The synthesis and application of novel profluorescent nitroxides as probes for polymer degradation

This PhD project has expanded the knowledge in the area of profluorescent nitroxides with regard to the synthesis and characterisations of novel profluorescent nitroxide probes as well as physical characterisation of the probe molecules in various polymer/physical environments. The synthesis of the first example of an azaphenalene-based fused aromatic nitroxide TMAO, [1,1,3,3-tetramethyl-2,3-dihydro-2-azaphenalen-2-yloxyl, was described. This novel nitroxide possesses some of the structural rigidity of the isoindoline class of nitroxides, as well as some properties akin to TEMPO nitroxides. Additionally, the integral aromatic ring imparts fluorescence that is switched on by radical scavenging reactions of the nitroxide, which makes it a sensitive probe for polymer degradation. In addition to the parent TMAO, 5 other azaphenalene derivatives were successfully synthesised. This new class of nitroxide was expected to have interesting redox properties when the structure was investigated by high-level ab initio molecular orbitals theory. This was expected to have implications with biological relevance as the calculated redox potentials for the azaphenalene ring class would make them potent antioxidant compounds. The redox potentials of 25 cyclic nitroxides from four different structural classes (pyrroline, piperidine, isoindoline and azaphenalene) were determined by cyclic voltammetry in acetonitrile. It was shown that potentials related to the one electron processes of the nitroxide were influenced by the type of ring system, ring substituents or groups surrounding the moiety. Favourable comparisons were found between theoretical and experimental potentials for pyrroline, piperidine and isoindoline ring classes. Substitution of these ring classes, were correctly calculated to have a small yet predictable effect on the potentials. The redox potentials of the azaphenalene ring class were underestimated by the calculations in all cases by at least a factor of two. This is believed to be due to another process influencing the redox potentials of the azaphenalene ring class which is not taken into account by the theoretical model. It was also possible to demonstrate the use of both azaphenalene and isoindoline nitroxides as additives for monitoring radical mediated damage that occurs in polypropylene as well as in more commercially relevant polyester resins. Polymer sample doped with nitroxide were exposed to both thermo-and photo-oxidative conditions with all nitroxides showing a protective effect. It was found that isoindoline nitroxides were able to indicate radical formation in polypropylene aged at elevated temperatures via fluorescence build-up. The azaphenalene nitroxide TMAO showed no such build-up of fluorescence. This was believed to be due to the more labile bond between the nitroxide and macromolecule and the protection may occur through a classical Denisov cycle, as is expected for commercially available HAS units. Finally, A new profluorescent dinitroxide, BTMIOA (9,10-bis(1,1,3,3- tetramethylisoindolin-2-yloxyl-5-yl)anthracene), was synthesised and shown to be a powerful probe for detecting changes during the initial stages of thermo-oxidative degradation of polypropylene. This probe, which contains a 9,10-diphenylanthracene core linked to two nitroxides, possesses strongly suppressed fluorescence due to quenching by the two nitroxide groups. This molecule also showed the greatest protective effect on thermo-oxidativly aged polypropylene. Most importantly, BTMIOA was found to be a valuable tool for imaging and mapping free-radical generation in polypropylene using fluorescence microscopy.

Fathers as informants of children’s fears and worries

The recognition of excessive fears and worries in children is important for early intervention. Despite current knowledge about the important contribution fathers make to their children’s emotional, social and cognitive development, more emphasis is often given to the views of mothers in both research and practice. This paper reports on a community study of 220 families. Fathers, mothers and children reported on children’s fears and worries using three different methods. While father and mother ratings were moderately correlated on two of the measures, there was relatively poor parent-child agreement. Implications for the role of fathers in the assessment of childhood fears and worries are discussed.

