Mining patterns and factors contributing to crash severity on road curves

Road curves are an important feature of road infrastructure and many serious crashes occur on road curves. In Queensland, the number of fatalities is twice as many on curves as that on straight roads. Therefore, there is a need to reduce drivers’ exposure to crash risk on road curves. Road crashes in Australia and in the Organisation for Economic Co-operation and Development(OECD) have plateaued in the last five years (2004 to 2008) and the road safety community is desperately seeking innovative interventions to reduce the number of crashes. However, designing an innovative and effective intervention may prove to be difficult as it relies on providing theoretical foundation, coherence, understanding, and structure to both the design and validation of the efficiency of the new intervention. Researchers from multiple disciplines have developed various models to determine the contributing factors for crashes on road curves with a view towards reducing the crash rate. However, most of the existing methods are based on statistical analysis of contributing factors described in government crash reports. In order to further explore the contributing factors related to crashes on road curves, this thesis designs a novel method to analyse and validate these contributing factors. The use of crash claim reports from an insurance company is proposed for analysis using data mining techniques. To the best of our knowledge, this is the first attempt to use data mining techniques to analyse crashes on road curves. Text mining technique is employed as the reports consist of thousands of textual descriptions and hence, text mining is able to identify the contributing factors. Besides identifying the contributing factors, limited studies to date have investigated the relationships between these factors, especially for crashes on road curves. Thus, this study proposed the use of the rough set analysis technique to determine these relationships. The results from this analysis are used to assess the effect of these contributing factors on crash severity. The findings obtained through the use of data mining techniques presented in this thesis, have been found to be consistent with existing identified contributing factors. Furthermore, this thesis has identified new contributing factors towards crashes and the relationships between them. A significant pattern related with crash severity is the time of the day where severe road crashes occur more frequently in the evening or night time. Tree collision is another common pattern where crashes that occur in the morning and involves hitting a tree are likely to have a higher crash severity. Another factor that influences crash severity is the age of the driver. Most age groups face a high crash severity except for drivers between 60 and 100 years old, who have the lowest crash severity. The significant relationship identified between contributing factors consists of the time of the crash, the manufactured year of the vehicle, the age of the driver and hitting a tree. Having identified new contributing factors and relationships, a validation process is carried out using a traffic simulator in order to determine their accuracy. The validation process indicates that the results are accurate. This demonstrates that data mining techniques are a powerful tool in road safety research, and can be usefully applied within the Intelligent Transport System (ITS) domain. The research presented in this thesis provides an insight into the complexity of crashes on road curves. The findings of this research have important implications for both practitioners and academics. For road safety practitioners, the results from this research illustrate practical benefits for the design of interventions for road curves that will potentially help in decreasing related injuries and fatalities. For academics, this research opens up a new research methodology to assess crash severity, related to road crashes on curves.

