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(2013)Journal ArticleBackground and Objectives: Thought-action fusion (TAF), or maladaptive cognitions regarding the relationship between mental events and behaviours, has been implicated in the development and maintenance of obsessive-compulsive disorder (OCD). As some religions promote TAF-like appraisals, it has been proposed that religiosity may play a role in the transformation of normally occurring intrusive thoughts into clinically distressing obsessions. No research, however, has experimentally investigated the mediating role of TAF on the relationship between religiosity and OC symptoms. Methods: 85 Christian, Jewish, and Atheist/Agnostic participants were exposed to an experimental thought-induction protocol and reported on their associated levels of distress, guilt, feelings of responsibility, and urge to suppress target intrusions experienced during a 5-minute monitoring period. Participants also completed measures of obsessive-compulsive symptomatology, TAF beliefs, and general psychopathology. Results: Using PROCESS and bootstrapping analyses, a test of the conditional indirect effects of religiosity on obsessive-compulsive symptoms revealed that Christianity moderated the effects of religiosity on moral TAF beliefs, which in turn mediated the relationship between religiosity and obsessive-compulsive symptoms. Furthermore, in the Christian group, moral TAF beliefs mediated the relationship between religiosity and ratings of guilt and responsibility following the experimental protocol. Limitations: The use of university students with moderate levels of religiosity. Conclusions: Collectively the results suggest that obsessional thinking is not attributable to religion per se, but that teachings underlying certain religious doctrines may fuel TAF beliefs that are implicated in the maintenance of OCD.
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(2012)Journal ArticleThe CACCC-box binding protein erythroid Krüppel-like factor (EKLF/KLF1) is a master regulator that directs the expression of many important erythroid genes. We have previously shown that EKLF drives transcription of the gene for a second KLF, basic Krüppel-like factor, or KLF3. We have now tested the in vivo role of KLF3 in erythroid cells by examining Klf3 knockout mice. KLF3-deficient adults exhibit a mild compensated anemia, including enlarged spleens, increased red pulp, and a higher percentage of erythroid progenitors, together with elevated reticulocytes and abnormal erythrocytes in the peripheral blood. Impaired erythroid maturation is also observed in the fetal liver. We have found that KLF3 levels rise as erythroid cells mature to become TER119(+). Consistent with this, microarray analysis of both TER119(-) and TER119(+) erythroid populations revealed that KLF3 is most critical at the later stages of erythroid maturation and is indeed primarily a transcriptional repressor. Notably, many of the genes repressed by KLF3 are also known to be activated by EKLF. However, the majority of these are not currently recognized as erythroid-cell-specific genes. These results reveal the molecular and physiological function of KLF3, defining it as a feedback repressor that counters the activity of EKLF at selected target genes to achieve normal erythropoiesis.
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(2014)Journal ArticleClimate extremes, such as heat waves and heavy precipitation events, have large impacts on ecosystems and societies. Climate models provide useful tools for studying underlying processes and amplifying effects associated with extremes. The Australian Community Climate and Earth System Simulator (ACCESS) has recently been coupled to the Community Atmosphere Biosphere Land Exchange (CABLE) model. We examine how this model represents climate extremes derived by the Expert Team on Climate Change Detection and Indices (ETCCDI) and compare them to observational data sets using the AMIP framework. We find that the patterns of extreme indices are generally well represented. Indices based on percentiles are particularly well represented and capture the trends over the last 60 years shown by the observations remarkably well. The diurnal temperature range is underestimated, minimum temperatures (T-MIN) during nights are generally too warm and daily maximum temperatures (T-MAX) too low in the model. The number of consecutive wet days is overestimated, while consecutive dry days are underestimated. The maximum consecutive 1-day precipitation amount is underestimated on the global scale. Biases in T-MIN correlate well with biases in incoming longwave radiation, suggesting a relationship with biases in cloud cover. Biases in T-MAX depend on biases in net shortwave radiation as well as evapotranspiration. The regions and season where the bias in evapotranspiration plays a role for the T-MAX bias correspond to regions and seasons where soil moisture availability is limited. Our analysis provides the foundation for future experiments that will examine how land-surface processes contribute to these systematic biases in the ACCESS modelling system.