The effect of social support derived from World of Warcraft on negative psychological symptoms

Previous research examining players of Massively-Multiplayer Online Games (MMOGs) suggests that players form meaningful relationships with each other. Other research indicates that people may derive social support from online sources and this social support has been associated with greater wellbeing. This study used an online survey of players (N = 206) of the MMOG “World of Warcraft” (WoW) to examine if social support can be derived from MMOGs, and to examine its relationship with negative psychological symptoms. Players of WoW were found to derive social support from playing and a positive relationship was found between game engagement and levels of in-game social support. Higher levels of in-game social support were associated with fewer negative psychological symptoms, although this effect was not maintained after accounting for social support derived from the offline sources. Additionally, a small subsample of players (N = 21) were identified that played for between 44 and 82 hours per week (M = 63.33). These players had significantly lower levels of offline social support and higher levels of negative symptoms compared to the rest of the sample. This study provides evidence that social support can be derived from MMOGs and the associated potential to promote well being, but also highlights the potential harm from spending excessive hours playing.

Integrating eco-efficiency assessment of commercial buildings into the design process : LCADesign

The ability to assess a commercial building for its impact on the environment at the earliest stage of design is a goal which is achievable by integrating several approaches into a single procedure directly from the 3D CAD representation. Such an approach enables building design professionals to make informed decisions on the environmental impact of building and its alternatives during the design development stage instead of at the post-design stage where options become limited. The indicators of interest are those which relate to consumption of resources and energy, contributions to pollution of air, water and soil, and impacts on the health and wellbeing of people in the built environment as a result of constructing and operating buildings. 3D object-oriented CAD files contain a wealth of building information which can be interrogated for details required for analysis of the performance of a design. The quantities of all components in the building can be automatically obtained from the 3D CAD objects and their constituent materials identified to calculate a complete list of the amounts of all building products such as concrete, steel, timber, plastic etc. When this information is combined with a life cycle inventory database, key internationally recognised environmental indicators can be estimated. Such a fully integrated tool known as LCADesign has been created for automated ecoefficiency assessment of commercial buildings direct from 3D CAD. This paper outlines the key features of LCADesign and its application to environmental assessment of commercial buildings.

Literacy, numeracy and learning in school-aged children identified as having speech and language impairment in early childhood

The progress of a nationally representative sample of 3632 children was followed from early childhood through to primary school, using data from the Longitudinal Study of Australian Children (LSAC). The aim was to examine the predictive effects of different aspects of communicative ability, and of early vs. sustained identification of speech and language impairment, on children's achievement and adjustment at school. Four indicators identified speech and language impairment: parent-rated expressive language concern; parent-rated receptive language concern; use of speech-language pathology services; below average scores on the adapted Peabody Picture Vocabulary Test-III. School outcomes were assessed by teachers' ratings of language/literacy ability, numeracy/mathematical thinking and approaches to learning. Comparison of group differences, using ANOVA, provided clear evidence that children who were identified as having speech and language impairment in their early childhood years did not perform as well at school, two years later, as their non-impaired peers on all three outcomes: Language and Literacy, Mathematical Thinking, and Approaches to Learning. The effects of early speech and language status on literacy, numeracy, and approaches to learning outcomes were similar in magnitude to the effect of family socio-economic factors, after controlling for child characteristics. Additionally, early identification of speech and language impairment (at age 4-5) was found to be a better predictor of school outcomes than sustained identification (at aged 4-5 and 6-7 years). Parent-reports of speech and language impairment in early childhood are useful in foreshadowing later difficulties with school and providing early intervention and targeted support from speech-language pathologists and specialist teachers.

Teacher leadership : interns crossing to the domain of higher professional learning with mentors?