Employee work motivation and discretionary work effort

The focus of this thesis is discretionary work effort, that is, work effort that is voluntary, is above and beyond what is minimally required or normally expected to avoid reprimand or dismissal, and is organisationally functional. Discretionary work effort is an important construct because it is known to affect individual performance as well as organisational efficiency and effectiveness. To optimise organisational performance and ensure their long term competitiveness and sustainability, firms need to be able to induce their employees to work at or near their peak level. To work at or near their peak level, individuals must be willing to supply discretionary work effort. Thus, managers need to understand the determinants of discretionary work effort. Nonetheless, despite many years of scholarly investigation across multiple disciplines, considerable debate still exists concerning why some individuals supply only minimal work effort whilst others expend effort well above and beyond what is minimally required of them (Le. they supply discretionary work effort). Even though it is well recognised that discretionary work effort is important for promoting organisational performance and effectiveness, many authors claim that too little is being done by managers to increase the discretionary work effort of their employees. In this research, I have adopted a multi-disciplinary approach towards investigating the role of monetary and non-monetary work environment characteristics in determining discretionary work effort. My central research questions were "What non-monetary work environment characteristics do employees perceive as perks (perquisites) and irks (irksome work environment characteristics)?" and "How do perks, irks and monetary rewards relate to an employee's level of discretionary work effort?" My research took a unique approach in addressing these research questions. By bringing together the economics and organisational behaviour (OB) literatures, I identified problems with the current definition and conceptualisations of the discretionary work effort construct. I then developed and empirically tested a more concise and theoretically-based definition and conceptualisation of this construct. In doing so, I disaggregated discretionary work effort to include three facets - time, intensity and direction - and empirically assessed if different classes of work environment characteristics have a differential pattern of relationships with these facets. This analysis involved a new application of a multi-disciplinary framework of human behaviour as a tool for classifying work environment characteristics and the facets of discretionary work effort. To test my model of discretionary work effort, I used a public sector context in which there has been limited systematic empirical research into work motivation. The program of research undertaken involved three separate but interrelated studies using mixed methods. Data on perks, irks, monetary rewards and discretionary work effort were gathered from employees in 12 organisations in the local government sector in Western Australia. Non-monetary work environment characteristics that should be associated with discretionary work effort were initially identified through a review of the literature. Then, a qualitative study explored what work behaviours public sector employees perceive as discretionary and what perks and irks were associated with high and low levels of discretionary work effort. Next, a quantitative study developed measures of these perks and irks. A Q-sorttype procedure and exploratory factor analysis were used to develop the perks and irks measures. Finally, a second quantitative study tested the relationships amongst perks, irks, monetary rewards and discretionary work effort. Confirmatory factor analysis was firstly used to confirm the factor structure of the measurement models. Correlation analysis, regression analysis and effect-size correlation analysis were used to test the hypothesised relationships in the proposed model of discretionary work effort. The findings confirmed five hypothesised non-monetary work environment characteristics as common perks and two of three hypothesised non-monetary work environment characteristics as common irks. Importantly, they showed that perks, irks and monetary rewards are differentially related to the different facets of discretionary work effort. The convergent and discriminant validities of the perks and irks constructs as well as the time, intensity and direction facets of discretionary work effort were generally confirmed by the research findings. This research advances the literature in several ways: (i) it draws on the Economics and OB literatures to redefine and reconceptualise the discretionary work effort construct to provide greater definitional clarity and a more complete conceptualisation of this important construct; (ii) it builds on prior research to create a more comprehensive set of perks and irks for which measures are developed; (iii) it develops and empirically tests a new motivational model of discretionary work effort that enhances our understanding of the nature and functioning of perks and irks and advances our ability to predict discretionary work effort; and (iv) it fills a substantial gap in the literature on public sector work motivation by revealing what work behaviours public sector employees perceive as discretionary and what work environment characteristics are associated with their supply of discretionary work effort. Importantly, by disaggregating discretionary work effort this research provides greater detail on how perks, irks and monetary rewards are related to the different facets of discretionary work effort. Thus, from a theoretical perspective this research also demonstrates the conceptual meaningfulness and empirical utility of investigating the different facets of discretionary work effort separately. From a practical perspective, identifying work environment factors that are associated with discretionary work effort enhances managers' capacity to tap this valuable resource. This research indicates that to maximise the potential of their human resources, managers need to address perks, irks and monetary rewards. It suggests three different mechanisms through which managers might influence discretionary work effort and points to the importance of training for both managers and non-managers in cultivating positive interpersonal relationships.

Dynamics of transformation and fragmentation of composite liquid nano-particles

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

Why common factors in international bond returns are not so common

This paper analyzes the common factor structure of US, German, and Japanese Government bond returns. Unlike previous studies, we formally take into account the presence of country-specific factors when estimating common factors. We show that the classical approach of running a principal component analysis on a multi-country dataset of bond returns captures both local and common influences and therefore tends to pick too many factors. We conclude that US bond returns share only one common factor with German and Japanese bond returns. This single common factor is associated most notably with changes in the level of domestic term structures. We show that accounting for country-specific factors improves the performance of domestic and international hedging strategies.

Bioactive inorganic materials/alginate composite microspheres with controllable drug-delivery ability

