A Theoretical Investigation of the Ni(II)-Catalyzed Hydrovinylation of Styrene

We report a detailed and full computational investigation on the hydrovinylation reaction of styrene with the Ni(II)-phospholane catalytic system, which was originally presumed to proceed through a cationic mechanism involving a nickel hydride intermediate. The following general features emerge from this study on a specific catalyst complex that was found to give quantitative yield and moderate selectivity: (a) the activation barrier for the initiation (18.8 kcal/mol) is higher than that for the reaction due to a low-lying square-planar pentenyl chelate intermediate originating from a Ni(II)-allyl catalyst precursor. Consequently there is an induction period for the catalysis; (b) the exit of product from the catalyst is via a β-H-transfer step instead of the usual β-H elimination pathway, which has a very high activation energy due to a trans effect of the phospholane ligand; (c) the turnover-limiting and enantio- determining transition state is also the β-H-transfer; (d) because of the absence of a hydride intermediate, the unwanted isomerization of the product is prevented; (e) since the enantio-discrimination is decided at the H-transfer stage itself, the configuration of the product in a catalytic cycle influences the enantioselectivity in the subsequent cycle; (f) the trans effect of the sole strong ligand in the d8 square-planar Ni(II), the stability of the η3-benzyl intermediate, and the availability of three coordination sites enable regioselective hydrovinylation over the possible oligomerization/polymerization of the olefin substrates and linear hydrovinylation. This work has also confirmed the previously recognized role of the hemilabile group at various stages in the mechanism.

Finnish Homicides and Mental Disorders: An investigation of offense and offender characteristics

Although the majority of people with mental illness are not violent, scientific studies over the last decades show that certain psychiatric disorders increase the risk of violent behavior, including homicide. This thesis examined crime scene behaviors and offender background characteristics among mentally ill Finnish homicide offenders. Previously, homicide crime scene behaviors have been investigated in relation to offender demographic characteristics, whereas this study compares the behaviors of offenders with various mental illnesses. The study design was a retrospective chart review of the forensic psychiatric statements of Finnish homicide offenders. The work consists of four substudies. The aims of the study were as follows: To describe differences in the childhood and family backgrounds as well as in the adolescent and adult adjustment of Finnish homicide offenders belonging to different diagnostic categories (schizophrenia, personality disorder, alcoholism, drug addiction or no diagnosis). Further, the study examined associations between the crime scene behaviors and mental status of these offenders. Also, the distinguishing characteristics between two groups of offenders with schizophrenia were examined: early starters, who present antisocial behavior before the onset of schizophrenia, and late starters, who first offend after the onset of mental disorder. Finally, it was investigated how the use of excessive violence is associated with clinical and circumstantial variables as well as offender background characteristics among homicide offenders with schizophrenia. The main findings of the study can be summarized as follows. First, offenders with personality disorder or drug addiction had experienced multiple difficulties in their early environments: both family and individual problems were typical. Offenders with schizophrenia were relatively well-adjusted in childhood compared to the other groups. However, in adolescence and adulthood, social isolation, withdrawal and other difficulties attributable to these offenders illness became evident. In several aspects, offenders with alcohol dependency resembled offenders with no diagnosis in that these offenders had less problematic backgrounds compared to other groups. Second, the results showed that crime scene behaviors, victim gender and the victim-offender relationship differ between the groups. In particular, offenders with a diagnosis of schizophrenia or drug addiction have some unique features in their crime scene behaviors and choice of victims. Offenders with schizophrenia were more likely to kill a blood relative, to use a sharp weapon and to injure the victim s face. Drug addiction was associated with stealing from the victim and trying to cover up the body. Third, the results suggest that the offense characteristics of early- and late-start offenders with schizophrenia differ only modestly. However, several significant differences between the groups were found in characteristics of offenders: early starters had experienced a multitude of problems in their childhood surroundings and also later in life. Fourth, violent acts where the offender did not commit the offense alone or had previous homicidal history were predictive of excessive violence among offenders with schizophrenia. Positive psychotic symptoms did not predict the use of excessive violence. Nearly one third of the cases in the sample involved multiple and severe violence, including features such as sadism, mutilation, sexual components or extreme stabbing. In sum, mentally disordered homicide offenders are heterogeneous in their offense characteristics as well as their background characteristics. Empirically based information on how the offender s mental state is associated with specific crime scene behaviors can be utilized within the police force in developing methods of prioritizing suspects in unsolved homicide cases. Also, these results emphasise the importance of early interventions for problem families and children at risk of antisocial behavior. They may also contribute to the development of effective treatment for violent offenders.

