Single crystal raman spectroscopy of natural finnemanite and comparison with the synthesised analogue

The single crystal Raman spectra of natural mineral finnemanite Pb5(AsO3)3Cl from the Långban locality, Filipstad district, Värmland province, Sweden are presented for the first time. It is a hexagonal mineral belonging to the ortho arsenite group, where the [AsO3]3- ion is isolated. The spectra of finnemanite are characterized by a strong band at 734 cm-1 overlying a shoulder at 726 cm-1, and broad overlapping bands in the lower wavenumber with the strongest band positioned at 174 cm-1. Band assignments were made based on band symmetry, experimental band positions from literature and DFT calculated Raman spectrum, and spectral comparison with other ortho arsenite minerals reinerite, cafarsite, and nealite and synthetic lead arsenite compounds Pb2(AsO2)3Cl, Pb2As2O5, and PbAs2O4 . The band at 734 cm-1 was assigned to υ1(AsO3), bands at 726 and 640 cm-1 assigned to υ3, 372 and 357 cm-1 to υ2, and 244, 239 and 207 cm-1 to υ4. The single crystal spectra of finnemanite showed good mode separation, allowing bands to be assigned a symmetry species of Ag, E1g, or E2g.

Single crystal raman spectroscopy of natural paulmooreite Pb2As2O5 and in comparison with the synthesised analogue

The single crystal Raman spectra of natural mineral paulmooreite Pb2As2O5 from the Långban locality, Filipstad district, Värmland province, Sweden are presented for the first time. It is a monoclinic mineral containing an isolated [As2O5]4-. Depolarised and single crystal spectra of the natural and synthetic sample compare favorably and are characterized by strong bands around 186 and 140 cm-1 and three medium bands at 800 – 700 cm-1. Band assignments were made based on band symmetry and spectral comparison between experimental band positions and those resulting from Hartree-Fock calculation of an isolated [As2O5]4- ion. Spectral comparison was also made with lead arsenites such as synthetic PbAs2O4 and Pb2(AsO2)3Cl and natural finnemanite in order to determine the contribution of the terminal and bridging O in paulmooreite. Bands at 760 – 733 cm-1 were assigned to terminal As-O vibrations, whereas stretches of the bridging O occur at 562 and 503 cm-1. The single crystal spectra showed good mode separation, allowing bands to be assigned a symmetry species of Ag or Bg.

Planning most-likely paths from overhead imagery

This paper is about planning paths from overhead imagery, the novelty of which is taking explicit account of uncertainty in terrain classification and spatial variation in terrain cost. The image is first classified using a multi-class Gaussian Process Classifier which provides probabilities of class membership at each location in the image. The probability of class membership at a particular grid location is then combined with a terrain cost evaluated at that location using a spatial Gaussian process. The resulting cost function is, in turn, passed to a planner. This allows both the uncertainty in terrain classification and spatial variations in terrain costs to be incorporated into the planned path. Because the cost of traversing a grid cell is now a probability density rather than a single scalar value, we can produce not only the most-likely shortest path between points on the map, but also sample from the cost map to produce a distribution of paths between the points. Results are shown in the form of planned paths over aerial maps, these paths are shown to vary in response to local variations in terrain cost.

Hydrothermal synthesis of single crystallin strontium titanate nanocubes

Strontium titanate nanocubes with an average edge length of 150mm have been successfully synthesized from a simple hydrothermal system. Characterization techniques such as X-ray powder diffraction analysis, scanning electron microscopy and energy-dispersive analysis of X-rays were used to investigate the products. The results showed that as-prepared powders are pure SrTiO3 with cubic shape, which consists with the growth habit of its intrinsic crystal structure. These uniform nanocubes with high crystallinity will exhibit superior physical properties in the practical applications. Furthermore, during the experimental process, it has been found that the dilute acid washing process is very important to obtain high pure SrTiO3.

Mathematical modelling of the drying of sol gel microspheres

This thesis presents a mathematical model of the evaporation of colloidal sol droplets suspended within an atmosphere consisting of water vapour and air. The main purpose of this work is to investigate the causes of the morphologies arising within the powder collected from a spray dryer into which the precursor sol for Synroc™ is sprayed. The morphology is of significant importance for the application to storage of High Level Liquid Nuclear Waste. We begin by developing a model describing the evaporation of pure liquid droplets in order to establish a framework. This model is developed through the use of continuum mechanics and thermodynamic theory, and we focus on the specific case of pure water droplets. We establish a model considering a pure water vapour atmosphere, and then expand this model to account for the presence of an atmospheric gas such as air. We model colloidal particle-particle interactions and interactions between colloid and electrolyte using DLVO Theory and reaction kinetics, then incorporate these interactions into an expression for net interaction energy of a single particle with all other particles within the droplet. We account for the flow of material due to diffusion, advection, and interaction between species, and expand the pure liquid droplet models to account for the presence of these species. In addition, the process of colloidal agglomeration is modelled. To obtain solutions for our models, we develop a numerical algorithm based on the Control Volume method. To promote numerical stability, we formulate a new method of convergence acceleration. The results of a MATLAB™ code developed from this algorithm are compared with experimental data collected for the purposes of validation, and further analysis is done on the sensitivity of the solution to various controlling parameters.

