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Promoting the production of hydrogen during steam pyrolysis of Victorian brown coal using a pressurized entrained flow reactor
Brown coal is an abundant and low cost resource with inherent properties which are superior to higher ranked coals in the thermal processing of solid fuels to tar and gaseous fuels. Brown coals contain low levels of ash and high levels of volatile matters, leading to a highly porous material which is suitable for the rapid generation of H₂ rich gases. Producing H₂ rich fuels is an emerging step in the thermal treatment of low grade materials leading to the development of more cost effective and efficient technologies. The current pilot scale technologies are equipped with pressurized fixed bed reactors and gasification systems, primarily for CH₄ production, slurry-based treatments and H₂ assisted pyrolysis with supercritical fluids as there have been advancements in laboratory–scale settings with H₂-rich donors. However, the high operating costs, exceedingly high temperatures and low selectivity to product yields are current issues for large scale industrial applications. The application of a continuous pressurized steam pyrolysis system was implemented in this research to produce H₂ rich tar and gas which is proposed as a combined steam pyrolysis and gasification system to enhance the H₂ gas yield. The aim of the research was to determine the feasibility of employing Victorian brown coal as a low cost precursor for producing high value products under a specified set of operating conditions using an entrained–flow reactor. Significant increases in the poly aromatic hydrocarbons in the tar were found with increased pressures and a 1 mL/min steam flow rate. The interaction of the steam in pressurized pyrolysis pressures were significant compared to results without steam. The composition of char was reduced significantly at 2 MPa and 4 MPa. The micro gas chromatography results showed a maximum H₂ fraction of 98.8 vol% at 900 °C and 1 Mpa with steam, approximately 15 vol% higher than without steam. H2 of 2.9 g/kg H2 in the gas was achieved. Steam significantly in the CH₄, CO and CO₂ in the produced gas
Investigation of 1,4-quinone bioisosteres and the synthesis of bolinaquinone analogues as clathrin inhibitors
Clathrin is a ubiquitous protein primarily acting as the major protein in clathrin mediated endocytosis (CME). CME is a major process by which extracellular cargo can cross the cell wall, allowing for transport of nutrients, receptors, and other material. Misfunctioning CME has been implicated in multiple diseases, acting in cancer, neurological conditions such as Alzheimer’s and epilepsy, and is a major pathway exploited by viruses for cellular entry. A recent secondary non-CME function has been found for clathrin wherein clathrin in a TACC3-clathrin-chTOG-GTSE1 complex crosslinks and stabilises microtubules allowing for mitosis progression and ultimately cell division. Small molecule inhibitors of clathrin, and by extension inhibitors of CME is a potential route to modulate the above diseases. The current scope of reported CME inhibitors is limited to the Pitstop® series of compounds and early lead compounds such as ES9-17. There are, however, disagreements on target specificity and mode of action. A marine sponge metabolite, bolinaquinone (BLQ) 1 containing a 1,4-quinone moiety, was shown to inhibit CME in vitro (IC50: not reported). Structurally, BLQ possesses a complex decalin region which has limited further synthetic development and analogue generation. Previous work in the McCluskey group identified AG1166 2 (CME: 4.6 ± 0.5 µM, Dyn1: 29.7 ± 3.3 µM, ELISA: 2.77 ± 0.9 µM) as a structurally simplified naphthoquinone lead, possessing low micromolar clathrin inhibition which translated well in cell CME studies. Molecular docking with BLQ found a potentially novel fifth site of interaction to the clathrin terminal domain (CTD). This is yet to be experimentally validated. This thesis elaborates on the BLQ and AG1166 scaffolds, with the aim to replace the 1,4-quinone moiety found in these structures, in efforts to reduce potential promiscuity. Quinones are known to redox cycle, producing reactive oxygen species (ROS) which can result in DNA damage and unwanted cytotoxicity. In addition, this moiety is prone to covalent adduct formation, a potentially undesirable off-target effect. These investigations detail the molecular docking and ab initio calculation lead design of non-quinone containing leads through the synthesis and biological testing of five potential quinone bioisosteres. This ultimately resulted in the identification of three new quinone-free leads, 3-(cyclohexylmethylene)isochroman-1,4-dione 240 (CME: 10.9 µM, Dyn1: 20% at 100 µM, ELISA: not tested), octyl 4-((3-bromo-1,1-dioxido-4-oxo-4H-thiochromen-2-yl)amino)benzoate 355 (CME: not tested, Dyn1: not tested, ELISA: 6.09 µM) and 2-cyclohexylethyl 4-((3-bromo-1,1-dioxido-4-oxo-4H-thiochromen-2-yl)amino)benzoate 356 (CME: not tested, Dyn1: not tested, ELISA: 6.63 µM) of unique chemotype, with activities within 2- to 3- fold of the AG1166 lead. DFT ab initio and molecular docking methods were developed in order to guide synthetic elaboration
