The syntheses of C6CH2.– and the corresponding carbenoid cumulene C6CH2 in the gas phase

The ion (C6CH2)(.-) is formed in the gas phase by the process -C=C-C=C-C=CH2OEt --> (C6CH2)(.-) + EtO., and charge stripping of the product radical anion yields the carbenoid neutral C6CH2; this can be either a singlet (the ground state), which is best represented as the carbene :C=C=C=C=C=C=CH2, or a triplet; the adiabatic electron affinity and the dipole moment of the carbenoid neutral are calculated to be 2.82 eV and 7.33 D respectively.

Potential interstellar molecules : Formation of neutral C6CO from C6CO- in the gas phase

Computations at the RCCSD(T)/aug-cc-pVDZ//B3LYP/6-31G* level of theory indicate that neutral C6CO is a stable species. The ground state of this neutral is the singlet cumulene oxide :C=C=C=C=C=C=C=O. The adiabatic electron affinity and dipole moment of singlet C6CO are 2.47 eV and 4.13 D, respectively, at this level of theory. The anion (C6CO)(-.) should be a possible precursor to this neutral. It has been formed by an unequivocal synthesis in the ion source of a mass spectrometer by the S(N)2(Si) reaction between (CH3)(3)Si-C=C-C=C-C=C-CO-CMe3 and F- to form C-=C-C=C-C=C-CO-CMe3 which loses Me3C in the source to form C6CO-.. Charge stripping of this anion by vertical Franck-Condon oxidation forms C6CO, characterised by the neutralisation-reionisation spectrum (-NR+) of C6CO-., which is stable during the timeframe of this experiment (10(-6) s), Copyright (C) 2000 John Wiley & Sons, Ltd.

High pressure in situ diffraction studies of metal–hydrogen systems

“Hybrid” hydrogen storage, where hydrogen is stored in both the solid material and as a high pressure gas in the void volume of the tank can improve overall system efficiency by up to 50% compared to either compressed hydrogen or solid materials alone. Thermodynamically, high equilibrium hydrogen pressures in metal–hydrogen systems correspond to low enthalpies of hydrogen absorption–desorption. This decreases the calorimetric effects of the hydride formation–decomposition processes which can assist in achieving high rates of heat exchange during hydrogen loading—removing the bottleneck in achieving low charging times and improving overall hydrogen storage efficiency of large hydrogen stores. Two systems with hydrogenation enthalpies close to −20 kJ/mol H2 were studied to investigate the hydrogenation mechanism and kinetics: CeNi5–D2 and ZrFe2−xAlx (x = 0.02; 0.04; 0.20)–D2. The structure of the intermetallics and their hydrides were studied by in situ neutron powder diffraction at pressures up to 1000 bar and complementary X-ray diffraction. The deuteration of the hexagonal CeNi5 intermetallic resulted in CeNi5D6.3 with a volume expansion of 30.1%. Deuterium absorption filled three different types of interstices, Ce2Ni2 and Ni4 tetrahedra, and Ce2Ni3 half-octahedra and was accompanied by a valence change for Ce. Significant hysteresis was observed between deuterium absorption and desorption which profoundly decreased on a second absorption cycle. For the Al-modified Laves-type C15 ZrFe2−xAlx intermetallics, deuteration showed very fast kinetics of H/D exchange and resulted in a volume increase of the FCC unit cells of 23.5% for ZrFe1.98Al0.02D2.9(1). Deuterium content, hysteresis of H/D uptake and release, unit cell expansion and stability of the hydrides systematically change with the amount of Al content. In the deuteride D atoms exclusively occupy the Zr2(Fe,Al)2 tetrahedra. Observed interatomic distances are Zr–D = 1.98–2.11; (Fe, Al)–D = 1.70–1.75A˚ . Hydrogenation slightly increases the magnetic moment of the Fe atoms in ZrFe1.98Al0.02 and ZrFe1.96Al0.04 from 1.9 �B at room temperature for the alloy to 2.2 �B for its deuteride.

Impinging jet simulation of stationary downburst flow over topography

A non-translating, long duration thunderstorm downburst has been simulated experimentally and numerically by modelling a spatially stationary steady flow impinging air jet. Velocity profiles were shown to compare well with an upper-bound of velocity measurements reported for full-scale microbursts. Velocity speed-up over a range of topographic features in simulated downburst flow was also tested with comparisons made to previous work in a similar flow, and also boundary layer wind tunnel experiments. It was found that the amplification measured above the crest of topographic features in simulated downburst flow was up to 35% less than that observed in boundary layer flow for all shapes tested. From the computational standpoint we conclude that the Shear Stress Transport (SST) model performs the best from amongst a range of eddy-viscosity and second moment closures tested for modelling the impinging jet flow.