Alginate microspheres are considered a promising material as a drug carrier in bone repair due to excellent biocompatibility, but their main disadvantage is low drug entrapment efficiency and non-controllable release. The aim of this study was to investigate the effect of incorporating mesoporous bioglass (MBG), non-mesoporous bioglass (BG) or hydroxyapatite (HAp) into alginate microspheres on their drug-loading and release properties. X-ray diffraction (XRD), transmission electron microscopy (TEM), scanning electron microscopy (SEM), Fourier transform infrared spectroscopy (FTIR), and atomic emission spectroscopy (AES) were used to analyse the composition, structure and dissolution of bioactive inorganic materials and their microspheres. Dexamethasone (DEX)-loading and release ability of four microspheres were tested in phosphate buffered saline with varying pHs. Results showed that the drug-loading capacity was enhanced with the incorporation of bioactive inorganic materials into alginate microspheres. The MBG/Alginate microspheres had the highest drug loading ability. DEX release from alginate microspheres correlated to the dissolution of MBG, BG and HAp in PBS, and that the pH was an efficient factor in controlling the DEX release; a high pH resulted in greater DEX release, whereas a low pH delayed DEX release. In addition, MBG/alginate, BG/alginate and HAp/alginate microspheres had varying apatite-formation and dissolution abilities, which indicate that the composites would behave differently with respect to bioactivity. The study suggests that microspheres made of a composite of bioactive inorganic materials and alginate have a bioactivity and degradation profile which greatly improves their drug delivery capacity, thus enhancing their potential applications as bioactive filler materials for bone tissue regeneration.

Customer-oriented deviance (COD) : a conceptualisation, development and validation of a behavioural measure

Frontline employee behaviours are recognised as vital for achieving a competitive advantage for service organisations. The services marketing literature has comprehensively examined ways to improve frontline employee behaviours in service delivery and recovery. However, limited attention has been paid to frontline employee behaviours that favour customers in ways that go against organisational norms or rules. This study examines these behaviours by introducing a behavioural concept of Customer-Oriented Deviance (COD). COD is defined as, “frontline employees exhibiting extra-role behaviours that they perceive to defy existing expectations or prescribed rules of higher authority through service adaptation, communication and use of resources to benefit customers during interpersonal service encounters.” This thesis develops a COD measure and examines the key determinants of these behaviours from a frontline employee perspective. Existing research on similar behaviours that has originated in the positive deviance and pro-social behaviour domains has limitations and is considered inadequate to examine COD in the services context. The absence of a well-developed body of knowledge on non-conforming service behaviours has implications for both theory and practice. The provision of ‘special favours’ increases customer satisfaction but the over-servicing of customers is also counterproductive for the service delivery and costly for the organisation. Despite these implications of non-conforming service behaviours, there is little understanding about the nature of these behaviours and its key drivers. This research builds on inadequacies in prior research on positive deviance, pro-social and pro-customer literature to develop the theoretical foundation of COD. The concept of positive deviance which has predominantly been used to study organisational behaviours is applied within a services marketing setting. Further, it addresses previous limitations in pro-social and pro-customer behavioural literature that has examined limited forms of behaviours with no clear understanding on the nature of these behaviours. Building upon these literature streams, this research adopts a holistic approach towards the conceptualisation of COD. It addresses previous shortcomings in the literature by providing a well bounded definition, developing a psychometrically sound measure of COD and a conceptually well-founded model of COD. The concept of COD was examined across three separate studies and based on the theoretical foundations of role theory and social identity theory. Study 1 was exploratory and based on in-depth interviews using the Critical Incident Technique (CIT). The aim of Study 1 was to understand the nature of COD and qualitatively identify its key drivers. Thematic analysis was conducted to analyse the data and the two potential dimensions of COD behaviours of Deviant Service Adaptation (DSA) and Deviant Service Communication (DSC) were revealed in the analysis. In addition, themes representing the potential influences of COD were broadly classified as individual factors, situational factors, and organisational factors. Study 2 was a scale development procedure that involved the generation and purification of items for the measure based on two student samples working in customer service roles (Pilot sample, N=278; Initial validation sample, N=231). The results for the reliability and Exploratory Factor Analyses (EFA) on the pilot sample suggested the scale had poor psychometric properties. As a result, major revisions were made in terms of item wordings and new items were developed based on the literature to reflect a new dimension, Deviant Use of Resources (DUR). The revised items were tested on the initial validation sample with the EFA analysis suggesting a four-factor structure of COD. The aim of Study 3 was to further purify the COD measure and test for nomological validity based on its theoretical relationships with key antecedents and similar constructs (key correlates). The theoretical model of COD consisting of nine hypotheses was tested on a retail and hospitality sample of frontline employees (Retail N=311; Hospitality N=305) of a market research panel using an online survey. The data was analysed using Structural Equation Modelling (SEM). The results provided support for a re-specified second-order three-factor model of COD which consists of 11 items. Overall, the COD measure was found to be reliable and valid, demonstrating convergent validity, discriminant validity and marginal partial invariance for the factor loadings. The results showed support for nomological validity, although the antecedents had differing impact on COD across samples. Specifically, empathy and perspective-taking, role conflict, and job autonomy significantly influenced COD in the retail sample, whereas empathy and perspective-taking, risk-taking propensity and role conflict were significant predictors in the hospitality sample. In addition, customer orientation-selling orientation, the altruistic dimension of organisational citizenship behaviours, workplace deviance, and social desirability responding were found to correlate with COD. This research makes several contributions to theory. First, the findings of this thesis extend the literature on positive deviance, pro-social and pro-customer behaviours. Second, the research provides an empirically tested model which describes the antecedents of COD. Third, this research contributes by providing a reliable and valid measure of COD. Finally, the research investigates the differential effects of the key antecedents in different service sectors on COD. The research findings also contribute to services marketing practice. Based on the research findings, service practitioners can better understand the phenomenon of COD and utilise the measurement tool to calibrate COD levels within their organisations. Knowledge on the key determinants of COD will help improve recruitment and training programs and drive internal initiatives within the firm.