Rhizoremediation of petroleum hydrocarbon contaminated soil using Australian native vegetation
Rhizoremediation relies on the mutualistic symbiosis between plants and soil microorganisms in the root zones (rhizosphere microbiota). Plant root exudates facilitate microbial community establishment and dynamics (chemistry and biology) in the rhizosphere. In return, rhizosphere microbiota has a significant effect on the surrounding soil by encouraging the uptake of nutrients and contaminants. In the case of organic pollutants (e.g., petroleum hydrocarbons), the microbial consortia in the rhizosphere are capable of breaking down organic compounds, thereby ameliorating soil conditions and reducing phytotoxicity. Owing to the cooperative evolution and adaptation of microorganisms in the soil-plant-microbial systems and higher survivability under extreme conditions, the use of native wild plants is generally preferred over introduced plant species for hydrocarbon degradation. To date, most rhizoremediation studies have focused on grass species belonging to the Poaceae family. Despite this, there were only few studies evaluating the rhizoremediation potential of some grass species in Australia, and those of wild native plants outside grasses remain untapped. The overall objective of the thesis was to examine the potential of Australian native wild plant species on rhizoremediation of hydrocarbon contaminated soils and effectiveness of various soil amendments on the remediation. In order to achieve that, a microcosm system was developed using eight Australian native wild plants belonging to three families, namely Poaceae, Fabaceae and Proteaceae. These plants were selected due to their habitation of different climates and soil conditions, diverse taxa, and varied root morphologies. A clean clay loam soil collected from an area in Cobar Shire, New South Wales (-31.502085, 145.781435) was artificially contaminated with a 1:1 diesel/engine oil mixture. Plant tolerance to hydrocarbon compounds, which is the prerequisite factor in the rhizoremediation, was evaluated at selected contamination levels (5,000, 10,000 and 15,000 mg kg-1). In addition, various soil amendments were applied to the contaminated soil to enhance plant growth, soil microbial population and activity, and bioavailability of hydrocarbons, which all were expected to facilitate the removal of hydrocarbons in the rhizosphere. Plant growth and photosynthesis, soil microbial activity and specific gene abundance, and hydrocarbon removal rate were quantified. Data from a series of microcosm experiments provided evidence for varying tolerance of the selected plant species to hydrocarbon compounds. Only four out of eight plant species were considerably tolerant to soil hydrocarbon contamination. However, only two plant species, namely Chloris truncata (a member of Poaceae) and Hakea prostrata (a shrub and a member of Proteaceae) showed consistent tolerance and significant hydrocarbon removal throughout the experiments. Plant growth in the contaminated soil was significantly enhanced by the addition of nutrients such as mineral fertilizers and composted animal manure but hindered by a wood-chip-based biochar. Natural surface-active agents (surfactants) derived from an Australian native plant species significantly favoured plant and rhizosphere microbe performance and stimulated hydrocarbon bioavailability whereas an anionic synthetic surfactant (Triton-X100) caused adverse impact to the plants and their associated microbiota. Total soil microbial activity (assessed via dehydrogenase activity DHA and soil respiration) was not a good indicator for the presence and activity of hydrocarbon-degrading microorganisms in the soil because not all the microorganisms have the ability to metabolize petroleum hydrocarbon compounds. The abundance of alkane hydroxylase gene, which was driven by plant identity and soil amendment type, proved to be an excellent biomarker to monitor the efficiency of the remediation process. Similarly, photosynthesis via chlorophyll fluorescence measurement can be used as a quick and accurate assessment of plant performance in the polluted soil. This investigation identified two Australian native wild plant species (a grass and a shrub) which can be used for further in situ investigation about their rhizoremediation potential at any hydrocarbon contaminated site. There are considerable scopes for operational improvements in rhizoremediation of hydrocarbon contaminated sites regarding root exudate composition and metabolomes, genetic backgrounds of hydrocarbon-degrading microorganisms and microbial changes under various soil conditions, and methods to introduce exogenous beneficial microorganisms (i.e., bioaugmentation)
