Investigation of the gas phase reactivity of the 1-adamantyl radical using a distonic radical anion approach

The gas phase reactions of the bridgehead 3-carboxylato-1-adamantyl radical anion were observed with a series of neutral reagents using a modified electrospray ionisation linear ion trap mass spectrometer. This distonic radical anion was observed to undergo processes suggestive of radical reactivity including radical-radical combination reactions, substitution reactions and addition to carbon-carbon double bonds. The rate constants for reactions of the 3-carboxylato-1-adamantyl radical anion with the following reagents were measured ( in units 10(-12) cm(3) molecule(-1) s(-1)): O-18(2) ( 85 +/- 4), NO ( 38.4 +/- 0.4), I-2 ( 50 +/- 50), Br-2 ( 8 +/- 2), CH3SSCH3 ( 12 +/- 2), styrene ( 1.20 +/- 0.03), CHCl3 ( H abstraction 0.41 +/- 0.06, Cl abstraction 0.65 +/- 0.1), CDCl3 ( D abstraction 0.035 +/- 0.01, Cl abstraction 0.723 +/- 0.005), allyl bromide (Br abstraction 0.53 +/- 0.04, allylation 0.25 +/- 0.01). Collision rates were calculated and reaction efficiencies are also reported. This study represents the first quantitative measurement of the gas phase reactivity of a bridgehead radical and suggests that distonic radical anions are good models for the study of their elusive uncharged analogues.

Molecular sliding filament model for muscular contraction based on multiscale investigation

A multiscale approach that bridges the biophysics of the actin molecules at nanoscale and the biomechanics of actin filament at microscale level is developed and used to evaluate the mechanical performances of actin filament bundles. In order to investigate the contractile properties of skeletal muscle which is induced by the protein motor of myosin, a molecular model is proposed in the prediction of the dynamic behaviors of skeletal muscle based on classic sliding filament model. Randomly distributed myosin motors are applied on a 2.2 μm long sarcomere, whose principal components include actin and myosin filaments. It can be found that, the more myosin motors on the sarcomere, the faster the sarcomere contracts. The result demonstrates that the sarcomere shortening speed cannot increase infinitely by the modulation of myosin, thus providing insight into the self-protective properties of skeletal muscles. This molecular filament sliding model provides a theoretical way to evaluate the properties of skeletal muscles, and contributes to the understandings of the molecular mechanisms in the physiological phenomenon of muscular contraction.

Radiographic imaging for traumatic ankle injuries : a demand profile and investigation of radiological reporting timeframes from an Australian tertiary facility

Background Radiographic examinations of the ankle are important in the clinical management of ankle injuries in hospital emergency departments. National (Australian) Emergency Access Targets (NEAT) stipulate that 90 percent of presentations should leave the emergency department within 4 hours. For a radiological report to have clinical usefulness and relevance to clinical teams treating patients with ankle injuries in emergency departments, the report would need to be prepared and available to the clinical team within the NEAT 4 hour timeframe; before the patient has left the emergency department. However, little is known about the demand profile of ankle injuries requiring radiographic examination or time until radiological reports are available for this clinical group in Australian public hospital emergency settings. Methods This study utilised a prospective cohort of consecutive cases of ankle examinations from patients (n=437) with suspected traumatic ankle injuries presenting to the emergency department of a tertiary hospital facility. Time stamps from the hospital Picture Archiving and Communication System were used to record the timing of three processing milestones for each patient's radiographic examination; the time of image acquisition, time of a provisional radiological report being made available for viewing by referring clinical teams, and time of final verification of radiological report. Results Radiological reports and all three time stamps were available for 431 (98.6%) cases and were included in analysis. The total time between image acquisition and final radiological report verification exceeded 4?hours for 404 (92.5%) cases. The peak demand for radiographic examination of ankles was on weekend days, and in the afternoon and evening. The majority of examinations were provisionally reported and verified during weekday daytime shift hours. Conclusions Provisional or final radiological reports were frequently not available within 4 hours of image acquisition among this sample. Effective and cost-efficient strategies to improve the support provided to referring clinical teams from medical imaging departments may enhance emergency care interventions for people presenting to emergency departments with ankle injuries; particularly those with imaging findings that may be challenging for junior clinical staff to interpret without a definitive radiological report.