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(2013)Journal ArticleThe last interglaciation (similar to 130 to 116 ka) is a time period with a strong astronomically induced seasonal forcing of insolation compared to the present. Proxy records indicate a significantly different climate to that of the modern, in particular Arctic summer warming and higher eustatic sea level. Because the forcings are relatively well constrained, it provides an opportunity to test numerical models which are used for future climate prediction. In this paper we compile a set of climate model simulations of the early last interglaciation (130 to 125 ka), encompassing a range of model complexities. We compare the simulations to each other and to a recently published compilation of last interglacial temperature estimates. We show that the annual mean response of the models is rather small, with no clear signal in many regions. However, the seasonal response is more robust, and there is significant agreement amongst models as to the regions of warming vs cooling. However, the quantitative agreement of the model simulations with data is poor, with the models in general underestimating the magnitude of response seen in the proxies. Taking possible seasonal biases in the proxies into account improves the agreement, but only marginally. However, a lack of uncertainty estimates in the data does not allow us to draw firm conclusions. Instead, this paper points to several ways in which both modelling and data could be improved, to allow a more robust model-data comparison.
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(2021)ThesisThe electrochemical water splitting reaction, which consists of hydrogen reduction at the cathode and oxygen evolution (OER) at the anode, is one of the core processes for the utilization of sustainable and green energy sources. However, the sluggish kinetics of the oxygen evolution reaction requires a higher overpotential than the theoretical potential (1.23 V). Engineering a high-performance electrocatalyst is an avenue to improve the reaction kinetics for OER. Bimetallic branched nanoparticles offer substantial benefits for OER electrocatalysts; which include a greatly increased exposed surface area, highly crystalline hcp branches and stable surfaces. This thesis aims to design branched nanoparticles as electrocatalysts for enhanced OER in the following ways: (i) extending the cubic-core hexagonal-branch growth approach for a new bimetallic (Co, Au) system, (ii) leveraging the advantages of the Ru-Pd branched nanoparticles by tuning the surface facets and branch number, and (iii) making branched nanoparticles consisting of a cubic core (Pd) and alloyed branches (RuCo). Chapter one discusses the literature on the oxygen evolution reaction and Co- and Ru-based electrocatalysts for OER as well as the organic solution-phase synthesis method. The limiting factors of Co- and Ru- based catalysts and the strategies for improving their catalytic performance are also summarized. Also outlined is the fundamental understanding for synthesizing metallic nanoparticles using a seed-mediated growth approach in an organic solution phase and controlling the shape and size of the final products. Chapter two describes the synthetic methodology, sample purification, ink preparation for electrochemical measurements and characterization techniques in more detail. Chapter three provides the synthetic approaches and challenges in making Co and Ru branched nanoparticles. Chapter four compares the OER catalytic activity and stability of the Co-Au branched nanoparticles with the Co-Au core-shell and Co3O4 nanoparticles in alkaline media. The improved catalytic performance of the branched nanoparticles can be attributed to the formation of an active and stable oxide layer on the branch surface. Chapter five investigates the effect of branch number, and surface facets on the catalytic properties of the Ru-Pd branched nanoparticles with tunable branch number and surface facets. It is found that tuning surface facets and branch length is essential for enhancing catalytic performance by increasing the exposure of more active sites and improving the accessibility of the catalytic surface to the catalytic reaction. Chapter six explores alloyed branched nanoparticles consisting of a Pd core and RuCo branches and assesses their catalytic activity for OER electrocatalysts. It is demonstrated that Co leaching during catalytic activation in acid solution increases the exposure of highly catalytically active sites on the branch surface resulting in enhanced catalytic activity. Chapter seven concludes the overall results and achievements of this thesis and also discusses future opportunities.