Brain-derived neurotrophic factor (BDNF) gene : no major impact on antidepressant treatment response

The brain-derived neurotrophic factor (BDNF) has been suggested to play a pivotal role in the aetiology of affective disorders. In order to further clarify the impact of BDNF gene variation on major depression as well as antidepressant treatment response, association of three BDNF polymorphisms [rs7103411, Val66Met (rs6265) and rs7124442] with major depression and antidepressant treatment response was investigated in an overall sample of 268 German patients with major depression and 424 healthy controls. False discovery rate (FDR) was applied to control for multiple testing. Additionally, ten markers in BDNF were tested for association with citalopram outcome in the STAR*D sample. While BDNF was not associated with major depression as a categorical diagnosis, the BDNF rs7124442 TT genotype was significantly related to worse treatment outcome over 6 wk in major depression (p=0.01) particularly in anxious depression (p=0.003) in the German sample. However, BDNF rs7103411 and rs6265 similarly predicted worse treatment response over 6 wk in clinical subtypes of depression such as melancholic depression only (rs7103411: TT

Influence of smectite suspension structure on sheet orientation in dry sediments : XRD and AFM applications

The structure-building phenomena within clay aggregates are governed by forces acting between clay particles. Measurements of such forces are important to understand in order to manipulate the aggregate structure for applications such as dewatering of mineral processing tailings. A parallel particle orientation is required when conducting XRD investigation on the oriented samples and conduct force measurements acting between basal planes of clay mineral platelets using at. force microscopy (AFM). To investigate how smectite clay platelets were oriented on silicon wafer substrate when dried from suspension range of methods like SEM, XRD and AFM were employed. From these investigations, we conclude that high clay concns. and larger particle diams. (up to 5 μm) in suspension result in random orientation of platelets in the substrate. The best possible laminar orientation in the clay dry film, represented in the XRD 0 0 1/0 2 0 intensity ratio of 47 was obtained by drying thin layers from 0.02 wt.% clay suspensions of the natural pH. Conducted AFM investigations show that smectite studied in water based electrolytes show very long-range repulsive forces lower in strength than electrostatic forces from double-layer repulsion. It was suggested that these forces may have structural nature. Smectite surface layers rehydrate in water environment forms surface gel with spongy and cellular texture which cushion approaching AFM probe. This structural effect can be measured in distances larger than 1000 nm from substrate surface and when probe penetrate this gel layer, structural linkages are forming between substrate and clay covered probe. These linkages prevent subsequently smooth detachments of AFM probe on way back when retrieval. This effect of tearing new formed structure apart involves larger adhesion-like forces measured in retrieval. It is also suggested that these effect may be enhanced by the nano-clay particles interaction.

