Direct detection of additives and degradation products from polymers by liquid extraction surface analysis employing chip-based nanospray mass spectrometry

RATIONALE: Polymer-based surface coatings in outdoor applications experience accelerated degradation due to exposure to solar radiation, oxygen and atmospheric pollutants. These deleterious agents cause undesirable changes to the aesthetic and mechanical properties of the polymer, reducing its lifetime. The use of antioxidants such as hindered amine light stabilisers (HALS) retards these degradative processes; however, mechanisms for HALS action and polymer degradation are poorly understood. METHODS: Detection of the HALS TINUVINW123 (bis(1-octyloxy-2,2,6,6-tetramethyl-4-piperidyl) sebacate) and the polymer degradation products directly from a polyester-based coil coating was achieved by liquid extraction surface analysis (LESA) coupled to a triple quadrupole QTRAPW 5500 mass spectrometer. The detection of TINUVINW123 and melamine was confirmed by the characteristic fragmentation pattern observed in LESA-MS/MS spectra that was identical to that reported for authentic samples. RESULTS: Analysis of an unstabilised coil coating by LESA-MS after exposure to 4 years of outdoor field testing revealed the presence of melamine (1,3,5-triazine-2,4,6-triamine) as a polymer degradation product at elevated levels. Changes to the physical appearance of the coil coating, including powder-like deposits on the coating's surface, were observed to coincide with melamine deposits and are indicative of the phenomenon known as polymer ' blooming'. CONCLUSIONS: For the first time, in situ detection of analytes from a thermoset polymer coating was accomplished without any sample preparation, providing advantages over traditional extraction-analysis approaches and some contemporary ambient MS methods. Detection of HALS and polymer degradation products such as melamine provides insight into the mechanisms by which degradation occurs and suggests LESA-MS is a powerful new tool for polymer analysis. Copyright (C) 2012 John Wiley & Sons, Ltd.

Teacher understandings of orientation and transition programs from action research in five schools

Discontinuity between prior-to-school and school sectors in Australia reflects an historical, philosophical and pedagogical schism. This is most evident as children transition from one sector to the other. However, contemporary international research, alongside an intensive focus on policy and practice in early years education has challenged many of the taken-for-granted assumptions that perpetuate this rift. Drawing on data collected in a recent action research project, we present evidence of how a group of primary school kindergarten teachers define differences between orientation and transition programs, understand the importance of transition and how they position themselves in this process. The absence of Australian policy mandating and guiding the work of teachers across sectors is a significant factor perpetuating discontinuity in transition practices between prior–to-school and school sectors.

Teaching fractions to adult learners enrolled in a civil construction course : knowledge, action and materials action in tandem

This paper investigates the teaching and learning of fractions to Indigenous adult learners in a Civil Construction Certificate Course. More specifically it explores why the use of materials is critical to building knowledge and understanding. This focus is important for two reasons. First, it allows for considerations of a trainer’s approach for teaching fractions and, second it provides insights into how adult learners can be supported with representing their practical experiences of fractions to make generalisation thus building on their knowledge and learning experiences. The paper draws on teaching episodes from an Australian Research Council funded Linkage project that investigates how mathematics is taught and learned in Certificate Courses, here, Certificate 11 in Civil Construction. Action research and decolonising methods (Smith, 1999) were used to conduct the research. Video excerpts which feature one trainer and three students are analysed and described. Findings from the data indicate that adult learners need to be supported with materials to assist with building their capacity to know and apply understandings of fractions in a range of contexts, besides construction. Without materials and where fractions are taught via pen and paper tasks, students are less likely to retain and apply fraction ideas to their Certificate Course. Further they are less likely to understand decimals because of limited understanding of fractions.

Constrained predictive control of ship fin stabilizers to prevent dynamic stall

In moderate to high sea states, the effectiveness of ship fin stabilizers can severely deteriorate due to nonlinear effects arising from unsteady hydrodynamic characteristics of the fins: dynamic stall. These nonlinear effects take the form of a hysteresis, and they become very significant when the effective angle of attack of the fins exceeds a certain threshold angle. Dynamic stall can result in a complete loss of control action depending on how much the fins exceed the threshold angle. When this is detected, it is common to reduce the gain of the controller that commands the fins. This approach is cautious and tends to reduce performance when the conditions leading to dynamic stall disappear. An alternative approach for preventing the effects while keeping high performance, consists of estimating the effective angle of attack and set a conservative constraint on it as part of the control objectives. In this paper, we investigate the latter approach, and propose the use of a model predictive control (MPC) to prevent the development of these nonlinear effects by considering constraints on both the mechanical angle of the fins and the effective angle of attack.

