Development and application of a microelectrode based scanning voltammetric detector

A large part of the work presented in this thesis describes the development and use of a novel electrochemical detector designed to allow the electrochemical characterisation of compounds in flowing solution by means of cyclic voltammetry. The detector was microprocessor controlled, which provides digital generation of the potential waveform and collection of data for subsequent analysis. Microdisk working electrodes are employed to permit both thermodynamic and kinetically controlled processes to be studied under steady-state conditions in flowing solutions without the distortion or hysteresis normally encountered with larger sized electrodes. The effect of electrode size, potential scan rate, and solution flow rate are studied extensively with the oxidation of ferrocene used as an example of a thermodynamically controlled process and a series of catecholamines as examples of a kinetically controlled process. The performance of the detector was best demonstrated when used as a HPLC post-column detector. The 3-dimensional chromatovoltammograms obtained allow on-line characterisation of each fraction as it elutes from the column. The rest of the work presented in this thesis involves the study of the oxidative degradation pathway of dithranol. The oxidative pathway was shown to involve a complex free radical mechanism, dependent on the presence of both oxygen and, in particular light. The pathway is further complicated by the fact that dithranol may exist in either a keto or enol form, the enol being most susceptible to oxidation. A likely mechanism is proposed from studies performed with cyclic voltammetry and controlled potential electrolysis, then defined by subsequent kinetic studies.

Children's liking and wanting of snack products : influence of shape and flavour

Background : Children's food choices are guided by their preferences. However, these preferences may change due to repeated exposure.

Methods : This study investigated children's (n = 242, 7–12 yrs-old) liking and wanting for snacks over 3 weeks of daily consumption. The snacks differed in size (small vs large) or flavour (sweet vs sweet-sour). Two conditions were designed: 1) a monotonous group in which children continuously consumed the same snack across the 3 weeks, and 2) a free choice group in which children were allowed to freely choose amongst 3 different flavours of the snack each day during 3 weeks.

Results : Shape influenced long-term liking, i.e. small shaped snacks remained stable in liking over repeated consumption, whereas large shaped snacks with the same flavour decreased in liking. Mean wanting ratings for all snack products decreased over 3 weeks daily consumption. Flavour did not significantly influence liking and wanting over time. The ability to freely choose amongst different flavours tended to decrease children's liking (p < 0.1) and wanting (p < 0.001) for these products. Changes in liking rather than initial liking was the best predictor of snack choice during the intervention.

Conclusion : Wanting rather than liking was most affected by repeated daily consumption of snack foods over three weeks. In order to increase the likelihood that children will repeatedly eat a food product, smaller sized healthy snacks are preferred to larger sized snacks. Future research should focus on stabilizing wanting over repeated consumption.

Differential expression of ATP7A, ATP7B and CTR1 in adult rat dorsal root ganglion tissue

Background: ATP7A, ATP7B and CTR1 are metal transporting proteins that control the cellular disposition of copper and platinum drugs, but their expression in dorsal root ganglion (DRG) tissue and their role in platinum-induced neurotoxicity are unknown. To investigate the DRG expression of ATP7A, ATP7B and CTR1, lumbar DRG and reference tissues were collected for real time quantitative PCR, RT-PCR, immunohistochemistry and Western blot analysis from healthy control adult rats or from animals treated with intraperitoneal oxaliplatin (1.85 mg/kg) or drug vehicle twice weekly for 8 weeks.
Results: In DRG tissue from healthy control animals, ATP7A mRNA was clearly detectable at levels similar to those found in the brain and spinal cord, and intense ATP7A immunoreactivity was localised to the cytoplasm of cell bodies of smaller DRG neurons without staining of satellite cells, nerve fibres or co-localisation with phosphorylated heavy neurofilament subunit (pNF-H). High levels of CTR1 mRNA were detected in all tissues from healthy control animals, and strong CTR1 immunoreactivity was associated with plasma membranes and vesicular cytoplasmic structures of the cell bodies of larger-sized DRG neurons without co-localization with ATP7A. DRG neurons with strong expression of ATP7A or CTR1 had distinct cell body size profiles with minimal overlap between them. Oxaliplatin treatment did not alter the size profile of strongly ATP7A-immunoreactive neurons but significantly reduced the size profile of strongly CTR1-immunoreactive neurons. ATP7B mRNA was barely detectable, and no specific immunoreactivity for ATP7B was found, in DRG tissue from healthy control animals.
Conclusions: In conclusion, adult rat DRG tissue exhibits a specific pattern of expression of copper transporters with distinct subsets of peripheral sensory neurons intensely expressing either ATP7A or CTR1, but not both or ATP7B. The neuron subtype-specific and largely non-overlapping distribution of ATP7A and CTR1 within rat DRG tissue may be required to support the potentially differing cuproenzyme requirements of distinct subsets of sensory neurons, and could influence the transport and neurotoxicity of oxaliplatin.