The association between depression, anxiety, and heart disease in males: a longitudinal study
Depression, anxiety, and heart disease are prevalent conditions that contribute a significant burden to Australian males. While depression is well researched in relation to heart disease, the association with anxiety is less understood, particularly in males. Thus, the purpose of this study was to explore whether depression and/or anxiety contributed to the onset of heart disease, and whether heart disease contributed to the onset of depression and/or anxiety. The sample used longitudinal data collected from Australian males in 2014 and 2016. Analyses were conducted using firth’s penalized logistic regression model and adjusted for covariates. Results showed that depression alone, and co-occurring depression and anxiety significantly increased a person’s risk of developing new onset heart disease. Results also found that heart disease did not significantly increase a person’s risk of new onset depression or anxiety over a two-year period. These findings have important implications for our theoretical understanding of the association between depression, anxiety, and heart disease among males. Mental health is an important consideration when assessing heart disease risk among males
Proteomic analysis of neuroproteins in pancreatic cancer
Pancreatic cancer has one of the highest mortality rates among cancers and this is primarily attributed to the absence of early diagnostic biomarkers and no effective targeted therapies. Recent findings have indicated that the infiltration of nerves can generate a positive tumour microenvironment for pancreatic cancer cell growth and dissemination. At the same time, pancreatic cancer cells can drive the outgrowth of nerves in the tumour microenvironment. Fully understanding the molecular mechanisms and mediators involved in this nerve-cancer cells crosstalk, not only provides a better understanding the stimulatory role of nerves in pancreatic cancer progression, but also constitutes a resource for delineating future biomarkers and therapeutic targets. However, detailed understanding of the molecular mechanisms and mediators underpinning the crosstalk between nerves and pancreatic cancer cells remains largely undone. Novel liquid chromatography tandem mass spectrometry (LC-MS/MS) based techniques, shotgun discovery proteomics and parallel reaction monitoring (PRM) targeted proteomics, have provided a wonderful platform to investigate crucial protein events at play in the crosstalk between nerves and pancreatic cancer cells, and to exploit this knowledge for early detection and better intervention in pancreatic cancer. The aims of this thesis were to use LC-MS/MS-based proteomics to discover novel neuroproteins in pancreatic cancer and to understand the role of these proteins in tumour progression and dissemination. More specifically, using shotgun and PRM proteomics analysis, the cellular proteome and secretome of pancreatic cancer cell lines were investigated and compared with that of normal pancreatic ductal epithelial cells. Moreover, we have also analysed the proteome and secretome of Schwann cells, which are the glial cells in peripheral nerves. Several candidate neuroproteins have been identified including cold shock domain containing E1 (CSDE1), galectin-3-binding protein (Gal-3BP), matrix metalloproteinase-2 (MMP-2), cathepsin D (CTSD), plasminogen activator inhibitor-1 (PAI-1), biglycan (BGN), tissue inhibitor of metalloproteinases-2 (TIMP-2), and galectin-1 (Gal-1) and the neurotrophin receptor sortilin. In addition, the function of these proteins in pancreatic cancer was further examined
A Personality Based Eating Awareness Program: participant workbook
The Personality Based Eating Awareness Program was developed by the TRACE Dietetics team at the University of Newcastle to offer a personalised approach, based on personality traits, to support individuals in improving their symptoms of addictive eating and dietary intake. Based on scientific research, the workbook contains five modules that individuals can work through at their own pace or be complemented by face-to-face sessions with a dietitian. The modules cover practical information for understanding addictive eating behaviours and provides a range of skill-building and goal setting exercises with the aim to create eating awareness. Developed in consultation with health professionals and consumers with lived experience of addictive eating, the program will assist individuals in in creating an ‘Addictive Eating Action Plan’ and improving their relationship with food
Development and assessment of bare and hybrid nanomaterials for the sensing of different analytes