A biomechanical investigation of fusionless growth modulation implants for spinal scoliosis treatment

This thesis studied a new minimally invasive implant for scoliosis correction that aims to correct the deformity without fusing the spine, thereby allowing movement and growth in the spine following surgery. The effect of two different vertebral body implant (staple) designs on the stiffness of the spine, using calf spines as an in vitro model, was studied. The results showed that the implants decreased spinal stiffness, with associated potential damage to the growth plates due to the staple tips. There were no significant differences in stiffness between the two staple designs tested.

Coastal Wetlands Resources Investigation of the Burdekin Delta for declaration as fisheries reserves. Report to Ocean Rescue 2000

A project to investigate the coastal wetland resources of the Burdekin Delta, north Queensland, was undertaken as part of the long-term assessment of the coastal fisheries resources of Queensland. Extending from November 1993 to May 1995, fieldwork was undertaken in November 1993 and August 1994. The scope of the coastal wetlands resources investigation of the Burdekin Delta for declaration as a Fish Habitat Area was: 1. To document and map the marine wetland vegetation communities in the Burdekin River delta. 2. To document levels of existing disturbance to wetlands, existing recreational and commercial fisheries resources, and existing fishing activities. 3. To evaluate the conservation values of the areas investigated from the viewpoint of fisheries productivity and as habitat for important/threatened species. 4. To initiate Fish Habitat Area declaration under Section 120 of the Queensland Fisheries Act 1994 with formal consultation to all stakeholders. This report concentrates on Points 1 and 3, the documentation of the marine wetland vegetation communities and the evaluation of conservation values from a fisheries viewpoint. Dataset URL Link: Queensland Coastal Wetlands Resources Mapping data. [Dataset]

Queensland Coastal Wetland Resource Investigation of the Bowen Region: Cape Upstart to Gloucester Island

The wetland resources of the Queensland coastline have been mapped as a baseline dataset for Marine Protected Area investigation and particularly Fish Habitat Area (FHA) declaration, Ramsar site nomination and continued monitoring of these important fish habitats. This report summarises the results of the mapping undertaken in the Bowen region from the East Coast of Cape Upstart (Abbot Bay) to Gloucester Island (encompassing Edgecumbe Bay). The study was undertaken in order to: 1. document and map the coastal wetland communities within the Bowen region; 2. document levels of existing disturbance to and protection of the wetlands; 3. examine existing recreational and commercial fisheries in the region; and 4. evaluate the significance of the coastal wetlands in the region. Dataset URL Link: Queensland Coastal Wetlands Resources Mapping data. [Dataset]

An exploratory investigation of the practice of assessment for learning in Vietnamese higher education: Three case studies of lecturers' practice

In response to limited research conducted on the practice of assessment for learning (AfL) in higher education and in Asian educational settings, this qualitative study, using sociocultural theories of learning and a multiple case study approach, investigates how AfL was implemented by three lecturers in one Vietnamese university. Findings revealed that the lecturers engaged with AfL principles and practices to some extent. However, despite the lecturers' significant efforts, Vietnamese sociocultural factors such as respect for harmony, hierarchy, and examination-oriented learning, impacted on their practice of AfL. This study therefore argues that AfL requires adaptation for it to be effective in the Vietnamese tertiary context.

An investigation of solid adamantane by a modified isothermal-isobaric ensemble Monte Carlo simulation

Isothermal-isobaric ensemble Monte Carlo simulation studies of adamantane have been carried out at different temperatures. Thermodynamic properties and radial distribution functions calculated by employing a simple potential model based on sitesite interactions show good agreement with experiment and suggest that the solid is orientationally disordered at high temperatures.

Photoacoustic investigation of phase transitions in solids

The use of the photoacoustic effect in the investigation of first- and second-order phase transitions has been examined. Changes in the amplitude of the photoacoustic signal across the phase transition are compared with changes in thermal properties such as specific heat and thermal diffusivity. The systemsstudied include NaN02, TlN03, CsN03, NH4N03, BaTiO,, COO, Cu,HgI,, V02 andV305. The current photoacoustic studies are discussed in the light of the theoretical models available.