Over the last two decades, the notion of teacher leadership has emerged as a key concept in both the teaching and leadership literature. While researchers have not reached consensus regarding a definition, there has been some agreement that teacher leadership can operate at both a formal and informal level in schools and that it includes leadership of an instructional, organisational and professional development nature (York-Barr & Duke, 2004). Teacher leadership is a construct that tends not to be applied to pre-service teachers as interns, but is more often connected with the professional role of mentors who collaborate with them as they make the transition to being a beginning teacher. We argue that teacher leadership should be recognised as a professional and career goal during this formative learning phase and that interns should be expected to overtly demonstrate signs, albeit early ones, of leadership in instruction and other professional areas of development. The aim of this paper is to explore the extent to which teacher education interns at one university in Queensland reported on activities that may be deemed to be ‘teacher leadership.’ The research approach used in this study was an examination of 145 reflective reports written in 2008 by final Bachelor of Education (primary) pre-service teachers. These reports recorded the pre-service teachers’ perceptions of their professional learning with a school-based mentor in response to four outcomes of internship that were scaffolded by their mentor or initiated by them. These outcomes formed the bases of our research questions into the professional learning of the interns and included, ‘increased knowledge and capacity to teach within the total world of work as a teacher;’ ‘to work autonomously and interdependently’; to make ‘growth in critical reflectivity’, and the ‘ability to initiate professional development with the mentoring process’. Using the approaches of the constant comparative method of Strauss and Corbin (1998) key categories of experiences emerged. These categories were then identified as belonging to main meta-category labelled as ‘teacher leadership.’ Our research findings revealed that five dimensions of teacher leadership – effective practice in schools; school curriculum work; professional development of colleagues; parent and community involvement; and contributions to the profession – were evident in the written reports by interns. Not surprisingly, the mentor/intern relationship was the main vehicle for enabling the intern to learn about teaching and leadership. The paper concludes with some key implications for developers of preservice education programmes regarding the need for teacher leadership to be part of the discourse of these programmes.

A longitudinal study of motivation and competence in children with Down syndrome : early childhood to early adolescence

Background Motivation has been identified as an area of difficulty for children with Down syndrome. Although individual differences in mastery motivation are presumed to have implications for subsequent competence, few longitudinal studies have addressed the stability of motivation and the predictive validity of early measures for later academic achievement, especially in atypical populations. Method The participants were 25 children with Down syndrome. Mastery motivation, operationalised as persistence, was measured in early childhood and adolescence using tasks and parent report. At the older age, preference for challenge, another aspect of mastery motivation, was also measured and the children completed assessments of academic competence. Results There were significant concurrent correlations among measures of persistence at both ages, and early task persistence was associated with later persistence. Persistence in early childhood was related to academic competence in adolescence, even when the effects of cognitive ability at the younger age were controlled. Conclusions For children with Down syndrome, persistence appears to be an individual characteristic that is relatively stable from early childhood to early adolescence. The finding that early mastery motivation is significant for later achievement has important implications for the focus of early interventions.

The NOURISH randomised control trial : positive feeding practices and food preferences in early childhood - a primary prevention program for childhood obesity

Background Primary prevention of childhood overweight is an international priority. In Australia 20-25% of 2-8 year olds are already overweight. These children are at substantially increased the risk of becoming overweight adults, with attendant increased risk of morbidity and mortality. Early feeding practices determine infant exposure to food (type, amount, frequency) and include responses (eg coercion) to infant feeding behaviour (eg. food refusal). There is correlational evidence linking parenting style and early feeding practices to child eating behaviour and weight status. A focus on early feeding is consistent with the national focus on early childhood as the foundation for life-long health and well being. The NOURISH trial aims to implement and evaluate a community-based intervention to promote early feeding practices that will foster healthy food preferences and intake and preserve the innate capacity to self-regulate food intake in young children. Methods/Design This randomised controlled trial (RCT) aims to recruit 820 first-time mothers and their healthy term infants. A consecutive sample of eligible mothers will be approached postnatally at major maternity hospitals in Brisbane and Adelaide. Initial consent will be for re-contact for full enrolment when the infants are 4-7 months old. Individual mother- infant dyads will be randomised to usual care or the intervention. The intervention will provide anticipatory guidance via two modules of six fortnightly parent education and peer support group sessions, each followed by six months of regular maintenance contact. The modules will commence when the infants are aged 4-7 and 13-16 months to coincide with establishment of solid feeding, and autonomy and independence, respectively. Outcome measures will be assessed at baseline, with follow up at nine and 18 months. These will include infant intake (type and amount of foods), food preferences, feeding behaviour and growth and self-reported maternal feeding practices and parenting practices and efficacy. Covariates will include sociodemographics, infant feeding mode and temperament, maternal weight status and weight concern and child care exposure. Discussion Despite the strong rationale to focus on parents’ early feeding practices as a key determinant of child food preferences, intake and self-regulatory capacity, prospective longitudinal and intervention studies are rare. This trial will be amongst to provide Level II evidence regarding the impact of an intervention (commencing prior to age 12 months) on children’s eating patterns and behaviours. Trial Registration: ACTRN12608000056392