Colorimetric biosensors show good potential for the detection of various analytes, including drugs, metals, dyes, pollutants, and others. These sensors have several advantages, including easy fabrication, quick detection, high selectivity and sensitivity, and visual colour-based detection, making them inexpensive and simple compared to other biosensors. The broad applicability of colorimetric biosensors can be utilized to design Point-of-Care (POC) sensors or assays for the detection of important analytes in the fields of environmental protection and disease diagnosis. However, the efficiency of these sensors is highly dependent on the material employed for their fabrication and hence the development of ideal materials for selected analyte detection using optical sensing is highly desirable. Nanozymes, a class of nanomaterials, exhibit properties similar to natural enzymes but can withstand harsh conditions such as high pH and extreme temperatures. With proper modifications, nanozymes have the potential to become low-cost, stable and highly efficient colorimetric biosensors with higher selectivity and sensitivity as compared to enzymes. Cerium oxide nanoparticle (nanoceria) is a promising nanozyme due to its dual oxidation states (Ce3+ and Ce4+) assisted by oxygen vacancies on its surface, which mimic enzyme activity and eliminate the need for external oxidizing agents in analyte detection. Surface modification or hybridization could further enhance the enzyme-like activity and analyte detection ability of nanoceria. Surface functionalisation and hybridisation has also been applied for other materials including mesoporous carbon nitrides (MCN) to explore their enzyme mimetic activity. MCN are a metal-free organic semiconductor with unique electronic and basic characteristics and exhibit mesoporous structure and high specific surface area and surface functional groups. Owing to these features, MCN can serve as a suitable platform for anchoring metal or metal oxide nanoparticles and creating hybrid nanozymes for improved colorimetric biosensing of different analytes. The proposed thesis focuses on the synthesis, functionalisation and characterisation of nano materials including nanoceria with varying oxidation states and copper functionalized and high nitrogen containing MCN (Cu-C3N5) and their application for sensing of different molecules. These functionalized nanostructures exhibit enzyme-mimetic activity for superoxide dismutase (SOD), catalase, oxidase, and peroxidase enzymes, based on their electronic and surface properties, allowing for oxidation and reduction reactions. Presence of prominent enzyme like activity of these materials enables detection of fluoride ions (environmental sensing), glutathione (cancer detection), and glucose (disease diagnosis) with a high detection range. The proposed thesis consists of five chapters. The first chapter focuses on the literature review of various MCN with different structures, nitrogen contents and morphologies, and their applications in sensing. This chapter highlights the research gaps in the synthesis and characterization of various MCN and specifically addresses their role in colorimetric sensing. Among the carbon nitrides, graphitic carbon nitride has shown a wide range of applications in sensing analytes, with major applications in environmental remediation, cancer prognosis, and organ dysfunction. Especially, MCN possess versatile textural, sensing and catalytic properties and are widely used in fields such as catalysis, gas capture, and remediation. The properties of MCNs are majorly dependent on several parameters such as precursors, temperature conditions, and templates which can be appropriately tuned to synthesise several different carbon nitrides with varying nitrogen contents. The recent development of new forms of MCNs with higher nitrogen content, such as C3N5, C3N6, and C3N7, has further expanded their potential into various promising applications. Their application in oxidation-reduction reactions (ORR), batteries and energy generation were highlighted on previous occasions. However, their use in sensing has been limited. The first chapter aims to provide a comprehensive review of recent findings in the synthesis of various MCNs with different nitrogen contents and their potential for photoelectrochemical, optical, and quartz microbalance-based sensing applications. Building upon the findings of the first chapter, which discussed the current limitations in the field of MCN for sensing different analytes, the second chapter aims to overcome those limitations. Previous studies have shown that carbon nitride has a high photocatalytic activity and in the presence of light, it can be used to sense glucose. However, achieving the similar sensing performance in the absence of light has rarely been addressed. To overcome this, high nitrogen containing MCN with a stoichiometry of C3N5 and Cu-C3N5 were synthesized for enhanced enzyme mimetic activity. The functionalization of MCN with Cu and the presence of higher nitrogen content in the framework