Evidence from genetic and Lagrangian drifter data for transatlantic transport of small juvenile green turtles

Aim  A key life-history component for many animals is the need for movement between different geographical locations at particular times. Green turtle (Chelonia mydas) hatchlings disperse from their natal location to spend an early pelagic stage in the ocean, followed by a neritic stage where small juveniles settle in coastal areas. In this study, we combined genetic and Lagrangian drifter data to investigate the connectivity between natal and foraging locations. In particular we focus on the evidence for transatlantic transport. Location  Atlantic Ocean.

Methods  We used mitochondrial DNA (mtDNA) sequences (n = 1567) from foraging groups (n = 8) and nesting populations (n = 12) on both sides of the Atlantic. Genetic data were obtained for Cape Verde juvenile turtles, a foraging group not previously sampled for genetic study. Various statistical methods were used to explore spatial genetics and population genetic structure (e.g. exact tests of differentiation, Geneland and analysis of molecular variance). Many-to-many mixed stock analysis estimated the connectivity between nesting and foraging groups.

Results  Our key new finding is robust evidence for connectivity between a nesting population on the South American coast (25% of the Surinam nesting population are estimated to go to Cape Verde) and a foraging group off the coast of West Africa (38% of Cape Verde juveniles are estimated to originate from Surinam), thus extending the results of previous investigations by confirming that there is substantial transatlantic dispersal in both directions. Lagrangian drifter data demonstrated that transport by drift across the Atlantic within a few years is possible.

Main conclusions  Small juvenile green turtles seem capable of dispersing extensively, and can drop out of the pelagic phase on a transatlantic scale (the average distance between natal and foraging locations was 3048 km). Nevertheless, we also find support for the ‘closest-to-home’ hypothesis in that the degree of contribution from a nesting population to a foraging group is correlated with proximity. Larger-sized turtles appear to feed closer to their natal breeding grounds (the average distance was 1133 km), indicating that those that have been initially transported to far-flung foraging grounds may still be able to move nearer to home as they grow larger.

Exercise as an intervention to improve metabolic outcomes after intrauterine growth restriction

Individuals born after intrauterine growth restriction (IUGR) are at an increased risk of developing diabetes in their adult life. IUGR impairs β-cell function and reduces β-cell mass, thereby diminishing insulin secretion. IUGR also induces insulin resistance, with impaired insulin signaling in muscle in adult humans who were small for gestational age (SGA) and in rodent models of IUGR. There is epidemiological evidence in humans that exercise in adults can reduce the risk of metabolic disease following IUGR. However, it is not clear whether adult IUGR individuals benefit to the same extent from exercise as do normal-birth-weight individuals, as our rat studies suggest less of a benefit in those born IUGR. Importantly, however, there is some evidence from studies in rats that exercise in early life might be able to reverse or reprogram the long-term metabolic effects of IUGR. Studies are needed to address gaps in current knowledge, including determining the mechanisms involved in the reprogramming effects of early exercise in rats, whether exercise early in life or in adulthood has similar beneficial metabolic effects in larger animal models in which insulin resistance develops after IUGR. Human studies are also needed to determine whether exercise training improves insulin secretion and insulin sensitivity to the same extent in IUGR adults as in control populations. Such investigations will have implications for customizing the recommended level and timing of exercise to improve metabolic health after IUGR.

Participant characteristics associated with greater reductions in waist circumference during a four-month, pedometer-based, workplace health program

BACKGROUND: Workplace health programs have demonstrated improvements in a number of risk factors for chronic disease. However, there has been little investigation of participant characteristics that may be associated with change in risk factors during such programs. The aim of this paper is to identify participant characteristics associated with improved waist circumference (WC) following participation in a four-month, pedometer-based, physical activity, workplace health program.