Liability in negligence and the failure to disclose multiple risks in surgery : I would have been willing to run the risk

It has been 21 years since the decision in Rogers v Whitaker and the legal principles concerning informed consent and liability for negligence are still strongly grounded in this landmark High Court decision. This paper considers more recent developments in the law concerning the failure to disclose inherent risks in medical procedures, focusing on the decision in Wallace v Kam [2013] HCA 19. In this case, the appellant underwent a surgical procedure that carried a number of risks. The surgery itself was not performed in a sub-standard way, but the surgeon failed to disclose two risks to the patient, a failure that constituted a breach of the surgeon’s duty of care in negligence. One of the undisclosed risks was considered to be less serious than the other, and this lesser risk eventuated causing injury to the appellant. The more serious risk did not eventuate, but the appellant argued that if the more serious risk had been disclosed, he would have avoided his injuries completely because he would have refused to undergo the procedure. Liability was disputed by the surgeon, with particular reference to causation principles. The High Court of Australia held that the appellant should not be compensated for harm that resulted from a risk he would have been willing to run. We examine the policy reasons underpinning the law of negligence in this specific context and consider some of the issues raised by this unusual case. We question whether some of the judicial reasoning adopted in this case, represents a significant shift in traditional causation principles.

School-based physical activity programs for adolescent wellness improvement : an investigation of the association between wellness and physical activity

This thesis by publication included seven manuscripts that advanced contemporary understanding of the association between physical activity and wellness among adolescents. The findings suggested that due to potential interrelatedness between various aspects of wellness, changes in physical activity may also influence co-existing wellness domains; highlighting the potential for physical activity interventions to have a broad range of benefits among youth. These findings also added to the body of literature supporting the potential inclusion of physical activity as a component within multifaceted youth wellness programs. Findings reported in this thesis have implications for those seeking to initiate youth wellness interventions.

Depression and belongingness in general and workplace contexts : a cross-lagged longitudinal investigation

Belongingness has been linked to depression. Prior studies have been cross-sectional with few addressing distinct belongingness contexts. This study used structural equation modelling to investigate cross-lagged longitudinal relationships between general belonging, workplace belonging and depressive symptoms in a community sample of 221 working adults measured at two time points three months apart. Measures were: Sense of Belonging Instrument-Psychological (SOBI-P); Psychological Sense of Organizational Membership (PSOM); Depression Anxiety Stress Scales (DASS-21); Kessler Psychological Distress Scale (K10). General belonging was predicted more strongly by depressive symptoms than by baseline general belonging, suggesting that depressive symptoms not only linger but also influence future belongingness cognitions. Neither general nor workplace belonging longitudinally predicted depressive symptoms, however cross-sectional correlations were substantial. The concurrent path between general belongingness and depressive symptoms was strong. Results are consistent with daily process studies suggesting that reduced belongingness precipitates a rapid increase in depressive symptoms which influence longer term belongingness cognitions. Congruent with interpersonal descriptions of depression such as the social-cognitive interpersonal process model, results further suggest that belongingness cognitions are the proximal antecedent of a depressive response. Practitioners should monitor both a general sense of belonging as well as perceived relational value cues in specific contexts.

Numerical investigation on stable crack growth in plane stress

Large deformation finite element analysis has been carried out to investigate the stress-strain fields ahead of a growing crack for compact tension .a=W D 0:5/ and three-point bend .a=W D 0:1 and 0:5/ specimens under plane stress condition. The crack growth is controlled by the experimental J -integral resistance curves measured by Sun et al. The results indicate that the distributions of opening stress, equivalent stress and equivalent strain ahead of a growing crack are not sensitive to specimen geometry. For both stationary and growing cracks, similar distributions of opening stress and triaxiality can be found along the ligament. During stable crack growth, the crack-tip opening displacement (CTOD) resistance curve and the cohesive fracture energy in the fracture process zone are independent of specimen geometry and may be suitable criteria for characterizing stable crack growth in plane stress.

An investigation of Staphylococcus aureus and related species from flood affected and other environmental sources

This research investigated the microbial air quality of flooded houses in Brisbane suburbs following the January 2011 flood event. Flood waters can carry and spread human pathogenic bacteria, and these organisms can be dispersed into residential air by aerosolisation. This study found that the bacterial load was significantly different for indoor and outdoor areas of flood affected houses, but no significant differences were observed between flooded and non-flooded houses. This could be due to the rapid clean-up of flooded houses following the event. Molecular methods were used to identify and characterise staphylococcal species in residential air of flooded and non-flooded houses. A major finding was the diverse population of airborne staphylococci as well as the high rate of methicillin-resistance in these strains. By determining the genetic relatedness of residential air sourced staphylococci, a potential source for pathogenic strains can be identified.

