementia, caregivers. appraisal of role strain and role gain, negative and positive well-being outcomes, and health related quality of life. Furthermore, four influencing factors (i.e., filial piety, social support, resilience, and personal mastery) were studied respectively. Methods: A cross-sectional, comparative design was used to achieve the aims of the study. A questionnaire, which was designed based on the literature review and on Kramer.s (1997) caregiver adaptation model, was completed by 401 adult-child caregivers caring for their parents with dementia from the mental health outpatient departments in five hospitals in the Yunnan province, P.R. China. Structural equation modelling (SEM) was employed as the main statistical technique for data analyses. Other statistical techniques (e.g., t-tests and Chi-Square tests) were also conducted to compare the demographic characteristics and the measured variables between rural and urban groups. Results: For the first research aim, the results indicated that urban adult-child caregivers in China experienced significantly greater strain and negative well-being outcomes than their rural peers; whereas, the difference on the appraisal of role gain and positive outcomes was nonsignificant between the two groups. The results also indicated that the amounts of severity of care receivers. dementia and caregivers. health related quality of life do not have the same meanings between the two groups. Thus, the levels of these two concepts were not comparable between the rural and urban groups in this study. Moreover, the results also demonstrated that the negative direct effect of gain on negative outcomes in urban caregivers was stronger than that in rural caregivers, suggesting that the urban caregivers tended to use appraisal of role gain to protect themselves from negative well-being outcomes to a greater extent. In addition, the unexplained variance in strain in the urban group was significantly more than that in the rural group, suggesting that there were other unmeasured variables besides the severity of care receivers. dementia which would predict strain in urban caregivers compared with their rural peers. For the second research aim, the results demonstrated that rural adult-child caregivers reported a significantly higher level of filial piety and more social support than their urban counterparts, although the two groups did not significantly differ on the levels of their resilience and personal mastery. Furthermore, although the mediation effects of these four influencing factors on both positive and negative aspects remained constant across rural and urban adult-child caregivers, urban caregivers tended to be more effective in using personal mastery to protect themselves from role strain than rural caregivers, which in turn protects them more from the negative well-being outcomes than was the case with their rural peers. Conclusions: The study extends the application of Kramer.s caregiving adaptation process model (Kramer, 1997) to a sample of adult-child caregivers in China by demonstrating that both positive and negative aspects of caregiving may impact on the caregiver.s health related quality of life, suggesting that both aspects should be targeted in supportive interventions for Chinese family caregivers. Moreover, by demonstrating partial mediation effects, the study provides four influencing factors (i.e., filial piety, social support, resilience, and personal mastery) as specific targets for clinical interventions. Furthermore, the study found evidence that urban adult-child caregivers had more negative but similar positive experience compared to their rural peers, suggesting that the establishment of supportive services for urban caregivers may be more urgent at present stage in China. Additionally, since urban caregivers tended to use appraisal of role gain and personal mastery to protect themselves from negative well-being outcomes than rural caregivers to a greater extend, interventions targeting utility of gain or/and personal mastery to decrease negative outcomes might be more effective in urban caregivers than in rural caregivers. On the other hand, as cultural expectations and expression of filial piety tend to be more traditional in rural areas, interventions targeting filial piety could be more effective among rural caregivers. Last but not least, as rural adult-child caregivers have more existing natural social support than their urban counterparts, mobilising existing natural social support resources may be more beneficial for rural caregivers, whereas, formal supports (e.g., counselling services, support groups and adult day care centres) should be enhanced for urban caregivers.

The molecular structure of the multianion mineral hidalgoite PbAl3(AsO4)(SO4)(OH)6 : implications for arsenic removal from soils

The objective of this research is to determine the molecular structure of the mineral hidalgoite PbAl3(AsO4)(SO4)(OH)6 using vibrational spectroscopy. The mineral is found in old mine sites. Observed bands are assigned to the stretching and bending vibrations of (SO4)2- and (AsO4)3- units, stretching and bending vibrations of hydrogen bonded (OH)- ions and Al3+-(O,OH) units. The approximate range of O-H...O hydrogen bond lengths is inferred from the Raman and infrared spectra. Values of 2.6989 Å, 2.7682 Å, 2.8659 Å were obtained. The formation of hidalgoite may offer a mechanism for the removal of arsenic from the environment.