Exploration of mechanisms underlying the strain-rate-dependent mechanical property of single chondrocytes

Based on the characterization by Atomic Force Microscopy (AFM), we report that the mechanical property of single chondrocytes has dependency on the strain-rates. By comparing the mechanical deformation responses and the Young’s moduli of living and fixed chondrocytes at four different strain-rates, we explore the deformation mechanisms underlying this dependency property. We found that the strain-rate-dependent mechanical property of living cells is governed by both of the cellular cytoskeleton (CSK) and the intracellular fluid when the fixed chondrocytes is mainly governed by their intracellular fluid which is called the consolidation-dependent deformation behavior. Finally, we report that the porohyperelastic (PHE) constitutive material model which can capture the consolidation-dependent behavior of both living and fixed chondrocytes is a potential candidature to study living cell biomechanics.

Engaging creativity through an action learning and action research process to develop an Indigenous art exhibition

In most art exhibitions, the creative part of the exhibition is assumed to be the artworks on display. But for the Capricornia Arts Mob’s first collective art exhibition in Rockhampton during NAIDOC Week in 2012, the process of developing the exhibition became the focus of creative action learning and action research. In working together to produce a multi-media exhibition, we learned about the collaborative processes and time required to develop a combined exhibition. We applied Indigenous ways of working – including yarning, cultural respect, cultural protocols, mentoring young people, providing a culturally safe working environment and sharing both time and food – to develop our first collective art exhibition. We developed a process that allowed us to ask deep questions, engage in a joint journey of learning, and develop our collective story. This paper explores the processes that the Capricornia Arts Mob used to develop the exhibition for NAIDOC 2012.

Mechanisms of glycerol dehydration

Dehydration of neutral and protonated glycerol was investigated using quantum mechanical calculations (CBS-QB3). Calculations on neutral glycerol show that there is a high barrier for simple 1,2-dehydration, E-a = 70.9 kcal mol(-1), which is lowered to 65.2 kcal mol(-1) for pericyclic 1,3-dehydration. In contrast, the barriers for dehydration of protonated glycerol are much lower. Dehydration mechanisms involving hydride transfer, pinacol rearrangement, or substitution reactions have barriers between 20 and 25 kcal mol(-1). Loss of water from glycerol via substitution results in either oxirane or oxetane intermediates, which can interconvert over a low barrier. Subsequent decomposition of these intermediates proceeds via either a second dehydration step or loss of formaldehyde. The computed mechanisms for decomposition of protonated glycerol are supported by the gas-phase fragmentation of protonated glycerol observed using a triple-quadrupole mass spectrometer.

Innovating urban policymaking and planning mechanisms to deliver knowledge-based agendas : a methodological approach

This paper aims to develop a comprehensive approach to innovate urban policymaking and planning to successfully deliver the knowledge-based agenda. The paper, first, examines the concept of knowledge-based urban development, which has become a popular urban development policy and strategy in recent years, through a comprehensive review of the literature. It, then, introduces and discusses a novel methodological approach for effective policymaking and planning mechanism to deliver the knowledge-based agenda of cities. The paper, with the proposed methodology, brings together urban policymaking and planning approaches, and introduces a novel way to assess knowledge-based urban development achievements and potentials of emerging and prosperous knowledge cities. The paper, thus, provides an invaluable instrument to inform local and regional decision and plan making mechanisms to deliver their knowledge-based agendas and help them in moving towards building their sustainable knowledge cities.

Modulation of breast cancer progression and differentiation by the gp30/neregulin

In the last decade we have come to understand that the growth of cancer cells in general and of breast cancer in particular depends, in many cases, upon growth factors that will bind to and activate their receptors. One of these growth factor receptors is the erbB-2 protein which plays an important role in the prognosis of breast cancer and is overexpressed in nearly 30% of human breast cancer patients. While evidence accumulates to support the relationship between erbB-2 overexpression and poor overall survival in breast cancer, understanding of the biological consequence(s) of erbB-2 overexpression remains elusive. Our recent discovery of the gp30 has allowed us to identify a number of related but distinct biological endpoints which appear responsive to signal transduction through the erbB-2 receptor. These endpoints of growth, invasiveness, and differentiation have clear implications for the emergence, maintenance and/or control of malignancy, and represent established endpoints in the assessment of malignant progression in breast cancer. We have shown that gp30 induces a biphasic growth effect on cells with erbB-2 over-expression. We have recently determined the protein sequence of gp30 and cloned its full length cDNA sequence. We have also cloned two additional forms to the ligand, that are believed to be different isoforms. We are currently expressing the different forms in order to determine their biological effects. To elucidate the cellular mechanisms underlying cell growth inhibition by gp30, we tested the effect of this ligand on cell growth and differentiation of the human breast cancer cells which overexpress erbB-2 and cells which express low levels of this protooncogene. High concentrations of ligand induced differentiation of cells overexpressing erbB-2, as measured by inhibition of cell growth, and increased synthesis of milk components, and modulation of E-cadherin and up- regulation of c-jun and c-fos. These findings indicate that ligand-induced growth inhibition in cells overexpressing erbB-2 is associated with an apparent induction of differentiation. The availability of gp30 derived synthetic peptides and its full cDNAs provides tools necessary to acquire a better understanding of the mechanism of action of the this ligands and the erbB-2 receptor in breast cancer.

