Isolation and characterization of charge-tagged phenylperoxyl radicals in the gas phase : direct evidence for products and pathways in low temperature benzene oxidation

The phenylperoxyl radical has long been accepted as a critical intermediate in the oxidation of benzene and an archetype for arylperoxyl radicals in combustion and atmospheric chemistry. Despite being central to many contemporary mechanisms underpinning these chemistries, reports of the direct detection or isolation of phenylperoxyl radicals are rare and there is little experimental evidence connecting this intermediate with expected product channels. We have prepared and isolated two charge-tagged phenyl radical models in the gas phase [i.e., 4-(N,N,N-trimethylammonium) phenyl radical cation and 4-carboxylatophenyl radical anion] and observed their reactions with dioxygen by ion-trap mass spectrometry. Measured reaction rates show good agreement with prior reports for the neutral system (k(2)[(Me3N+)C6H4 center dot + O-2] = 2.8 x 10(-11) cm(3) molecule(-1) s(-1), Phi = 4.9%; k(2)[(-O2C)C6H4 center dot + O-2] = 5.4 x 10(-1)1 cm(3) molecule(-1) s(-1), Phi = 9.2%) and the resulting mass spectra provide unequivocal evidence for the formation of phenylperoxyl radicals. Collisional activation of isolated phenylperoxyl radicals reveals unimolecular decomposition by three pathways: (i) loss of dioxygen to reform the initial phenyl radical; (ii) loss of atomic oxygen yielding a phenoxyl radical; and (iii) ejection of the formyl radical to give cyclopentadienone. Stable isotope labeling confirms these assignments. Quantum chemical calculations for both charge-tagged and neutral phenylperoxyl radicals confirm that loss of formyl radical is accessible both thermodynamically and entropically and competitive with direct loss of both hydrogen atom and carbon dioxide.

Assembly and disassembly of temporary public spaces : establishing the theoretical needs

Contemporary cities no longer offer the same types of permanent environments that we planned for in the latter part of the twentieth century. Our public spaces are increasingly temporary, transient, and ephemeral. The theories, principles and tactics with which we designed these spaces in the past are no longer appropriate. We need a new theory for understanding the creation, use, and reuse of temporary public space. Moe than a theory, we need new architectural tactics or strategies that can be reliably employed to create successful temporary public spaces. This paper will present ongoing research that starts that process through critical review and technical analysis of existing and historic temporary public spaces. Through the analysis of a number of public spaces, that were either designed for temporary use or became temporary through changing social conditions, this research identifies the tactics and heuristics used in such projects. These tactics and heuristics are then analysed to extract some broader principles for the design of temporary public space. The theories of time related building layers, a model of environmental sustainability, and the recycling of social meaning, are all explored. The paper will go on to identify a number of key questions that need to be explored and addressed by a theory for such developments: How can we retain social meaning in the fabric of the city and its public spaces while we disassemble it and recycle it into new purposes? What role will preservation have in the rapidly changing future; will exemplary temporary spaces be preserved and thereby become no longer temporary? Does the environmental advantage of recycling materials, components and spaces outweigh the removal or social loss of temporary public space? This research starts to identify the knowledge gaps and proposes a number of strategies for making public space in the age of temporary, recyclable, and repurposing of our urban infrastructure; a way of creating lighter, cheaper, quicker, and temporary interventions.

Confessions of a Non-Emigrant

Confessions of a Non-Emigrant is innovative in combining two areas of investigation in creative writing and literature. I investigate both the idea of life writing as therapeutic for the author, and the (reflexive and enabling) blurred boundary between life writing and fiction. I set up a dynamic where the narrative of the story (fictionalised memoir) proposes the therapeutic advantage of utilising one’s life-story in fiction (increased sense of coherent identity and agency) and a perspective (through the device of multiple selves), on the constructedness and instability of identity. I mobilise and explore Pennebaker’s argument that making a narrative of one’s life enhances the writer’s sense of a connection with community and place (represented by Brisbane).