METHODS: 762 adults employed in primarily sedentary occupations and voluntarily enrolled in a four-month workplace program aimed at increasing physical activity were recruited from ten Australian worksites in 2008. Seventy-nine percent returned at the end of the health program. Data included demographic, behavioural, anthropometric and biomedical measurements. WC change (before versus after) was assessed by multivariable linear and logistic regression analyses. Seven groupings of potential associated variables from baseline were sequentially added to build progressively larger regression models.

RESULTS: Greater improvement in WC during the program was associated with having completed tertiary education, consuming two or less standard alcoholic beverages in one occasion in the twelve months prior to baseline, undertaking less baseline weekend sitting time and lower baseline total cholesterol. A greater WC at baseline was strongly associated with a greater improvement in WC. A sub-analysis in participants with a 'high-risk' baseline WC revealed that younger age, enrolling for reasons other than appearance, undertaking less weekend sitting time at baseline, eating two or more pieces of fruit per day at baseline, higher baseline physical functioning and lower baseline body mass index were associated with greater odds of moving to 'low risk' WC at the end of the program.

CONCLUSIONS: While employees with 'high-risk' WC at baseline experienced the greatest improvements in WC, the other variables associated with greater WC improvement were generally indicators of better baseline health. These results indicate that employees who started with better health, potentially due to lifestyle or recent behavioural changes, were more likely to respond positively to the program. Future health program initiators should think innovatively to encourage all enrolees along the health spectrum to achieve a successful outcome.

Modelling solute transport in structured soils: performance evaluation of the ADR and TRM models

The movement of chemicals through the soil to the groundwater or discharged to surface waters represents a degradation of these resources. In many cases, serious human and stock health implications are associated with this form of pollution. The chemicals of interest include nutrients, pesticides, salts, and industrial wastes. Recent studies have shown that current models and methods do not adequately describe the leaching of nutrients through soil, often underestimating the risk of groundwater contamination by surface-applied chemicals and overestimating the concentration of resident solutes. This inaccuracy results primarily from ignoring soil structure and nonequilibrium between soil constituents, water, and solutes. A multiple sample percolation system (MSPS), consisting of 25 individual collection wells, was constructed to study the effects of localized soil heterogeneities on the transport of nutrients (NO−3, Cl−, PO3−4) in the vadose zone of an agricultural soil predominantly dominated by clay. Very significant variations in drainage patterns across a small spatial scale were observed (one-way ANOVA, p < 0.001 indicating considerable heterogeneity in water flow patterns and nutrient leaching. Using data collected from the multiple sample percolation experiments, this paper compares the performance of two mathematical models for predicting solute transport, the advective-dispersion model with a reaction term (ADR), and a two-region preferential flow model (TRM) suitable for modelling nonequilibrium transport. These results have implications for modelling solute transport and predicting nutrient loading on a larger scale.

Enabling industrial scale simulation / emulation models

OLE Process Control (OPC) is an industry standard that facilitates the communication between PCs and Programmable Logic Controllers (PLC). This communication allows for the testing of control systems with an emulation model. When models require faster and higher volume communications, limitations within OPC prevent this. In this paper an interface is developed to allow high speed and high volume communications between a PC and PLC enabling the emulation of larger and more complex control systems and their models. By switching control of elements within the model between the model engine and the control system it is possible to use the model to validate the system design, test the real world control systems and visualise real world operation.

A systematic review of the impact of including both waist and hip circumference in risk models for cardiovascular diseases, diabetes and mortality

Both a larger waist and narrow hips are associated with heightened risk of diabetes, cardiovascular diseases and premature mortality. We review the risk of these outcomes for levels of waist and hip circumferences when terms for both anthropometric measures were included in regression models. MEDLINE and EMBASE were searched (last updated July 2012) for studies reporting the association with the outcomes mentioned earlier for both waist and hip circumferences (unadjusted and with both terms included in the model). Ten studies reported the association between hip circumference and death and/or disease outcomes both unadjusted and adjusted for waist circumference. Five studies reported the risk associated with waist circumference both unadjusted and adjusted for hip circumference. With the exception of one study of venous thromboembolism, the full strength of the association between either waist circumference or hip circumference with morbidity and/or mortality was only apparent when terms for both anthropometric measures were included in regression models. Without accounting for the protective effect of hip circumference, the effect of obesity on risk of death and disease may be seriously underestimated. Considered together (but not as a ratio measure), waist and hip circumference may improve risk prediction models for cardiovascular disease and other outcomes.