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(2021)ThesisWith a theoretical capacity of 1672 mA h g-1, more than five times higher than any commercially available lithium-ion (Li-ion) cell systems, the lithium-sulfur (Li-S) cell is an attractive candidate for next generation energy storage. Despite this high theoretical capacity, Li-S cells generally suffer from poor capacity retention and working lifetimes that prevent them from mass commercialisation. This is mainly due to current limitations in managing the inherent Li-S redox reactions which involve diffusion and migration of electrochemically active polysulfides. One approach to prevent polysulfide migration is by rational design of the sulfur electrode framework. The aim of this research is to investigate the electrochemical implications of using different frameworks for entrapment of redox active species, mainly designed for the Li-S cell system. The two types of frameworks investigated are: (1) mixed-morphology carbon feeds derived from waste sources wherein the intention is for the carbon to purely act as a structural framework to trap lithium polysulfides, and (2) sulfur-rich copolymers wherein redox active sulfur is covalently bound within the framework. More specifically, the goals involve determining: (1) whether carbon acts purely as a structural framework to trap redox active species during electrochemistry, and (2) whether sulfur-rich copolymers act purely as a sulfur feed. Achieving these goals requires a thorough understanding of what properties in each framework are ideal for the Li-S cell. The main conclusion drawn from this work is that neither of the materials studied behaved as pure structural or covalent frameworks partaking in various side processes. Using specialised techniques such as X-ray powder diffraction, solid-state NMR, and X-ray absorption near-edge structure spectroscopy, the beneficial and parasitic side processes involved in each framework are able to be determined. Overall, a significantly enhanced understanding of the Li S cell chemistry when using these materials is presented in this work.
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(2021)ThesisPhotosynthesis has played a key role in the evolutionary trajectory of life on Earth. The ways in which organisms harvest sunlight have diversified over the billions of years since photosynthesis emerged in the quest for more efficient use of this energy source. The evolutionary origins of some organisms’ light harvesting apparatus, however, have remained elusive as have the causes for stark architectural changes between evolutionarily related organisms. In this thesis, I firstly provide a detailed exploration of published data describing photosynthetic efficiency through the lens of structural biology and quantum mechanics, examining observations from a range of antenna systems. After having built a framework for how an efficient photosynthetic antenna may be constructed, the rest of this thesis explores the evolutionary trajectory of the light harvesting antenna of the cryptophyte algae. Cryptophytes are a clade of secondary endosymbiotic algae which gained their photosynthetic chloroplasts from an engulfed red alga, but produced in an architecturally distinct antenna. Red algae have an antenna comprised of stacked protein rings that form an energetic funnel to the photosynthetic reaction centre which generates chemical energy from photon excitations. Cryptophytes took this energy funnel and dismantled it; complexing one of its component proteins with a peptide of unknown origin (‘cryptophyte alpha’) and packing them at high density within the chloroplast. By examining recently published cryo-electron microscopy maps of red algal antennas, I have discovered the evolutionary ancestor of the unique cryptophyte alpha subunit. Through this discovery, I reveal possible evolutionary events following secondary endosymbiosis leading to the origin of the cryptophyte light harvesting system. Finally, I examine the light harvesting antenna of a particular cryptophyte species, Hemiselmis andersenii, isolating multiple protein components and determining their crystal structures at high resolution. Through this, I discover a more complex antenna than previously thought with multiple protein components and a rich energetic structure. Some of these antenna proteins show previously unrecognised spectral properties and chromophore architecture. This structural data aids in understanding the architectural change between the red algal and cryptophyte light harvesting antennas and further diversification within the cryptophyte clade.
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(2006)Conference PaperThe erosion of hearth refractories typically governs the asset life of a blast furnace. Since operating conditions within the hearth make it practically impossible for direct measurement and visualisation, physical and mathematical models play an important role in understanding and assessing the cause-effect phenomena between the liquid iron, coke bed and refractories. A numerical model has been developed to predict the iron flow and temperature distribution within the packed bed and refractories. A number of case studies have been investigated for Port Kembla's No. 5 blast furnace, which is entering the 15th year of its current campaign. These case studies considered the effects of coke free layers (floating/sitting deadman), hearth deposits, coke bed fouling and localised refractory erosion. The refractory temperature distributions predicted by the model compare well with the blast furnace thermocouple measurements and as a result, the model has become a valuable predictive tool for hearth design and control.