Improving Usability of Software Refactoring Tools

Post-deployment maintenance and evolution can account for up to 75% of the cost of developing a software system. Software refactoring can reduce the costs associated with evolution by improving system quality. Although refactoring can yield benefits, the process includes potentially complex, error-prone, tedious and time-consuming tasks. It is these tasks that automated refactoring tools seek to address. However, although the refactoring process is well-defined, current refactoring tools do not support the full process. To develop better automated refactoring support, we have completed a usability study of software refactoring tools. In the study, we analysed the task of software refactoring using the ISO 9241-11 usability standard and Fitts' List of task allocation. Expanding on this analysis, we reviewed 11 collections of usability guidelines and combined these into a single list of 38 guidelines. From this list, we developed 81 usability requirements for refactoring tools. Using these requirements, the software refactoring tools Eclipse 3.2, Condenser 1.05, RefactorIT 2.5.1, and Eclipse 3.2 with the Simian UI 2.2.12 plugin were studied. Based on the analysis, we have selected a subset of the requirements that can be incorporated into a prototype refactoring tool intended to address the full refactoring process.

Study on road traffic noise prediction model taking into account the citywide network

For the further noise reduction in the future, the traffic management which controls traffic flow and physical distribution is important. To conduct the measure by the traffic management effectively, it is necessary to apply the model for predicting the traffic flow in the citywide road network. For this purpose, the existing model named AVENUE was used as a macro-traffic flow prediction model. The traffic flow model was integrated with the road vehicles' sound power model, and the new road traffic noise prediction model was established. By using this prediction model, the noise map of entire city can be made. In this study, first, the change of traffic flow on the road network after the establishment of new roads was estimated, and the change of the road traffic noise caused by the new roads was predicted. As a result, it has been found that this prediction model has the ability to estimate the change of noise map by the traffic management. In addition, the macro-traffic flow model and our conventional micro-traffic flow model were combined, and the coverage of the noise prediction model was expanded.

Better to light a single candle than to curse the darkness : promoting law student well-being through a first year law subject

Australian law teachers are increasingly recognising that psychological distress is an issue for our students. This article describes how the Queensland University of Technology Law School is reforming its curriculum to promote student psychological well-being. Part I of the article examines the literature on law student psychological distress in Australia. It is suggested that cross-sectional and longitudinal studies undertaken in Australia provide us with different, but equally important, information with respect to law student psychological well-being. Part II describes a subject in the QUT Law School - Lawyering and Dispute Resolution – which has been specifically designed as one response to declines in law student psychological well-being. Part III then considers two key elements of the design of the subject: introducing students to the idea of a positive professional identity, and introducing students to non-adversarial lawyering and the positive role of lawyers in society as dispute resolvers. These two areas of focus specifically promote law student psychological well-being by encouraging students to engage with elements of positive psychology – in particular, hope and optimism.

Ureaplasma parvum : understanding the complexities of intra-amniotic infection in an ovine model