render the material even more susceptible to enzyme mimetic activity specially peroxidase, even in the absence of light. Using this enhanced peroxidase mimetic activity, it was possible to successfully sense glucose and glutathione within a detection limit of 0.4 mM and 2.0 ppm, respectively. These biomolecules are associated with organ dysfunction and cancer prognosis and therefore the findings of this chapter demonstrate a huge potential of Cu-C3N5 for sensing these significant analytes with a high selectivity and sensitivity. The third chapter focuses on using nanoceria, a prominent nanoparticle in the field of nanozymes, for enzyme mimetic activity to sense different analytes. There are numerous studies demonstrating the various enzyme mimetic activities, such as catalase, SOD, oxidase, and peroxidase, of nanoceria. However, the mechanism behind the oxidase mimetic activity of nanoceria is not yet fully understood. To shed light on this mechanism, we synthesized nanoceria with different oxidation states and evaluated its enzyme mimetic activities. Our findings indicate that these activities are largely dependent on the oxidation state of surface cerium atoms. Once this relationship was established, we utilized the oxidase mimetic activity of nanoceria to sense fluoride ions within a linear range of 1 – 10 ppm effectively. This chapter represents a novel contribution to the field of sensing by being the first study to demonstrate the sensing of glutathione using another analyte, fluoride ion. In presence of fluoride ion, nanoceria can detect glutathione in a detection range of 2.5 – 50 ppm with LOD of 3.8 ppm. This work highlights the potential of nanoceria and its enzyme mimetic activity for sensing a wide range of important analytes. The overall thesis focuses on the use of enzyme mimetic activity of bare and functionalized materials specially nanoceria and MCNs for colorimetric sensing of various analytes. Specifically, the oxidase and peroxidase-like activity of these materials can oxidize the redox- active dyes, which change colour upon oxidation. This change in colour intensity is proportional to the concentration of the analyte, providing a means for sensing. The thesis explains this mechanism and demonstrates its use for sensing of fluoride ions, glucose, and glutathione, which play a role in environmental remediation, organ dysfunction, and cancer prognosis. The fourth chapter of the thesis highlights the concluding remarks and provides the directions for further research in the future. The fifth chapter of the thesis contains the information on the supplementary material for the experimental portion of chapter 2 and 3
A multisensory experience of art: transforming everyday spaces into 'otherworldly' places to support health and wellbeing
There is an emergence of interest in trans-disciplinary research exploring the arts and health sciences in order to solve contemporary health problems. Together they may play a proactive role in supporting the health and wellbeing of individuals and communities. Evidence for these benefits are attributed to, and range across, a breadth of research fields. However, one thing remains constant: “We are sensory beings in a sensory world – inseparable from it” (Erwine 2017, p. 36). It is now time to pursue research that sees a co-operative engagement between art and the health sciences for its benefits in the non-clinical health sector. This thesis uses a trans-disciplinary approach to explore the notion of an artistically created, multisensory environment and its potential to improve health and wellbeing outcomes in non-clinical and community contexts. A creative ‘practice-led’ research approach was used to navigate traditional health territories, producing a hybrid thesis that incorporates three manuscripts and a creative component. The creative component of this research involved the making of an artistically created multisensory environment, The Sensory-Art Space (SAS), which is documented in three artist books. The SAS formed the intervention for the subsequent research. In the thesis, I report on the research that investigated the experience and effects of spending time in the SAS on aspects of mental health and wellbeing using a mixed-methods approach. Participants in the research included 224 students and staff members of a university community. The collective research findings support the SAS as a restorative environment and a potential self-care strategy for positive emotion regulation, relaxation and stress reduction. This research is the first to explore the use of an artistically designed sensory room for non-clinical populations and encourages the potential use for multisensory interventions in everyday built environments. The findings identify new territory for artists as an important resource in the creation and development of new restorative and health-promoting spaces in public health