A molecular dynamics investigation of the structure of PbO---PbF2 glasses*1

The structure of PbO---PbF2 glasses has been studied using molecular dynamics (MD). The existence of [OPb4] structural units is observed over the entire glass-forming range, in conformity with a model proposed earlier based on various structural investigations of this system. Various other features of the structural model are also supported by the MD calculations.

An investigation of migration and possible stock structuring by the stout whiting, Sillago robusta, in southern Queensland waters, and its impact on managing the fishery. Final Report on the Pilot Program

A highly polymorphic genetic locus of Stout Whiting was examined for evidence of geographical subdivision amongst samples collected from three locales in southern Queensland waters. Statistical indicators of subdivision were not significantly different from zero, suggesting that it is unlikely that the Stout Whiting resource in southern Queensland is genetically subdivided into separate stocks. It is recommended that the full-scale genetic program not proceed and that the resource be managed as a single stock.

An Electron-Microscopic Investigation Of Oxides Related To Beta-Alumina

High resolution electron microscopic (HREM) investigation of potassiumbeta-alumina and the related gallate and ferrite has revealed that whereas the aluminate and gallate are highly disordered, consisting of random sequence ofbeta andbetaPrime units, the ferrite is more ordered. The aluminate and gallate are sensitive to electron beam irradiation exhibiting beam-induced damage similar to sodiumbetaPrime-alumina. Significantly, the ferrite is beamstable, the difference in behaviour amongst these related oxides arising from the different mechanisms by which alkali metal nonstoichiometry is accommodated. Barium hexaaluminate and hexaferrite are both highly ordered; specimens prepared by the barium borate flux method exhibit a new radic3a×radic3a superstructure of the hexagonal magnetoplumbite cell.

A novel investigation of vapor-phase charge-transfer complexes of halogens with n-donors by electron energy loss spectroscopy

Complexes of I2 with diethyl ether and triethylamine and of Br, with diethyl ether have been investigated in the vapor phase for the first time by employing electron energy loss spectroscopy. Besides the CT bands, blue-shifted vacuum-UV bands of the halogens have been assigned; the amine-I, system appears to exhibit two CT bands,associated with two different excited states of the complex.

Preliminary investigation into the induction of reproduction in Ulva spp. in Southeast Queensland for mass cultivation purposes

Ulva is a common component of marine intertidal flora in Australia with many species frequently observed along the Queensland coastline. Three species of Ulva, U. lactuca, U. intestinalis and U. prolifera were found to naturally occur at the Bribie Island Research Centre (BIRC) in Southeast Queensland. Studies were undertaken to establish the most optimal conditions for growing Ulva in the BIRC laboratory. These tests were conducted in order to condition the algal material prior to the sporulation studies, offering more controlled material to assess treatment effects conclusively, and helping eliminate other potentially confounding environmental factors. Results showed that a stocking density of between 5-20 grams of Ulva per litre along with the addition of the soluble fertiliser Aquasol at a rate of 87 mg/L of seawater was ideal for achieving a desired doubling of growth per week. In the wild the formation of Ulva fragments occurs naturally in the ocean through wave and storm action. This breakage can trigger a survival response mechanism which stimulates the algae to form and release gametes. By chopping the tissue, this process could be artificially simulated in the laboratory and creating a simple and easy way to produce new individuals. Studies performed into inducing sporulation in Ulva through a combination of fragmentation and renewal of medium at BIRC showed that sporulation can be successfully induced in all three species of Ulva through these methods, however it was found to be to a degree that would not meet the demands of commercial production with on average a rate of only 33% achieved. While the current study did not find a method suitable for a commercial application the results presented here contribute to increasing our understanding about Ulva reproduction and set a platform for future work in to cultivating Ulva within Southeast Queensland.

EQCM Investigation of the Electrodeposition of MnO2 and Its Capacitance Behavior

Electro-oxidation of Mn2+ to MnO2 by cyclic voltammetry on gold in acidic (0.1 M H2SO4) and neutral (0.1 M Na2SO4) media was studied using electrochemical quartz-crystal microbalance (EQCM). The cyclic voltammetric behavior of Au is different in these electrolytes. From EQCM data of mass variation during cycling, the rate of electrodeposition of MnO2 is higher in the neutral medium than in the acidic medium. Specific capacitance of MnO2 deposited from the neutral medium is higher than that deposited from the acidic medium owing to different crystallographic structures.