A longitudinal study comparing bereavement phenomena in recently bereaved spouses, adult children and parents

Objective: The study investigated previous research findings and clinical impressions which indicated that the intensity of grief for parents who had lost a child was likely to be higher than that for widows/widowers, who in turn were likely to have more intense reactions than adult children losing a parent. Method: In order to compare the intensities of the bereavement reactions among representative community samples of bereaved spouses (n = 44), adult children (n = 40) and parents (n = 36), and to follow the course of such phenomena, a detailed Bereavement Questionnaire was administered at four time points over a 13-month period following the loss. Results: Measures based on items central to the construct of bereavement showed significant time and group differences in accordance with the proposed hypothesis. More global items associated with the construct of resolution showed a significant time effect, but without significant group differences. Conclusions: Evidence from this study supports the hypothesis that in non-clinical, community-based populations the frequency with which core bereavement phenomena are experienced is in the order: bereaved parents bereaved spouses bereaved adult children.

Listening, sharing understanding and facilitating consumer, family and community empowerment through a priority driven partnership in Far North Queensland

Objectives: This paper provides an example of a mental health research partnership underpinned by empowerment principles that seeks to foster strength among community organizations to support better outcomes for consumers, families and communities. It aims to raise awareness among researchers and service providers that empowerment approaches to assist communities to address mental health problems are not too difficult to be practical but require long-term commitment and appropriate support. Methods: A collaborative research strategy that has become known as the Priority Driven Research (PDR) Partnership emerged through literature review,consultations, Family Wellbeing Program delivery with community groups and activities in two discrete Indigenous communities. Progress to date on three of the four components of the strategy is described. Results: The following key needs were identified in a pilot study and are now being addressed in a research-based implementation phase: (i) gaining two-way understanding of perspectives on mental health and promoting universal awareness; (ii) supporting the empowerment of carers, families, consumers and at-risk groups through existing community organizations to gain greater understanding and control of their situation; (iii) developing pathways of care at the primary health centre level to enable support of social and emotional wellbeing as well as more integrated mental health care; (iv) accessing data to enable an ongoing process of analysis/sharing/planning and monitoring to inform future activity. Conclusion: One of the key learnings to emerge in this project so far is that empowerment through partnership becomes possible when there is a concerted effort to strengthen grassroots community organizations. These include social health teams and men’s and women’s groups that can engage local people in an action orientation. Key words: Aboriginal, empowerment, Indigenous, mental health.

Maternal age and paternal age are associated with distinct childhood behavioural outcomes in a general population birth cohort