Momentan

Momentan was envisaged and constructed as an abstract dance work investigating: • The body in the moment • The body in movement • The body as Solo performer • The body and its connectivity with others

Aligning in and through interaction : children getting in and out of spontaneous activity

Spontaneous play, important for forming the basis of friendships and peer relations, is a complex activity involving the management and production of talk-in-interaction. This paper focuses on the intricacies of social interaction, emphasising the link between alignment and affiliation, and the range and importance of verbal and nonverbal interactive devices available to children. Analysis of the way in which two girls, one of whom has been diagnosed with Asperger’s Syndrome, engage in spontaneous activities demonstrates the potential for interactional difficulty due to the unscripted nature of the interaction. The paper argues for further research into how improvised, unscripted interactions are initiated within moment-by-moment talk, how they unfold, and how they are brought to a close in everyday contexts in order to understand how children create their social worlds.

The big data lottery

Big data is certainly the buzz term in executive networking circles at the moment. Heralded by management consultancies and research organisations alike as the next big thing in business efficiency, it is shooting up the Gartner hype cycle to the giddy heights of the peak of inflated expectations before it tumbles down in to the trough of disillusionment

Jumping the fence from dance to cross-disciplinary research

Introduction: reading the signs Inside the dance ethos, knowledge is rarely articulated other than through the experience of dance itself. On the surface, the dancer focuses on practical and specialist skills. However, a closer look reveals that their knowledge does not merely trigger an embodied way of thinking; it enables the dancer to map a trail of metaphors within the body. In effect, dancers acquire a distinct embodied culture with its own language, dialects, customs and traditions. In this paper, I shall firstly examine the way metaphors establish a link between reason and imagination between one set of embodied knowledge and another. It is in regards to this function, where metaphor welds opposites together or when interior and exterior information exist in the same moment that it is most useful for jumping the fence from dance to cross-disciplinary practice. Secondly, I shall discuss how metaphors can help sustain creative practice. For it is only by stepping outside the culture of dance that I could first unravel the experiences, processes and knowledges inscribed through a career in dance and begin to define the quality of my own voice.

Dormant but migratory tumour cells in desmoplastic stroma of invasive ductal carcinomas

Mortality in breast cancer is linked to metastasis and recurrence yet there is no acceptable biological model for cancer relapse. We hypothesise that there might exist primary tumour cells capable of escaping surgery by migration and resisting radiotherapy and chemotherapy to cause cancer recurrence. We investigated this possibility in invasive ductal carcinoma (IDC) tissue and observed the presence of solitary primary tumour cells (SPCs) in the dense collagen stroma that encapsulates intratumoural cells (ICs). In IDC tissue sections, collagen was detected with either Masson's Trichrome or by second harmonics imaging. Cytokeratin-19 (CK-19) and vimentin (VIM) antibodies were, respectively, used to identify epithelial-derived tumour cells and to indicate epithelial to mesenchymal transition (EMT). Confocal/multiphoton microscopy showed that ICs from acini were mainly CK-19 +ve and were encapsulated by dense stromal collagen. Within the stroma, SPCs were detected by their staining for both CK-19 and VIM (confirming EMT). ICs and SPCs were subsequently isolated by laser capture microdissection followed by multiplex tandem-PCR studies. SPCs were found to be enriched for pro-migratory and anti-proliferative genes relative to ICs. In vitro experiments using collagen matrices at 20 mg/cm 3, similar in density to tumour matrices, demonstrated that SPC-like cells were highly migratory but dormant, phenotypes that recapitulated the genotypes of SPCs in clinical tissue. These data suggest that SPCs located at the breast cancer perimeter are invasive and dormant such that they may exceed surgical margins and resist local and adjuvant therapies. This study has important connotations for a role of SPCs in local recurrence.

School physical education in the post-report era : an analysis from public health

The 1996 United States Surgeon General’s report on physical activity and health represents a watershed moment in the modern history of physical activity and public health. Based on a compelling body of scientific evidence from the fields of medicine, epidemiology, physiology, and health psychology, the Surgeon General’s report proclaimed that people of all ages could improve their health and quality of life through lifelong practice of moderate physical activity (United States Department of Health and Human Services [USDHHS], 1996). Physical Activity and Health: A Report of the Surgeon General was an especially important publication for school physical education. Not only did the report acknowledge the importance of regular physical activity during childhood and adolescence, it also identified school physical education as an important vehicle for promoting healthenhancing physical activity in young people. “With evidence that success in this arena is possible, every effort should be made to encourage schools to require daily physical education in each grade and to promote physical activities that can be enjoyed throughout life” (USDHHS, 1996, p. 6). The purpose of this article is to discuss the status of school physical education since the release of the Surgeon General’s report on physical activity and health nearly a decade ago. Specifically, the article will address four questions: 1) What has been the historical role of physical education in physical activity and public health? 2) What impact, if any, has the Surgeon General’s report has had on physical education programs? 3) What impact should physical education have on public health and physical activity? 4) What should teacher education programs in physical education do to prepare physical education teachers, given the current role of physical education?