Hydrate stabilization in the three-dimensional hydrogen-bonded structure of the brucinium compound, bis(2,3-dimethoxy-10-oxostrychnidinium) biphenyl-4,4'-disulfonate hexahydrate

The crystal structure of the 2:1 proton-transfer compound of brucine with biphenyl-4,4’-disulfonate, bis(2,3-dimethoxy-10-oxostrychnidinium) biphenyl-4,4'-disulfonate hexahydrate (1) has been determined at 173 K. Crystals are monoclinic, space group P21 with Z = 2 in a cell with a = 8.0314(2), b = 29.3062(9), c = 12.2625(3) Å, β = 101.331(2)o. The crystallographic asymmetric unit comprises two brucinium cations, a biphenyl-4,4'-disulfonate dianion and six water molecules of solvation. The brucinium cations form a variant of the common undulating and overlapping head-to-tail sheet sub-structure. The sulfonate dianions are also linked head-to-tail by hydrogen bonds into parallel zig-zag chains through clusters of six water molecules of which five are inter-associated, featuring conjoint cyclic eight-membered hydrogen-bonded rings [graph sets R33(8) and R34(8)], comprising four of the water molecules and closed by sulfonate O-acceptors. These chain structures occupy the cavities between the brucinium cation sheets and are linked to them peripherally through both brucine N+-H...Osulfonate and Ocarbonyl…H-Owater to sulfonate O bridging hydrogen bonds, forming an overall three-dimensional framework structure. This structure determination confirms the importance of water in the stabilization of certain brucine compounds which have inherent crystal instability.

The contribution of different androgen receptor domains to receptor dimerization and signaling

The androgen receptor (AR) is a ligand-activated transcription factor of the nuclear receptor superfamily that plays a critical role in male physiology and pathology. Activated by binding of the native androgens testosterone and 5-dihydrotestosterone, the AR regulates transcription of genes involved in the development and maintenance of male phenotype and male reproductive function as well as other tissues such as bone and muscle. Deregulation of AR signaling can cause a diverse range of clinical conditions, including the X-linked androgen insensitivity syndrome, a form of motor neuron disease known as Kennedy’s disease, and male infertility. In addition, there is now compelling evidence that the AR is involved in all stages of prostate tumorigenesis including initiation, progression, and treatment resistance. To better understand the role of AR signaling in the pathogenesis of these conditions, it is important to have a comprehensive understanding of the key determinants of AR structure and function. Binding of androgens to the AR induces receptor dimerization, facilitating DNA binding and the recruitment of cofactors and transcriptional machinery to regulate expression of target genes. Various models of dimerization have been described for the AR, the most well characterized interaction being DNA-binding domain- mediated dimerization, which is essential for the AR to bind DNA and regulate transcription. Additional AR interactions with potential to contribute to receptor dimerization include the intermolecular interaction between the AR amino terminal domain and ligand-binding domain known as the N-terminal/C-terminal interaction, and ligand-binding domain dimerization. In this review, we discuss each form of dimerization utilized by the AR to achieve transcriptional competence and highlight that dimerization through multiple domains is necessary for optimal AR signaling.

Phenyl-ring disorder in the two-dimensional hydrogen-bonded structure of the 1:1 proton-transfer salt of the diazo-dye precursor 4-(phenyldiazenyl)aniline (aniline yellow) with L-tartaric acid

The structure of the 1:1 proton-transfer compound from the reaction of L-tartaric acid with the azo-dye precursor aniline yellow [4-(phenylazo)aniline], 4-(phenyldiazenyl)anilinium hydrogen 2R,3R-tartrate C12H12N3+ . C4H6O6- has been determined at 200 K. The asymmetric unit of the compound contains two independent phenylazoanilinium cations and two hydrogen L-tartrate anions. The structure is unusual in that all four phenyl rings of both cations have identical 50% rotational disorder. The two hydrogen L-tartrate anions form independent but similar chains through head-to-tail carboxylic O--H...O~carboxyl~ hydrogen bonds [graph set C7] which are then extended into a two-dimensional hydrogen-bonded sheet structure through hydroxyl O--H...O hydrogen-bonding links. The anilinium groups of the phenyldiazenyl cations are incorporated into the sheets and also provide internal hydrogen-bonding extensions while their aromatic tails layer in the structure without significant interaction except for weak \p--\p interactions [minimum ring centroid separation, 3.844(3) \%A]. The hydrogen L-tartrate residues of both anions have the common short intramolecular hydroxyl O--H...O~carboxyl~ hydogen bonds. This work has provided a solution to the unusual disorder problem inherent in the structure of this salt as well as giving another example of the utility of the hydrogen tartrate in the generation of sheet substructures in molecular assembly processes.