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(2022)ThesisTime series models are used to model, simulate, and forecast the behaviour of a phenomenon over time based on data recorded over consistent intervals. The digital era has resulted in data being captured and archived in unprecedented amounts, such that vast amounts of information are available for analysis. Feature-rich time-series datasets are one of the data sets that have become available due to the expanding trend of data collection technologies worldwide. With the application of time series analysis to support financial and managerial decision-making, the development and advancement of time series models in the transportation domain are unavoidable. As a result, this thesis redefines time series models for transportation planning use with the following three aims: (1) To combine parametric and bootstrapping techniques within time series models; (2) to develop a time series model capable of modelling both temporal and spatial dependencies in time-series data; and (3) to leverage the hierarchical Bayesian modelling paradigm to accommodate flexible representations of heterogeneity in data. The first main chapter introduces an ensemble of ARIMA models. It compares its performance against conventional ARIMA (a parametric method) and LSTM models (a non-parametric method) for short-term traffic volume prediction. The second main chapter introduces a copula time series model that describes correlations between variables through time and space. Temporal correlations are modelled by an ARMA-GARCH model which enables a modeller to describe heteroscedastic data. The copula model has a flexible correlation structure and is used to model spatial correlations with the ability to model nonlinear, tailed and asymmetric correlations. The third main chapter provides a Bayesian modelling framework to raise awareness about using hierarchical Bayesian approaches for transport time series data. In addition, this chapter presents a Bayesian copula model. The combination of the two models provides a fully Bayesian approach to modelling both temporal and spatial correlations. Compared with frequentist models, the proposed modelling structures can incorporate prior knowledge. In the fourth main chapter, the fully Bayesian model is used to investigate mobility patterns before, during and after the COVID-19 pandemic using social media data. A more focused analysis is conducted on the mobility patterns of Twitter users from different zones and land use types.
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(2022)ThesisSinglet fission is a photo-physical process that generates two triplet excitons from one singlet exciton and can potentially enhance efficiency in photovoltaic systems. The combination of photovoltaics and singlet fission is a novel field for solar energy conversion when there is much interest in renewable, non-destructive, and continuously available energy sources. Singlet fission can also overcome thermalization losses in photovoltaics, which happens in traditional cells when the incident photon energy is higher than the silicon bandgap energy, using a carrier multiplication mechanism. This thesis will design, construct, and characterize photovoltaic devices incorporating singlet fission materials to study singlet fission in practical application. The research focuses on materials characterization, spin dynamics, and electron transfers between acene and the semiconductor layer in Au/TiO2 ballistic cells, and the incorporation of singlet fission layers on silicon-based cell structures. In detail, a set of investigations was developed and summarized by implementing singlet fission materials into a state-of-the-art ballistic photovoltaic device and silicon-based solar cell. The studies demonstrate proof of concept and rationally explain the process. The first part of the thesis investigates thin films of pentacene, TIPS-pentacene, and tetracene via crystallinity, morphology, absorption, and thickness characterization. Additionally, Au and TiO2 layers in Schottky device structures were optimized to achieve the best performance for energy transfer from an applied dye layer (merbromin). The drop-casted dye layer influences the device performance by increasing short-circuit current and open-circuit voltage, demonstrating the ability of charge transfer between the device and the applied film. This device structure provides a test bed for studying charge and energy transfer from singlet fission films. The latter part of the thesis describes several investigations to understand singlet fission in a thin film using this architecture. Magneto-photoconductivity measurements were primarily used to observe the spin dynamics via photoconductivity under an external magnetic field. Control experiments with bare Au/TiO2 devices showed no observable magneto-photoconductivity signal. In contrast, devices with pentacene and tetracene singlet fission layers showed a strong magnetoconductivity effect caused by ballistic electron transfer from the singlet fission layer into the TiO2 n-type semiconductor through an ultra-thin gold layer inserted between the layers. A qualitatively different behavior is seen between the pentacene and tetracene, which reveals that the energy alignment plays a crucial part in the charge transfer between the singlet fission layer and the device. The last section investigates the application of pentacene and tetracene evaporated thin-films as sensitizer layers to a silicon-based solar cell. The optimized Si cell structure with the annealing treatment improved the cell's performance by increasing short-circuit current and open-circuit voltage. The deposition of pentacene and tetracene as sensitizer layers into the device showed some results but posed several challenges that need to be addressed. As the current-voltage and external quantum efficiency measurements were taken, it was observed that material interfaces need to be designed to fully achieve the singlet fission of the acene layer into the Si devices.