In vitro strain measurements in cerebral aneurysm models for cyber-physical diagnosis

Background: The development of new diagnostic technologies for cerebrovascular diseases requires an understanding of the mechanism behind the growth and rupture of cerebral aneurysms. To provide a comprehensive diagnosis and prognosis of this disease, it is desirable to evaluate wall shear stress, pressure, deformation and strain in the aneurysm region, based on information provided by medical imaging technologies. Methods: In this research, we propose a new cyber-physical system composed of in vitro dynamic strain experimental measurements and computational fluid dynamics (CFD) simulation for the diagnosis of cerebral aneurysms. A CFD simulation and a scaled-up membranous silicone model of a cerebral aneurysm were completed, based on patient-specific data recorded in August 2008. In vitro blood flow simulation was realized with the use of a specialized pump. A vision system was also developed to measure the strain at different regions on the model by way of pulsating blood flow circulating inside the model. Results: Experimental results show that distance and area strain maxima were larger near the aneurysm neck (0.042 and 0.052), followed by the aneurysm dome (0.023 and 0.04) and finally the main blood vessel section (0.01 and 0.014). These results were complemented by a CFD simulation for the addition of wall shear stress, oscillatory shear index and aneurysm formation index. Diagnosis results using imaging obtained in August 2008 are consistent with the monitored aneurysm growth in 2011. Conclusion: The presented study demonstrates a new experimental platform for measuring dynamic strain within cerebral aneurysms. This platform is also complemented by a CFD simulation for advanced diagnosis and prediction of the growth tendency of an aneurysm in endovascular surgery.

Brand management in small to medium-sized enterprises

Although an impressive body of literature has emerged focusing on the critical activities involved in brand management for larger organizations with well-established brands and substantial marketing budgets, no research has been undertaken to examine branding within small to medium-sized enterprises (SMEs). The present study therefore seeks to assess the nature and scope of brand management within an SME context. Findings show significant differences between small and large organizations along 9 of the 10 brand management dimensions reported in Keller's brand report card. Moreover, different brand management practices are associated with business performance in SMEs. Implications of the study are highlighted, limitations noted, and directions for future research outlined.

Energy performance of medium-sized healthcare buildings in Victoria, Australia- a case study

This paper investigates the energy performance of three medium-sized healthcare buildings in Victoria, Australia, that operate only during the daytime. The aim is to provide preliminary understanding of energy consumption in this particular typology in Australia in relation to the available benchmarks. This paper also identifies the differences of energy consumption between different functional areas within medium health facilities. Building features and operational characteristics contributing to the variations in healthcare energy performance are discussed. The total annual energy consumption data ranging from 167-306 kWh/m(2) or 42-72 kWh/m(3) were compared against international data from various climatic zones. Some of the drivers of energy consumption were determined and potentials for energy and water conservation were identified. Comparison with international standards shows a possibility to achieve lower energy consumption in Victorian healthcare buildings.

Are quitting-related cognitions and behaviours predicted by proximal responses to plain packaging with larger health warnings? Findings from a national cohort study with Australian adult smokers

Background: Implementation of tobacco plain packaging (PP) with larger graphic health warnings (GHWs) in Australia had positive effects on responses reflecting the specific objectives of the PP policy and on follow-up quitting-related cognitions and behaviours. The aim of this study was to examine predictive relationships bewteen these proximal and distal outcomes.
Methods: A nationally representative sample of Australian adult cigarette smokers completed a baseline survey and a 1-month follow-up survey within the first year of policy implementation (n(weighted)=3215). Logistic regression analyses tested whether baseline measures of cigarette appeal, GHW effectiveness, perceived harm and concern/enjoyment predicted each of seven follow-up measures of quitted-related cognitions and behaviours, adjusting for baseline levels of the outcome and covariates.
Results: In multivariable models, we found consistent evidence that several baseline measures of GHW effectiveness positively and significantly predicted the likelihood that smokers at follow-up reported thinking about quitting at least daily, intending to quit, having a firm date to quit, stubbing out cigarettes prematurely, stopping oneself from smoking and having attempted to quit. Two of the quitting-related outcomes were also predicted by feeling more smoking-related concern than enjoyment. A smaller number of the appeal variables were prospectively associated with quitting-related outcomes, while believing that brands do not differ in harmlessness did not positively predict any outcomes.
Conclusions: These findings provide an initial insight into the pathways through which PP with larger GHWs may lead to changes in smoking behaviour. Future research should examine whether the effects are conditional on individual demographic and smoking characteristics.