Structure of selected basic copper (II) sulphate minerals based upon spectroscopy : implications for hydrogen bonding

The application of near-infrared and infrared spectroscopy has been used for identification and distinction of basic Cu-sulphates that include devilline, chalcoalumite and caledonite. Near-infrared spectra of copper sulphate minerals confirm copper in divalent state. Jahn-Teller effect is more significant in chalcoalumite where 2B1g ® 2B2g transition band shows a larger splitting (490 cm-1) confirming more distorted octahedral coordination of Cu2+ ion. One symmetrical band at 5145 cm-1 with shoulder band 5715 cm-1 result from the absorbed molecular water in the copper complexes are the combinations of OH vibrations of H2O. One sharp band at around 3400 cm-1 in IR common to the three complexes is evidenced by Cu-OH vibrations. The strong absorptions observed at 1685 and 1620 cm-1 for water bending modes in two species confirm strong hydrogen bonding in devilline and chalcoalumite. The multiple bands in v3 and v4(SO4)2- stretching regions are attributed to the reduction of symmetry to the sulphate ion from Td to C2V. Chalcoalumite, the excellent IR absorber over the range 3800-500 cm-1 is treated as most efficient heat insulator among the Cu-sulphate complexes.

Autocrine fibroblast growth factor 2 increases the multipotentiality of human adipose-derived mesenchymal stem cells

Multipotent mesenchymal stem cells (MSCs), first identified in the bone marrow, have subsequently been found in many other tissues, including fat, cartilage, muscle, and bone. Adipose tissue has been identified as an alternative to bone marrow as a source for the isolation of MSCs, as it is neither limited in volume nor as invasive in the harvesting. This study compares the multipotentiality of bone marrow-derived mesenchymal stem cells (BMSCs) with that of adipose-derived mesenchymal stem cells (AMSCs) from 12 age- and sex-matched donors. Phenotypically, the cells are very similar, with only three surface markers, CD106, CD146, and HLA-ABC, differentially expressed in the BMSCs. Although colony-forming units-fibroblastic numbers in BMSCs were higher than in AMSCs, the expression of multiple stem cell-related genes, like that of fibroblast growth factor 2 (FGF2), the Wnt pathway effectors FRAT1 and frizzled 1, and other self-renewal markers, was greater in AMSCs. Furthermore, AMSCs displayed enhanced osteogenic and adipogenic potential, whereas BMSCs formed chondrocytes more readily than AMSCs. However, by removing the effects of proliferation from the experiment, AMSCs no longer out-performed BMSCs in their ability to undergo osteogenic and adipogenic differentiation. Inhibition of the FGF2/fibroblast growth factor receptor 1 signaling pathway demonstrated that FGF2 is required for the proliferation of both AMSCs and BMSCs, yet blocking FGF2 signaling had no direct effect on osteogenic differentiation. Disclosure of potential conflicts of interest is found at the end of this article.

A new multilevel converter configuration for high power and high quality applications