Analysis of arm elevation muscle activity through different movement planes and speeds during in-water and dry-land exercise

Objective The objectives of this cross-sectional, analytical inference analysis were to compare shoulder muscle activation at arm elevations of 0° to 90° through different movement planes and speeds during in-water and dry-land exercise and to extrapolate this information to a clinical rehabilitation model. Methods Six muscles of right-handed adult subjects (n = 16; males/females: 50%; age: 26.1 ± 4.5 years) were examined with surface electromyography during arm elevation in water and on dry land. Participants randomly performed 3 elevation movements (flexion, abduction, and scaption) through 0° to 90°. Three movement speeds were used for each movement as determined by a metronome (30°/sec, 45°/sec, and 90°/sec). Dry-land maximal voluntary contraction tests were used to determine movement normalization. Results Muscle activity levels were significantly lower in water compared with dry land at 30°/sec and 45°/sec but significantly higher at 90°/sec. This sequential progressive activation with increased movement speed was proportionally higher on transition from gravity-based on-land activity to water-based isokinetic resistance. The pectoralis major and latissimus dorsi muscles showed higher activity during abduction and scaption. Conclusions These findings on muscle activation suggest protocols in which active flexion is introduced first at low speeds (30°/sec) in water, then at medium speeds (45°/sec) in water or on dry land, and finally at high speeds (90°/sec) on dry land before in water. Abduction requires higher stabilization, necessitating its introduction after flexion, with scaption introduced last. This model of progressive sequential movement ensures that early active motion and then stabilization are appropriately introduced. This should reduce rehabilitation time and improve therapeutic goals without compromising patient safety or introducing inappropriate muscle recruitment or movement speed.

Creative Arts in Counselling and Mental Health

Drawing on evidence-based discoveries in neuroscience, narrative psychology and creativity theory, this text explores the beneficial role of expressive arts within a recovery perspective. A framework of practice principles for the visual arts, creative writing, music, drama, dance, and digital storytelling is addressed across a number of settings and populations, providing readers with an accessible overview of theory and techniques relevant to counselling programs in the United States, Australia and the United Kingdom.

A comparative structural bioinformatics analysis of the insulin receptor family ectodomain based on phylogenetic information

The insulin receptor (IR), the insulin-like growth factor 1 receptor (IGF1R) and the insulin receptor-related receptor (IRR) are covalently-linked homodimers made up of several structural domains. The molecular mechanism of ligand binding to the ectodomain of these receptors and the resulting activation of their tyrosine kinase domain is still not well understood. We have carried out an amino acid residue conservation analysis in order to reconstruct the phylogeny of the IR Family. We have confirmed the location of ligand binding site 1 of the IGF1R and IR. Importantly, we have also predicted the likely location of the insulin binding site 2 on the surface of the fibronectin type III domains of the IR. An evolutionary conserved surface on the second leucine-rich domain that may interact with the ligand could not be detected. We suggest a possible mechanical trigger of the activation of the IR that involves a slight ‘twist’ rotation of the last two fibronectin type III domains in order to face the likely location of insulin. Finally, a strong selective pressure was found amongst the IRR orthologous sequences, suggesting that this orphan receptor has a yet unknown physiological role which may be conserved from amphibians to mammals.

Towards an understanding of the information dynamics of the handover process in aged care settings: A prerequisite for the safe and effective use of ICT

Background Poor clinical handover has been associated with inaccurate clinical assessment and diagnosis, delays in diagnosis and test ordering, medication errors and decreased patient satisfaction in the acute care setting. Research on the handover process in the residential aged care sector is very limited. Purpose The aims of this study were to: (i) Develop an in-depth understanding of the handover process in aged care by mapping all the key activities and their information dynamics, (ii) Identify gaps in information exchange in the handover process and analyze implications for resident safety, (iii) Develop practical recommendations on how information communication technology (ICT) can improve the process and resident safety. Methods The study was undertaken at a large metropolitan facility in NSW with more than 300 residents and a staff including 55 registered nurses (RNs) and 146 assistants in nursing (AINs). A total of 3 focus groups, 12 interviews and 3 observation sessions were conducted over a period from July to October 2010. Process mapping was undertaken by translating the qualitative data via a five-category code book that was developed prior to the analysis. Results Three major sub-processes were identified and mapped. The three major stages are Handover process (HOP) I “Information gathering by RN”, HOP II “Preparation of preliminary handover sheet” and HOP III “Execution of handover meeting”. Inefficient processes were identified in relation to the handover including duplication of information, utilization of multiple communication modes and information sources, and lack of standardization. Conclusion By providing a robust process model of handover this study has made two critical contributions to research in aged care: (i) a means to identify important, possibly suboptimal practices; and (ii) valuable evidence to plan and improve ICT implementation in residential aged care. The mapping of this process enabled analysis of gaps in information flow and potential impacts on resident safety. In addition it offers the basis for further studies into a process that, despite its importance for securing resident safety and continuity of care, lacks research.