The human Ureaplasma species are the most frequently isolated bacteria from the upper genital tract of pregnant women and can cause clinically asymptomatic, intra-uterine infections, which are difficult to treat with antimicrobials. Ureaplasma infection of the upper genital tract during pregnancy has been associated with numerous adverse outcomes including preterm birth, chorioamnionitis and neonatal respiratory diseases. The mechanisms by which ureaplasmas are able to chronically colonise the amniotic fluid and avoid eradication by (i) the host immune response and (ii) maternally-administered antimicrobials, remain virtually unexplored. To address this gap within the literature, this study investigated potential mechanisms by which ureaplasmas are able to cause chronic, intra-amniotic infections in an established ovine model. In this PhD program of research the effectiveness of standard, maternal erythromycin for the treatment of chronic, intra-amniotic ureaplasma infections was evaluated. At 55 days of gestation pregnant ewes received an intra-amniotic injection of either: a clinical Ureaplasma parvum serovar 3 isolate that was sensitive to macrolide antibiotics (n = 16); or 10B medium (n = 16). At 100 days of gestation, ewes were then randomised to receive either maternal erythromycin treatment (30 mg/kg/day for four days) or no treatment. Ureaplasmas were isolated from amniotic fluid, chorioamnion, umbilical cord and fetal lung specimens, which were collected at the time of preterm delivery of the fetus (125 days of gestation). Surprisingly, the numbers of ureaplasmas colonising the amniotic fluid and fetal tissues were not different between experimentally-infected animals that received erythromycin treatment or infected animals that did not receive treatment (p > 0.05), nor were there any differences in fetal inflammation and histological chorioamnionitis between these groups (p > 0.05). These data demonstrate the inability of maternal erythromycin to eradicate intra-uterine ureaplasma infections. Erythromycin was detected in the amniotic fluid of animals that received antimicrobial treatment (but not in those that did not receive treatment) by liquid chromatography-mass spectrometry; however, the concentrations were below therapeutic levels (<10 – 76 ng/mL). These findings indicate that the ineffectiveness of standard, maternal erythromycin treatment of intra-amniotic ureaplasma infections may be due to the poor placental transfer of this drug. Subsequently, the phenotypic and genotypic characteristics of ureaplasmas isolated from the amniotic fluid and chorioamnion of pregnant sheep after chronic, intra-amniotic infection and low-level exposure to erythromycin were investigated. At 55 days of gestation twelve pregnant ewes received an intra-amniotic injection of a clinical U. parvum serovar 3 isolate, which was sensitive to macrolide antibiotics. At 100 days of gestation, ewes received standard maternal erythromycin treatment (30 mg/kg/day for four days, n = 6) or saline (n = 6). Preterm fetuses were surgically delivered at 125 days of gestation and ureaplasmas were cultured from the amniotic fluid and the chorioamnion. The minimum inhibitory concentrations (MICs) of erythromycin, azithromycin and roxithromycin were determined for cultured ureaplasma isolates, and antimicrobial susceptibilities were different between ureaplasmas isolated from the amniotic fluid (MIC range = 0.08 – 1.0 mg/L) and chorioamnion (MIC range = 0.06 – 5.33 mg/L). However, the increased resistance to macrolide antibiotics observed in chorioamnion ureaplasma isolates occurred independently of exposure to erythromycin in vivo. Remarkably, domain V of the 23S ribosomal RNA gene (which is the target site of macrolide antimicrobials) of chorioamnion ureaplasmas demonstrated significant variability (125 polymorphisms out of 422 sequenced nucleotides, 29.6%) when compared to the amniotic fluid ureaplasma isolates and the inoculum strain. This sequence variability did not occur as a consequence of exposure to erythromycin, as the nucleotide substitutions were identical between chorioamnion ureaplasmas isolated from different animals, including those that did not receive erythromycin treatment. We propose that these mosaic-like 23S ribosomal RNA gene sequences may represent gene fragments transferred via horizontal gene transfer. The significant differences observed in (i) susceptibility to macrolide antimicrobials and (ii) 23S ribosomal RNA sequences of ureaplasmas isolated from the amniotic fluid and chorioamnion suggests that the anatomical site from which they were isolated may exert selective pressures that alter the socio-microbiological structure of the bacterial population, by selecting for genetic changes and altered antimicrobial susceptibility profiles. The final experiment for this PhD examined antigenic size variation of the multiple banded antigen (MBA, a surface-exposed lipoprotein and predicted ureaplasmal virulence factor) in chronic, intra-amniotic ureaplasma infections. Previously defined ‘virulent-derived’ and ‘avirulent-derived’ clonal U. parvum serovar 6 isolates (each expressing a single MBA protein) were injected into the amniotic fluid of pregnant ewes (n = 20) at 55 days of gestation, and amniotic fluid was collected by amniocentesis every two weeks until the time of near-term delivery of the fetus (at 140 days of gestation). Both the avirulent and virulent clonal ureaplasma strains generated MBA size variants (ranging in size from 32 – 170 kDa) within the amniotic fluid of pregnant ewes. The mean number of MBA size variants produced within the amniotic fluid was not different between the virulent (mean = 4.2 MBA variants) and avirulent (mean = 4.6 MBA variants) ureaplasma strains (p = 0.87). Intra-amniotic infection with the virulent strain was significantly associated with the presence of meconium-stained amniotic fluid (p = 0.01), which is an indicator of fetal distress in utero. However, the severity of histological chorioamnionitis was not different between the avirulent and virulent groups. We demonstrated that ureaplasmas were able to persist within the amniotic fluid of pregnant sheep for 85 days, despite the host mounting an innate and adaptive immune response. Pro-inflammatory cytokines (interleukin (IL)-1â, IL-6 and IL-8) were elevated within the chorioamnion tissue of pregnant sheep from both the avirulent and virulent treatment groups, and this was significantly associated with the production of anti-ureaplasma IgG antibodies within maternal sera (p < 0.05). These findings suggested that the inability of the host immune response to eradicate ureaplasmas from the amniotic cavity may be due to continual size variation of MBA surface-exposed epitopes. Taken together, these data confirm that ureaplasmas are able to cause long-term in utero infections in a sheep model, despite standard antimicrobial treatment and the development of a host immune response. The overall findings of this PhD project suggest that ureaplasmas are able to cause chronic, intra-amniotic infections due to (i) the limited placental transfer of erythromycin, which prevents the accumulation of therapeutic concentrations within the amniotic fluid; (ii) the ability of ureaplasmas to undergo rapid selection and genetic variation in vivo, resulting in ureaplasma isolates with variable MICs to macrolide antimicrobials colonising the amniotic fluid and chorioamnion; and (iii) antigenic size variation of the MBA, which may prevent eradication of ureaplasmas by the host immune response and account for differences in neonatal outcomes. The outcomes of this program of study have improved our understanding of the biology and pathogenesis of this highly adapted microorganism.