The Queensland University of Technology (QUT) allows the presentation of theses for the Degree of Doctor of Philosophy in the format of published or submitted papers, where such papers have been published, accepted or submitted during the period of candidature. This thesis is composed of ten published /submitted papers and book chapters of which nine have been published and one is under review. This project is financially supported by an Australian Research Council (ARC) Discovery Grant with the aim of investigating multilevel topologies for high quality and high power applications, with specific emphasis on renewable energy systems. The rapid evolution of renewable energy within the last several years has resulted in the design of efficient power converters suitable for medium and high-power applications such as wind turbine and photovoltaic (PV) systems. Today, the industrial trend is moving away from heavy and bulky passive components to power converter systems that use more and more semiconductor elements controlled by powerful processor systems. However, it is hard to connect the traditional converters to the high and medium voltage grids, as a single power switch cannot stand at high voltage. For these reasons, a new family of multilevel inverters has appeared as a solution for working with higher voltage levels. Besides this important feature, multilevel converters have the capability to generate stepped waveforms. Consequently, in comparison with conventional two-level inverters, they present lower switching losses, lower voltage stress across loads, lower electromagnetic interference (EMI) and higher quality output waveforms. These properties enable the connection of renewable energy sources directly to the grid without using expensive, bulky, heavy line transformers. Additionally, they minimize the size of the passive filter and increase the durability of electrical devices. However, multilevel converters have only been utilised in very particular applications, mainly due to the structural limitations, high cost and complexity of the multilevel converter system and control. New developments in the fields of power semiconductor switches and processors will favor the multilevel converters for many other fields of application. The main application for the multilevel converter presented in this work is the front-end power converter in renewable energy systems. Diode-clamped and cascade converters are the most common type of multilevel converters widely used in different renewable energy system applications. However, some drawbacks – such as capacitor voltage imbalance, number of components, and complexity of the control system – still exist, and these are investigated in the framework of this thesis. Various simulations using software simulation tools are undertaken and are used to study different cases. The feasibility of the developments is underlined with a series of experimental results. This thesis is divided into two main sections. The first section focuses on solving the capacitor voltage imbalance for a wide range of applications, and on decreasing the complexity of the control strategy on the inverter side. The idea of using sharing switches at the output structure of the DC-DC front-end converters is proposed to balance the series DC link capacitors. A new family of multioutput DC-DC converters is proposed for renewable energy systems connected to the DC link voltage of diode-clamped converters. The main objective of this type of converter is the sharing of the total output voltage into several series voltage levels using sharing switches. This solves the problems associated with capacitor voltage imbalance in diode-clamped multilevel converters. These converters adjust the variable and unregulated DC voltage generated by renewable energy systems (such as PV) to the desirable series multiple voltage levels at the inverter DC side. A multi-output boost (MOB) converter, with one inductor and series output voltage, is presented. This converter is suitable for renewable energy systems based on diode-clamped converters because it boosts the low output voltage and provides the series capacitor at the output side. A simple control strategy using cross voltage control with internal current loop is presented to obtain the desired voltage levels at the output voltage. The proposed topology and control strategy are validated by simulation and hardware results. Using the idea of voltage sharing switches, the circuit structure of different topologies of multi-output DC-DC converters – or multi-output voltage sharing (MOVS) converters – have been proposed. In order to verify the feasibility of this topology and its application, steady state and dynamic analyses have been carried out. Simulation and experiments using the proposed control strategy have verified the mathematical analysis. The second part of this thesis addresses the second problem of multilevel converters: the need to improve their quality with minimum cost and complexity. This is related to utilising asymmetrical multilevel topologies instead of conventional multilevel converters; this can increase the quality of output waveforms with a minimum number of components. It also allows for a reduction in the cost and complexity of systems while maintaining the same output quality, or for an increase in the quality while maintaining the same cost and complexity. Therefore, the asymmetrical configuration for two common types of multilevel converters – diode-clamped and cascade converters – is investigated. Also, as well as addressing the maximisation of the output voltage resolution, some technical issues – such as adjacent switching vectors – should be taken into account in asymmetrical multilevel configurations to keep the total harmonic distortion (THD) and switching losses to a minimum. Thus, the asymmetrical diode-clamped converter is proposed. An appropriate asymmetrical DC link arrangement is presented for four-level diode-clamped converters by keeping adjacent switching vectors. In this way, five-level inverter performance is achieved for the same level of complexity of the four-level inverter. Dealing with the capacitor voltage imbalance problem in asymmetrical diodeclamped converters has inspired the proposal for two different DC-DC topologies with a suitable control strategy. A Triple-Output Boost (TOB) converter and a Boost 3-Output Voltage Sharing (Boost-3OVS) converter connected to the four-level diode-clamped converter are proposed to arrange the proposed asymmetrical DC link for the high modulation indices and unity power factor. Cascade converters have shown their abilities and strengths in medium and high power applications. Using asymmetrical H-bridge inverters, more voltage levels can be generated in output voltage with the same number of components as the symmetrical converters. The concept of cascading multilevel H-bridge cells is used to propose a fifteen-level cascade inverter using a four-level H-bridge symmetrical diode-clamped converter, cascaded with classical two-level Hbridge inverters. A DC voltage ratio of cells is presented to obtain maximum voltage levels on output voltage, with adjacent switching vectors between all possible voltage levels; this can minimize the switching losses. This structure can save five isolated DC sources and twelve switches in comparison to conventional cascade converters with series two-level H bridge inverters. To increase the quality in presented hybrid topology with minimum number of components, a new cascade inverter is verified by cascading an asymmetrical four-level H-bridge diode-clamped inverter. An inverter with nineteen-level performance was achieved. This synthesizes more voltage levels with lower voltage and current THD, rather than using a symmetrical diode-clamped inverter with the same configuration and equivalent number of power components. Two different predictive current control methods for the switching states selection are proposed to minimise either losses or THD of voltage in hybrid converters. High voltage spikes at switching time in experimental results and investigation of a diode-clamped inverter structure raised another problem associated with high-level high voltage multilevel converters. Power switching components with fast switching, combined with hard switched-converters, produce high di/dt during turn off time. Thus, stray inductance of interconnections becomes an important issue and raises overvoltage and EMI issues correlated to the number of components. Planar busbar is a good candidate to reduce interconnection inductance in high power inverters compared with cables. The effect of different transient current loops on busbar physical structure of the high-voltage highlevel diode-clamped converters is highlighted. Design considerations of proper planar busbar are also presented to optimise the overall design of diode-clamped converters.