Using Bayesian methods for the estimation of uncertainty in complex statistical models

The research objectives of this thesis were to contribute to Bayesian statistical methodology by contributing to risk assessment statistical methodology, and to spatial and spatio-temporal methodology, by modelling error structures using complex hierarchical models. Specifically, I hoped to consider two applied areas, and use these applications as a springboard for developing new statistical methods as well as undertaking analyses which might give answers to particular applied questions. Thus, this thesis considers a series of models, firstly in the context of risk assessments for recycled water, and secondly in the context of water usage by crops. The research objective was to model error structures using hierarchical models in two problems, namely risk assessment analyses for wastewater, and secondly, in a four dimensional dataset, assessing differences between cropping systems over time and over three spatial dimensions. The aim was to use the simplicity and insight afforded by Bayesian networks to develop appropriate models for risk scenarios, and again to use Bayesian hierarchical models to explore the necessarily complex modelling of four dimensional agricultural data. The specific objectives of the research were to develop a method for the calculation of credible intervals for the point estimates of Bayesian networks; to develop a model structure to incorporate all the experimental uncertainty associated with various constants thereby allowing the calculation of more credible credible intervals for a risk assessment; to model a single day’s data from the agricultural dataset which satisfactorily captured the complexities of the data; to build a model for several days’ data, in order to consider how the full data might be modelled; and finally to build a model for the full four dimensional dataset and to consider the timevarying nature of the contrast of interest, having satisfactorily accounted for possible spatial and temporal autocorrelations. This work forms five papers, two of which have been published, with two submitted, and the final paper still in draft. The first two objectives were met by recasting the risk assessments as directed, acyclic graphs (DAGs). In the first case, we elicited uncertainty for the conditional probabilities needed by the Bayesian net, incorporated these into a corresponding DAG, and used Markov chain Monte Carlo (MCMC) to find credible intervals, for all the scenarios and outcomes of interest. In the second case, we incorporated the experimental data underlying the risk assessment constants into the DAG, and also treated some of that data as needing to be modelled as an ‘errors-invariables’ problem [Fuller, 1987]. This illustrated a simple method for the incorporation of experimental error into risk assessments. In considering one day of the three-dimensional agricultural data, it became clear that geostatistical models or conditional autoregressive (CAR) models over the three dimensions were not the best way to approach the data. Instead CAR models are used with neighbours only in the same depth layer. This gave flexibility to the model, allowing both the spatially structured and non-structured variances to differ at all depths. We call this model the CAR layered model. Given the experimental design, the fixed part of the model could have been modelled as a set of means by treatment and by depth, but doing so allows little insight into how the treatment effects vary with depth. Hence, a number of essentially non-parametric approaches were taken to see the effects of depth on treatment, with the model of choice incorporating an errors-in-variables approach for depth in addition to a non-parametric smooth. The statistical contribution here was the introduction of the CAR layered model, the applied contribution the analysis of moisture over depth and estimation of the contrast of interest together with its credible intervals. These models were fitted using WinBUGS [Lunn et al., 2000]. The work in the fifth paper deals with the fact that with large datasets, the use of WinBUGS becomes more problematic because of its highly correlated term by term updating. In this work, we introduce a Gibbs sampler with block updating for the CAR layered model. The Gibbs sampler was implemented by Chris Strickland using pyMCMC [Strickland, 2010]. This framework is then used to consider five days data, and we show that moisture in the soil for all the various treatments reaches levels particular to each treatment at a depth of 200 cm and thereafter stays constant, albeit with increasing variances with depth. In an analysis across three spatial dimensions and across time, there are many interactions of time and the spatial dimensions to be considered. Hence, we chose to use a daily model and to repeat the analysis at all time points, effectively creating an interaction model of time by the daily model. Such an approach allows great flexibility. However, this approach does not allow insight into the way in which the parameter of interest varies over time. Hence, a two-stage approach was also used, with estimates from the first-stage being analysed as a set of time series. We see this spatio-temporal interaction model as being a useful approach to data measured across three spatial dimensions and time, since it does not assume additivity of the random spatial or temporal effects.