Right-angle crash vulnerability of motorcycles at signalized intersections : mixed logit analysis

Motorcycles are particularly vulnerable in right-angle crashes at signalized intersections. The objective of this study is to explore how variations in roadway characteristics, environmental factors, traffic factors, maneuver types, human factors as well as driver demographics influence the right-angle crash vulnerability of motorcycles at intersections. The problem is modeled using a mixed logit model with a binary choice category formulation to differentiate how an at-fault vehicle collides with a not-at-fault motorcycle in comparison to other collision types. The mixed logit formulation allows randomness in the parameters and hence takes into account the underlying heterogeneities potentially inherent in driver behavior, and other unobserved variables. A likelihood ratio test reveals that the mixed logit model is indeed better than the standard logit model. Night time riding shows a positive association with the vulnerability of motorcyclists. Moreover, motorcyclists are particularly vulnerable on single lane roads, on the curb and median lanes of multi-lane roads, and on one-way and two-way road type relative to divided-highway. Drivers who deliberately run red light as well as those who are careless towards motorcyclists especially when making turns at intersections increase the vulnerability of motorcyclists. Drivers appear more restrained when there is a passenger onboard and this has decreased the crash potential with motorcyclists. The presence of red light cameras also significantly decreases right-angle crash vulnerabilities of motorcyclists. The findings of this study would be helpful in developing more targeted countermeasures for traffic enforcement, driver/rider training and/or education, safety awareness programs to reduce the vulnerability of motorcyclists.

Worthless and undeserving? : problematising the subjectivities of single parenthood

A considerable body of knowledge has been constructed perpetuating the notion single parenthood is a significant problem for society, and while this is supported by specific research designs and sampling practices, it is also maintained by two key discourses. The first constitutes single parenthood as a deficit, while the second identifies it as a risk. In both cases, these discourses are operationalised by the philosophy of neo-liberalism, which envisions good citizenship as economic autonomy. Historically, it has been the convergence of the risk and deficit discourses that has constituted single parenthood as a social problem. More recently, however, risk discourses have come to dominate thinking about single parenthood. As a result, this thesis terms risk discourses as dominant discourses. As dominant discourses, risk sidelines or discounts other ways of thinking about single parenthood. While a few exceptions are notable, including some feminist, poststructural and family resilience scholars, most researchers appear unable to see past the positioning of these discourses and envision another way of being for parents who are single. This means that alternative subjectivities are obscured and have limited influence in this field of research. Because this thesis aimed to problematise dominant subjectivities of single parenthood, a poststructural Foucauldian framework has been utilized in order to document the discursive constructions of single parenthood through literature, insider discourses, and outsider discourses. For the purposes of this thesis, outsider discourses are constituted as those outside the subjectivities of single parenthood, such as media and research discourses. An examination of the Australian media has been undertaken over a one year period, the results of which form the basis for the analysis of media discourses of single parenthood. Parents who are single were also targeted for self selection into this project to provide insider discourses about single parenthood. This analysis explored how respondents negotiated the discourses of single parenthood and how they themselves used or rejected the subjectivities constructed for them via these discourses to constitute their own subjectivities. This thesis aimed to explore the role of discourses in the construction of individuals' subjectivities. Specifically, it draws attention to the way in which knowledge and power work through discourses to emphasize what is allowable, both publicly and privately, in relation to single parenthood. Most importantly, this thesis offers alternative subjectivities for single parenthood to facilitate new ways of thinking about parents who are single.

Molecular investigation of the mechanical properties of single actin filaments based on vibration analyses

The mechanical vibration properties of single actin filaments from 50 to 288 nm are investigated by the molecular dynamics simulation in this study. The natural frequencies obtained from the molecular simulations agree with those obtained from the analytical solution of the equivalent Euler–Bernoulli beam model. Through the convergence study of the mechanical properties with respect to the filament length, it was found that the Euler–Bernoulli beam model can only be reliably used when the single actin filament is of the order of hundreds of nanometre scale. This molecular investigation not only provides the evidence for the use of the continuum beam model in characterising the mechanical properties of single actin filaments, but also clarifies the criteria for the effective use of the Euler–Bernoulli beam model.