Exploring the role of pharmacists in the primary care management of inflammatory bowel disease
Multidisciplinary care (MDC) is essential to chronic disease management and optimal patient outcomes. Inflammatory bowel disease (IBD) is a chronic condition with a high burden of disease with increased incidences, health care costs and a poor quality of life. As a result, IBD care remains suboptimal and MDC underutilised in healthcare management of people living with IBD. This thesis by publication explores and aims to understand the facets of primary care management of IBD and how pharmacists as primary healthcare professionals can be better utilised to optimise IBD care in an aim to improve the care received by people with IBD. The thesis explores different domains of IBD management: identifying gaps in care, establishing current IBD knowledge and confidence among pharmacists, eliciting potential opportunities for primary care pharmacists and understanding the needs and perceptions of people living with IBD towards healthcare professionals. The first study in this body of work identified the roles of healthcare professionals in the management of chronic gastrointestinal diseases and highlighted the gap in IBD care, whereby IBD is predominantly managed by gastroenterologists with very little involvement of other healthcare professionals, especially in primary care settings. As a result, the second study identified potential roles for primary care health professionals, including pharmacists, to contribute to IBD management. Pharmacists are readily accessible healthcare professionals with proven skills and expertise in chronic disease management; especially disease with high burden such as asthma and Type 2 diabetes. Therefore, as part of the primary healthcare professionals, pharmacists can play a proactive role in optimising IBD care. People with IBD have complex needs and require IBD-specific expertise in managing their disease. Thus, the third and fourth studies in this thesis explored knowledge and confidence among pharmacists when managing people with IBD and identified opportunities for improvement. These studies are the first of their kind to address this knowledge gap and could be used to inform development of appropriate training and educational resources for pharmacists to develop the expertise and skills essential in managing IBD. The final study reflects the patient perspective of what people living with IBD need from healthcare professionals who are involved in managing their IBD. It reinforces that some healthcare professionals including pharmacists, currently do not have adequate knowledge or IBD-specific expertise to optimise IBD care. In conclusion, this thesis synthesises new data and five published papers that support the need for timely access to specialised IBD care for people living with IBD. It provides an insight into the existing IBD knowledge of primary care pharmacists and how the IBD knowledge gap can be optimised. Furthermore, it provides patient perspectives that are currently lacking in key areas of IBD management along with relevant data to guide future large scale research and interventions
Bubble size distribution and turbulence characterization in a bubbly flow in the presence of surfactant
This study aimed to quantify the less explored complex multiphase hydrodynamics of a bubble swarm in the presence of surfactant which is the key to flotation process widely used in the resources and environmental engineering applications. Experiments were conducted in a rectangular column (cross-section: 100 mm × 100 mm) in batch mode by varying the gas flux (0.02 to and 0.08 cm/s) in the presence of an anionic surfactant sodium dodecyl sulphate (5 to 15 ppm). High-speed imaging was then used to visualise the unsteady bubble plume dispersion behaviour and estimate the bubble size distribution (BSD) which showed a reduction in the mean bubble size with the increasing gas flux and surfactant concentration. Next, particle image velocimetry (PIV) was utilised to measure the instantaneous velocity field which was used to determine the turbulence characteristics. It was shown that the bubble plume contributes to significant anisotropy in the flow field which increased in the higher surfactant concentration and gas flux cases. The energy containing turbulence length scale was characterized by the integral length scale, which was observed to increase linearly with both the gas flux and surfactant concentration. Also, the local turbulence energy dissipation rate exhibited a strong linear correlation with the bubble surface area flux parameter. In the presence of surfactant, the turbulence energy spectrum of the system exhibited a less steep slope in the inertial subrange regime compared to the Kolmogorov −5/3 slope. The spectrum also showed a leftward shift indicating energy addition to the larger turbulence length scales which was reflected in the formation of large recirculation zones around the bubble plume