An evaluation of the pattern and structure mathematics awareness program in the early school years

This paper reports a 2-year longitudinal study on the effectiveness of the Pattern and Structure Mathematical Awareness Program (PASMAP) on students’ mathematical development. The study involved 316 Kindergarten students in 17 classes from four schools in Sydney and Brisbane. The development of the PASA assessment interview and scale are presented. The intervention program provided explicit instruction in mathematical pattern and structure that enhanced the development of students’ spatial structuring, multiplicative reasoning, and emergent generalisations. This paper presents the initial findings of the impact of the PASMAP and illustrates students’ structural development.

Developing the Pattern and Structure Assessment (PASA) interview to inform early mathematics learning

The Pattern and Structure Mathematical Awareness Program(PASMAP) stems from a 2-year longitudinal study on students’ early mathematical development. The paper outlines the interview assessment the Pattern and Structure Assessment(PASA) designed to describe students’ awareness of mathematical pattern and structure across a range of concepts. An overview of students’ performance across items and descriptions of their structural development are described.

The motivation and structure of corrupt police networks : theorising the dark side of the ‘thin blue line’

In recent times considerable research attention has been directed to understanding dark networks, especially criminal and terrorist networks. Dark networks are those in which member motivations are self rather than public interested, achievements come at the cost of other individuals, groups or societies and, in addition, their activities are both ‘covert and illegal’ (Raab & Milward, 2003: 415). This ‘darkness’ has implications for the way in which these networks are structured, the strategies adopted and their recruitment methods. Such entities exhibit distinctive operating characteristics including most notably the tension between creating an efficient network structure while retaining the ability to hide from public view while avoiding catastrophic collapse should one member cooperate with authorities (Bouchard 2007). While theoretical emphasis has been on criminal and terrorist networks, recent work has demonstrated that corrupt police networks exhibit some distinctive characteristics. In particular, these entities operate within the shadows of a host organisation - the Police Force and distort the functioning of the ‘Thin Blue Line’ as the interface between the law abiding citizenry and the criminal society. Drawing on data derived from the Queensland Fitzgerald Commission of Enquiry into Police Misconduct and related documents, this paper examines the motivations, structural properties and operational practices of corrupt police networks and compares and contrasts these with other dark networks with ‘bright’ public service networks. The paper confirms the structural differences between dark corrupt police networks and bright networks and suggests. However, structural embeddedness alone is found to be an insufficient theoretical explanation for member involvement in networks and that a set of elements combine to impact decision-making. Although offering important insights into network participation, the paper’s findings are especially pertinent in identifying additional points of intervention for police corruption networks.

Complexity, evolution, and the structure of demand

This chapter argues that evolutionary economics should be founded upon complex systems theory rather than neo-Darwinian analogies concerning natural selection, which focus on supply side considerations and competition amongst firms and technologies. It suggests that conceptions such as production and consumption functions should be replaced by network representations, in which the preferences or, more correctly, the aspirations of consumers are fundamental and, as such, the primary drivers of economic growth. Technological innovation is viewed as a process that is intermediate between these aspirational networks, and the organizational networks in which goods and services are produced. Consumer knowledge becomes at least as important as producer knowledge in determining how economic value is generated. It becomes clear that the stability afforded by connective systems of rules is essential for economic flexibility to exist, but that too many rules result in inert and structurally unstable states. In contrast, too few rules result in a more stable state, but at a low level of ordered complexity. Economic evolution from this perspective is explored using random and scale free network representations of complex systems.