Why we should not cut P.E.

Thinking of cutting physical education? Think again. Even as we bemoan children's sedentary lifestyles, we often sacrifice school-based physical education in the name of providing more time for academics. In 2006, only 3.8 percent of elementary schools, 7.9 percent of middle schools, and 2.1 percent of high schools offered students daily physical education or its equivalent for the entire school year (Lee, Burgeson, Fulton, & Spain, 2007). We believe this marked reduction in school-based physical activity risks students' health and can't be justified on educational or ethical grounds. We'll get to the educational grounds in a moment. As to ethical reasons for keeping physical activity part of our young people's school days, consider the fact that childhood obesity is now one of the most serious health issues facing U.S. children (Ogden et al., 2006). School-based physical education programs engage students in regular physical activity and help them acquire skills and habits necessary to pursue an active lifestyle. Such programs are directly relevant to preventing obesity. Yet they are increasingly on the chopping block.

The importance of use and end-of-life phases to the life cycle greenhouse gas (GHG) emissions of concrete : a review

Global climate change is one of the most significant environmental impacts at the moment. One central issue for the building and construction industry to address global climate change is the development of credible carbon labelling schemes for building materials. Various carbon labelling schemes have been developed for concrete due to its high contribution to global greenhouse gas (GHG) emissions. However, as most carbon labelling schemes adopt cradle-to-gate as system boundary, the credibility of the eco-label information may not be satisfactory because recent studies show that the use and end-of-life phases can have a significant impact on the life cycle GHG emissions of concrete in terms of carbonation, maintenance and rehabilitation, other indirect emissions, and recycling activities. A comprehensive review on the life cycle assessment of concrete is presented to holistically examine the importance of use and end-of-life phases to the life cycle GHG quantification of concrete. The recent published ISO 14067: Carbon footprint of products – requirements and guidelines for quantification and communication also mandates the use of cradle-to-grave to provide publicly available eco-label information when the use and end-of-life phases of concrete can be appropriately simulated. With the support of Building Information Modelling (BIM) and other simulation technologies, the contribution of use and end-of-life phases to the life cycle GHG emissions of concrete should not be overlooked in future studies.

Limitation of actions - medical negligence

In Christensen v Salter [2002] QDC 082 the District Court of Queensland considered some issues on the limitation period applying to claims arising out of a failed sterilisation procedure

The stabilising role of the costovertebral joints and spinous processes on thoracic spine stability

Introduction The importance of in vitro biomechanical testing in today’s understanding of spinal pathology and treatment modalities cannot be stressed enough. Different studies have used differing levels of dissection of their spinal segments for their testing protocols[1, 2]. The aim of this study was to assess the impact of removing the costovertebral joints and partial resection of the spinous process sequentially, on the stiffness of the immature thoracic bovine spinal segment. Materials and Methods Thoracic spines from 6-8 week old calves were used. Each spine was dissected and divided into motion segments with 5cm of attached rib on each side and full spinous processes including levels T4-T11 (n=28). They were potted in polymethylemethacrylate. An Instron Biaxial materials testing machine with a custom made jig was used for testing. The segments were tested in flexion/extension, lateral bending and axial rotation at 37⁰C and 100% humidity, using moment control to a maximum 1.75 Nm with a loading rate of 0.3 Nm per second. They were first tested intact for ten load cycles with data collected from the tenth cycle. Progressive dissection was performed by removing first the attached ribs, followed by the spinous process at its base. Biomechanical testing was carried out after each level of dissection using the same protocol. Statistical analysis of the data was performed using repeated measures ANOVA. Results In combined flexion/extension there was a significant reduction in stiffness of 16% (p=0.002). This was mainly after resection of the ribs (14%, p=0.024) and mainly occurred in flexion where stiffness reduced by 22% (p=0.021). In extension, stiffness dropped by 13% (p=0.133). However there was no further significant change in stiffness on resection of the spinous process (<1%) (p=1.00). In lateral bending there was a significant decrease in stiffness of 13% (p<0.001). This comprised a drop of 11% on resection of the ribs (p=0.009) and a further 8% on resection of the spinous process (p=0.014). There was no difference between left and right bending. In axial rotation there was no significant change in stiffness after each stage of dissection (p=0.253). There was no difference between left and right rotation. Conclusion The costovertebral joints play a significant role in providing stability to the bovine thoracic spine in both flexion/extension and lateral bending, whereas the spinous processes play a minor role. Both elements have little effect on axial rotation stability.

Fast, energy-efficient synthesis of luminescent carbon quantum dots

A simple, fast, energy and labour efficient, carbon dot synthesis method involving only the mixing of a saccharide and base is presented. Uniform, green luminescent carbon dots with an average size of 3.5 nm were obtained, without the need for additional energy input or external heating. Detection of formation moment for fructose-NaOH-produced carbon dots is also presented.