Unidentified vehicle in multi-vehicle accident - failure to notify Nominal Defendant no bar to proceedings against it

In Kumar v Suncorp Metway Insurance Limited [2004] QSC 381 Douglas J examined s37 of the Motor Accident Insurance Act 1994 (Qld) in the context of an accident involving multiple insurers when a notice of accident had not been given to the Nominal Defendant

A qualitative investigation of adolescents’ perceived mechanisms of change from a universal school-based depression prevention program

A recent meta-analysis provides evidence supporting the universal application of school-based prevention programs for adolescent depression. The mechanisms underlying such successful interventions, however, are largely unknown. We report on a qualitative analysis of 109 Grade 9 students’ beliefs about what they gained from an evidence-based depression prevention intervention, the Resourceful Adolescent Program (RAP-A). Fifty-four percent of interviewees articulated at least one specific example of program benefit. A thematic analysis of responses revealed two major themes, improved interpersonal relationships and improved self-regulation, both stronger than originally assumed. A more minor theme also emerged—more helpful cognitions. It is postulated that both improved interpersonal relationships and improved self-regulation are likely to enhance one another, and more helpful cognitions may express its contribution through enhanced self-regulation. These findings broaden our understanding of the impact of depression prevention programs, beginning to illuminate how such programs benefit participants.

Failure of discontinuous railhead edges due to plastic strain accumulation

Railhead is perhaps the highest stressed civil infrastructure due to the passage of heavily loaded wheels through a very small contact patch. The stresses at the contact patch cause yielding of the railhead material and wear. Many theories exist for the prediction of these mechanisms of continuous rails; this process in the discontinuous rails is relatively sparingly researched. Discontinuous railhead edges fail due to accumulating excessive plastic strains. Significant safety concern is widely reported as these edges form part of Insulated Rail Joints (IRJs) in the signalling track circuitry. Since Hertzian contact is not valid at a discontinuous edge, 3D finite element (3DFE) models of wheel contact at a railhead edge have been used in this research. Elastic–plastic material properties of the head hardened rail steel have been experimentally determined through uniaxial monotonic tension tests and incorporated into a FE model of a cylindrical specimen subject to cyclic tension load- ing. The parameters required for the Chaboche kinematic hardening model have been determined from the stabilised hysteresis loops of the cyclic load simulation and imple- mented into the 3DFE model. The 3DFE predictions of the plastic strain accumulation in the vicinity of the wheel contact at discontinuous railhead edges are shown to be affected by the contact due to passage of wheels rather than the magnitude of the loads the wheels carry. Therefore to eliminate this failure mechanism, modification to the contact patch is essential; reduction in wheel load cannot solve this problem.

Experimental and finite element analysis to identify the source of vibration of a coach

This paper presents an investigation on the cause of severe vibration problem of a coach with four-cylinder engine running at an idle state using vibration and impact hammer modal experiments to obtain the main vibration frequency components and the natural characteristics of the coach. The vibration results indicate that the main vibration component comes from the vibration transmitted from the engine to the chassis frame, which is closely related with the engine idle speed. Based on structural simulation analysis of the coach’s chassis frame and comparison with modal testing, the coach severe vibration problem was due to coupling resonance between the engine idle frequency and the fourth natural frequency of the chassis frame. The solution to eliminate the vibration problem is provided by changing the local structure stiffness of the chassis frame. The contribution of this paper lies in providing a solution to solve similar problems.

Too much of a good thing?: An investigation into overparenting

This project investigated the concept of overparenting, parenting which over uses valued parenting practices, such as protection and care for offspring. It established a clearer definition of overparenting as related to school-aged children, created a measure of overparenting, and showed that overparenting actions/beliefs to do with homework may impact on a child/adolescent's sense of responsibility for their academic achievements. Previously, most parenting research and education focussed on parenting approaches which deliver insufficient effort for children. This project showed that excessive responsiveness or assistance may also be detrimental.

An investigation of goethite-seeded Al(OH)3 precipitation using in situ X-ray diffraction and Rietveld-based quantitative phase analysis

An in situ X-ray diffraction investigation of goethite-seeded Al(OH)3 precipitation from synthetic Bayer liquor at 343 K has been performed. The presence of iron oxides and oxyhydroxides in the Bayer process has implications for alumina reversion, which causes significant process losses through unwanted gibbsite precipitation, and is also relevant for the nucleation and growth of scale on mild steel process equipment. The gibbsite, bayerite and nordstrandite polymorphs of Al(OH)3 precipitated from the liquor; gibbsite appeared to precipitate first, with subsequent formation of bayerite and nordstrandite. A Rietveld-based approach to quantitative phase analysis was implemented for the determination of absolute phase abundances as a function of time, from which kinetic information for the formation of the Al(OH)3 phases was determined.