In vitro cultivation of adult human chondrocytes : importance of culture system, oxygen and zonal differences

Articular cartilage exhibits limited intrinsic regenerative capacity and focal tissue defects can lead to the development of osteoarthritis (OA), a painful and debilitating loss of cartilage tissue. In Australia, 1.4 million people are affected by OA and its prevalence is increasing in line with current demographics. As treatment options are limited, new therapeutic approaches are being investigated including biological resurfacing of joints with tissue-engineered cartilage. Despite some progress in the field, major challenges remain to be addressed for large scale clinical success. For example, large numbers of chondrogenic cells are required for cartilage formation, but chondrocytes lose their chondrogenic phenotype (dedifferentiate) during in vitro propagation. Additionally, the zonal organization of articular cartilage is critical for normal cartilage function, but development of zonal structure has been largely neglected in cartilage repair strategies. Therefore, we hypothesised that culture conditions for freshly isolated human articular chondrocytes from non-OA and OA sources can be improved by employing microcarrier cultures and a reduced oxygen environment and that oxygen is a critical factor in the maintenance of the zonal chondrocyte phenotype. Microcarriers have successfully been used to cultivate bovine chondrocytes, and offer a potential alternative for clinical expansion of human chondrocytes. We hypothesised that improved yields can be achieved by propagating human chondrocytes on microcarriers. We found that cells on microcarriers acquired a flattened, polygonal morphology and initially proliferated faster than monolayercultivated cells. However, microcarrier cultivation over four weeks did not improve growth rates or the chondrogenic potential of non-OA and OA human articular chondrocytes over conventional monolayer cultivation. Based on these observations, we aimed to optimise culture conditions by modifying oxygen tension, to more closely reflect the in vivo environment. We found that propagation at 5% oxygen tension (moderate hypoxia) did not improve proliferation or redifferentiation capacity of human osteoarthritic chondrocytes. Moderate hypoxia increased the expression of chondrogenic markers during redifferentiation. However, osteoarthritic chondrocytes cultivated on microcarriers exhibited lower expression levels of chondrogenic surface marker proteins and had at best equivalent redifferentiation capacities compared to monolayer-cultured cells. This suggests that monolayer culture with multiple passaging potentially selects for a subpopulation of cells with higher differentiation capacity, which are otherwise rare in osteoarthritic, aged cartilage. However, fibroblastic proteins were found to be highly expressed in all cultures of human osteoarthritic chondrocytes indicating the presence of a high proportion of dedifferentiated, senescent cells with a chondrocytic phenotype that was not rescued by moderate hypoxia. The different zones of cartilage support chondrocyte subpopulations, which exhibit characteristic protein expression and experience varying oxygen tensions. We, therefore, hypothesised that oxygen tension affects the zonal marker expression of human articular chondrocytes isolated from the different cartilage layers. We found that zonal chondrocytes maintained these phenotypic differences during in vitro cultivation. Low oxygen environments favoured the expression of the zonal marker proteoglycan 4 in superficial cells, most likely through the promotion of chondrogenesis. The putative zonal markers clusterin and cartilage intermediate layer protein were found to be expressed by all subpopulations of human osteoarthritic chondrocytes ex vivo and, thus, may not be reliable predictors of in vitro stratification using these clinically relevant cells. The findings in this thesis underline the importance of considering low oxygen conditions and zonal stratification when creating native-like cartilaginous constructs. We have not yet found the right cues to successfully cultivate clinically-relevant human osteoarthritic chondrocytes in vitro. A more thorough understanding of chondrocyte biology and the processes of chondrogenesis are required to ensure the clinical success of cartilage tissue engineering.