Application of species distribution models to explain and predict the distribution, abundance and assemblage structure of nearshore temperate reef fishes

 Aim: The purpose of this study was to create predictive species distribution models (SDMs) for temperate reef-associated fish species densities and fish assemblage diversity and richness to aid in marine conservation and spatial planning. Location: California, USA. Methods: Using generalized additive models, we associated fish species densities and assemblage characteristics with seafloor structure, giant kelp biomass and wave climate and used these associations to predict the distribution and assemblage structure across the study area. We tested the accuracy of these predicted extrapolations using an independent data set. The SDMs were also used to estimate larger scale abundances to compare with other estimates of species abundance (uniform density extrapolation over rocky reef and density extrapolations taking into account variations in geomorphic structure). Results: The SDMs successfully modelled the species-habitat relationships of seven rocky reef-associated fish species and showed that species' densities differed in their relationships with environmental variables. The predictive accuracy of the SDMs ranged from 0.26 to 0.60 (Pearson's r correlation between observed and predicted density values). The SDMs created for the fish assemblage-level variables had higher prediction accuracies with Pearson's r values of 0.61 for diversity and 0.71 for richness. The comparisons of the different methods for extrapolating species densities over a single marine protected area varied greatly in their abundance estimates with the uniform extrapolation (density values extrapolated evenly over the rocky reef) always estimating much greater abundances. The other two methods, which took into account variation in the geomorphic structure of the reef, provided much lower abundance estimates. Main conclusions: Species distribution models that combine geomorphic, oceanographic and biogenic habitat variables can reliably predict spatial patterns of species density and assemblage attributes of temperate reef fishes at spatial scales of 50 m. Thus, SDMs show great promise for informing spatial and ecosystem-based approaches to conservation and fisheries management. © 2015 John Wiley

Online distance education models and research implications

As a form of education, distance education is influenced by educationaltheories and ideologies. Hence, over time its various theoretical modelshave reflected varying emphases on students, both individually and ingroups, on content and process, and on administration and costs, and itsguiding philosophies have ranged from knowledge replication to knowledge creation, and from teacher direction to learner engagement. Its founding purpose was the provision of education to populations who were not able to access available residential education. The reasons were not only based on the individual situation, such as, geographic location, family commitments,work commitments, or cost factors, but also included state issues such as insufficient institutions or a lack of enrolment places, full-time funding, or sufficient staff. These factors have contributed in various ways to the growth of distance education, both historically as when distance education was a major focus in many European countries after WWII, and as a current imperative in many countries where the need and desire for education outstrips the supply through residential institutions, regardless of their fiscal capacities. Education is seen by both individuals and states as essential for the development of a better socio-economic environment, hence, distance education has become the cost-affordable means of provision for millions worldwide.Distance education, then, is framed within larger socio-economic andpolitical contexts. These are not only reflective of societal characteristics like those identified by Keegan (2000): immediacy, globalization, privatization, and industrialization, to which we added professional learning, but also reflective of current social, political, and economic circumstances, such as the sequence of global economic crises this century.Within these contexts then, the provision of distance education seldomarises from the desire of an institution alone; rather there are likely to becomplex national, local, and individual aspirations where distance education is seen as the best solution. The realization of this provision depends on the issues being addressed and the various influences on the particular configuration of design and provision. It may be publicly or privately funded; it may seek to emulate or extend educational provision in residential institutions; its focus may be on increasing access or openness or convenience.Models or designs for distance education, then, have generally arisen from consideration of these instances, in part to provide a framework for researchers and in part to provide a means to reflect on issues that the models themselves have tried to resolve and sometimes inadvertently create.