Abstract Background Recent studies show that advanced paternal age (APA) is associated with an increased risk of neurodevelopmental disorders such as autism, bipolar disorder and schizophrenia. A body of evidence also suggests that individuals who develop schizophrenia show subtle deviations in a range of behavioural domains during their childhood. The aim of the study was to examine the relationship between paternal and maternal ages and selected behavioural measures in children using a large birth cohort. Method Participants were singleton children (n = 21,753) drawn from the US Collaborative Perinatal Project. The outcome measures were assessed at 7 years. The main analyses examined the relationship between parental age and behavioural measures when adjusted for a range of potentially confounding variables, including age of the other parent, maternal race, socio-economic measures, sex, gestation length, maternal marital status, parental mental illness, and child's age-at-testing. Results Advanced paternal age was associated with a significantly increased risk of adverse ‘externalizing’ behaviours at age seven years. For every five year increase in paternal age, the odds of higher ‘externalizing’ behaviours was increased by 12% (OR = 1.12; 95% CI = 1.03, 1.21, p < 0.0001). The relationship persisted after adjusting for potential confounding factors. ‘Internalizing’ behavioural outcome was not associated with advanced paternal age. In contrast, advanced maternal age was significantly protective against adverse ‘externalizing’ behavioural outcomes, but associated with an increased risk of adverse ‘internalizing’ behavioural outcomes. Discussion The offspring of older fathers show a distinctly different pattern of behaviours compared to the offspring of older mothers. The diverse socio-cultural and biologically-mediated factors that underpin these findings remain to be clarified. In light of secular trends related to delayed parenthood, the mechanisms underlying these findings warrant closer scrutiny.

Postpartum fatigue and driving : relating experiences, thoughts and opinions 12 weeks post-birth

Fatigue in the postnatal period is such a common experience for most mothers that the term ‘postpartum fatigue’ (PPF) has been coined to describe it. When new mothers experience extreme fatigue, it follows that their physical health, mental health, and social-wellbeing is negatively affected. It is interesting to note that there is a distinct lack of empirical investigations focusing on the link between PPF and increased risk of injury; particularly when the links between fatigue and increased risk of road crashes are well documented. The purpose of this investigation was to undertake pilot research to develop an understanding of the duration of PPF and the performance impairments experienced by new mothers when involved in safety-sensitive activities, such as driving a motor vehicle. Semi-structured interviews were undertaken with women (N = 24) at 12 weeks postpartum living in South-east Queensland, Australia. Key themes were identified; with a particular emphasis towards understanding the link between the participant’s experience of postpartum fatigue and the impact this has on their overall cognitive and physiological functioning, as well as their experience of the driving task. Further, sleep/wake data was collected and using the Karolinska Sleepiness Scale (KSS) the potential crash risk for this group of mothers is discussed. It is proposed that the findings of this investigation could be used to improve current knowledge among new mothers and practitioners regarding the mechanisms and consequences of fatigue and to inform interventions that lead to a decreased risk of injury associated with postpartum fatigue.

A Review of Customer Involvement in Evaluations of Case Management : Consistency with a recovery paradigm

This Open Forum examines research on case management that draws on consumer perspectives. It clarifies the extent of consumer involvement and whether evaluations were informed by recovery perspectives. Searches of three databases revealed l3 studies that sought to investigate consumer perspectives. Only one study asked consumers about experiences of recovery. Most evaluations did not adequately assess consumers' views, and active consumer participation in research was rare. Supporting an individual's recovery requires commitment to a recovery paradigm that incorporates traditional symptom reduction and improved functioning, with broader recovery principles, and a shift in focus from illness to wellbeing. It also requires greater involvement of consumers in the implementation of case management and ownership of their own recovery process, not just in research that evaluates the practice.

Exploring how parents and peers influence the behaviour of young drivers

Despite ongoing enhancements to graduated licensing systems, young drivers continue to have a high risk of being killed or injured in car crashes. This study investigated the influence of parents and peers on the risky behaviour of young drivers, utilising Akers’ social learning theory. The specific factors examined related to parent and peer norms perceived by the young driver, and the rewards and punishments anticipated by the young driver from their parents and peers. A questionnaire was completed by 165 young drivers. Regression analysis revealed that these factors explained 54% of the variance in risky driving. The strongest predictor was anticipated parent rewards, followed by peer norms, and anticipated peer rewards. Exploratory analyses however revealed the profile of predictors varied for male and female participants, and for self-reported offenders and non-offenders. The results highlight the role of psychosocial factors in the risky behaviour of young drivers and the need for road safety policies and programs to consider the influence of both parents and peers upon this behaviour.