Planes, trains, automobiles and the action per quod servitium amisit

The action per quod servitium amisit compensates an employer for the loss of an employee’s services, where such loss is caused due to the commission of a tort by a third party which injures the employee. Although not commonly pleaded, such actions often arise when employees are harmed due to transportation accidents. For example, where allowed, physical injury caused by the negligent driving of automobiles, and the psychiatric injury suffered by an engine driver upon averting a collision with a motorcyclist crossing before an oncoming train...

Structural identification of hindered amine light stabilisers in coil coatings using electrospray ionisation tandem mass spectrometry

Hindered amine light stabilisers (HALS) are the most effective antioxidants currently available for polymer systems in post-production, in-service applications, yet the mechanism of their action is still not fully understood. Structural characterisation of HALS in polymer matrices, particularly the identification of structural modifications brought about by oxidative conditions, is critical to aid mechanistic understanding of the prophylactic effects of these molecules. In this work, electrospray ionisation tandem mass spectrometry (ESI-MS/MS) was applied to the analysis of a suite of commercially available 2,2,6,6-tetramethylpiperidine-based HALS. Fragmentation mechanisms for the \[M + H](+) ions are proposed, which provide a rationale for the product ions observed in the MS/MS and MS(3) mass spectra of N-H, N-CH(3), N-C(O)CH(3) and N-OR containing HALS (where R is an alkyl substituent). A common product ion at m/z 123 was identified for the group of antioxidants containing N-H, N-CH3 or N-C(0)CH3 functionality, and this product ion was employed in precursor ion scans on a triple quadrupole mass spectrometer to identify the HALS species present in a crude extract from of a polyester-based coil coating. Using MS/MS, two degradation products were unambiguously identified. This technique provides a simple and selective approach to monitoring HALS structures within complex matrices. Copyright (C) 2010 John Wiley & Sons, Ltd.

Mechanisms of tumour invasion and metastasis : emerging targets for therapy

The progression of a tumour from one of benign and delimited growth to one that is invasive and metastatic is the major cause of poor clinical outcome in cancer patients. The invasion and metastasis of tumours is a highly complex and multistep process that requires a tumour cell to modulate its ability to adhere, degrade the surrounding extracellular matrix, migrate, proliferate at a secondary site and stimulate angiogenesis. Knowledge of the process has greatly increased and this has resulted in the identification of a number of molecules that are fundamental to the process. The involvement of these molecules has been shown to relate not only to the survival and proliferation of the tumour cell but, also to the processes of tumour cell adhesion, migration, and the tumour cells ability to degrade and escape the primary site as well as play a role in angiogenesis. These molecules may provide important therapeutic targets that represent the ability to target specific steps in the process of invasion and metastasis and provide additional therapies. The review focuses on representative key targets in each of these processes and summarises the state of play in each case.

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.

The role of core protest group members in sustaining protest against controversial construction and engineering projects

Community-based protests against major construction and engineering projects are becoming increasingly common as concerns over issues such as corporate social accountability, climate change and corruption become more prominent in the public's mind. Public perceptions of risk associated with these projects can have a contagious effect, which mismanaged can escalate into long-term and sometimes acrimonious protest stand-offs that have negative implications for the community, firms involved and the construction industry as a whole. This paper investigates the role of core group members in sustaining community-based protest against construction and engineering projects. Using a thematic story telling approach which draws on ethnographic method and social contagion theories, it presents an in-depth analysis of a single case study - one of Australia's longest standing community protests against a construction project. It concludes that core group members play a critical role, within anarchic structures which provide a high degree of spontaneity and improvisation, in sustaining movement continuity by building collective identity, mobilising resources and a moving interface which developers find hard to communicate with.