Direct observation of the gas phase reaction of the cyclohexyl radical with dioxygen using a distonic radical ion approach

Alkylperoxyl radicals are intermediates in the oxidation Of hydrocarbons. The reactive nature of these intermediates, however, has made therin elusive to direct observation and isolation. We have employed ion trap mass spectrometry to synthesize and characterize 4-carboxylatocyclohexyl radical anions ((center dot)C(6)H(10)-CO(2)(-)) and observe their reactivity in the presence of dioxygen. The resulting reaction is facile (k = 1.8 x 10(-10) cm(3) molecule(-1) s(-1) or 30% of calculated collision rate) and results in (i) the addition Of O(2) to form stabilized 4-carboxylatocyclohexylperoxyl radical anions ((center dot)OO-C(6)H(10)-CO(2)(-)), providing the first direct observation of a cyclohexylperoxyl radical, and (ii) elimination of HO(2)(center dot) and HO(center dot) radicals consistent with recent laser-induced fluorescence studies of the reaction of neutral cyclohexyl radicals with O(2). Electronic structure calculations at the B3LYP/6-31+G(d) level of theory reveal viable pathways for the observed reactions showing that formation of the peroxyl radical is exothermic by 37 kcal mol(-1) with subsequent transition states its low as -6.6 kcal mol(-1) (formation of HO(2)(center dot)) and -9.1 kcal mol(-1) (formation of HO(center dot)) with respect to the entrance channel. The combined computational and experimental data Suggest that the structures of the reaction products correspond to cyclohexenes and epoxides from HO(2)(center dot) and HO(center dot) loss, respectively, while alternative pathways leading to cyclohexanone or ring-opened isomers ate not observed, Activation of the charged peroxyl radical (center dot)OO-C(6)H(10)-CO(2)(-) by collision induced disassociation also results in the loss Of HO(2)(center dot) and HO(center dot) radicals confirming that these products are directly connected to the peroxyl radical intermediate.

Reconstruction of critical-sized ovine mandibular defects - a pilot study

Establishing the sheep model for translational research of mandible (jaw) segmental defect regeneration. Providing a framework from which additional experimentation and evaluation of novel tissue engineered constructs may be undertaken, compared and collated. For current and future novel approaches to mandible segmental defect reconstruction that may be transferable to the human condition and, ultimately, the operative table.

Surface reconstruction of wheat leaf morphology from three-dimensional scanned data

Realistic virtual models of leaf surfaces are important for a number of applications in the plant sciences, such as modelling agrichemical spray droplet movement and spreading on the surface. In this context, the virtual surfaces are required to be sufficiently smooth to facilitate the use of the mathematical equations that govern the motion of the droplet. While an effective approach is to apply discrete smoothing D2-spline algorithms to reconstruct the leaf surfaces from three-dimensional scanned data, difficulties arise when dealing with wheat leaves that tend to twist and bend. To overcome this topological difficulty, we develop a parameterisation technique that rotates and translates the original data, allowing the surface to be fitted using the discrete smoothing D2-spline methods in the new parameter space. Our algorithm uses finite element methods to represent the surface as a linear combination of compactly supported shape functions. Numerical results confirm that the parameterisation, along with the use of discrete smoothing D2-spline techniques, produces realistic virtual representations of wheat leaves.

Morphometric modelling of ageing in the human pubic symphysis : sexual dimorphism in an Australian population

Despite the prominent use of the pubic symphysis for age estimation in forensic anthropology, little has been documented regarding the quantitative morphological and micro-architectural changes of this surface. Specifically, utilising post-mortem computed tomography data from a large, contemporary Australian adult population, this study aimed to evaluate sexual dimorphism in the morphology and bone composition of the symphyseal surface; and temporal characterisation of the pubic symphysis in individuals of advancing age. The sample consisted of multi-slice computed tomography (MSCT) scans of the pubic symphysis(slice thickness: 0.5 mm, overlap: 0.1 mm) of 200 individuals of Caucasian ancestry aged 15–70 years, obtained in 2011. Surface rendering reconstruction of the symphyseal surface was conducted in OsiriX1 (v.4.1) and quantitative analyses in Rapidform XOSTM and OsteomeasureTM. Morphometric variables including inter-pubic distance, surface area, circumference, maximum height and width of the symphyseal surface and micro-architectural assessment of cortical and trabecular bone compositions were quantified using novel automated engineering software capabilities. The major results of this study are correlated with the macroscopic ossification and degeneration pattern of the symphyseal surface, demonstrating significant age-related changes in the morphometric and bone tissue variables between 15 and 70 years. Regardless of sex, the overall dimensions of the symphyseal surface increased with age, coupled with a decrease in bone mass in the trabecular and cortical bone compartments. Significant differences between the ventral, dorsal and medial cortical surfaces were observed, which may be correlated to bone formation activity dependent on muscle activity and ligamentous attachments. Our study demonstrates significant sexual dimorphism at this site, with males exhibiting greater surface dimensions than females. These baseline results provide a detailed insight into the changes in the structure of the pubic symphysis with ageing and sexually dimorphic features associated with the cortical and trabecular bone profiles.

Analysis of the extreme diversity of salivary alpha-amylase isoforms generated by physiological proteolysis using liquid chromatography-tandem mass spectrometry

Saliva is a crucial biofluid for oral health and is also of increasing importance as a non-invasive source of disease biomarkers. Salivary alpha-amylase is an abundant protein in saliva, and changes in amylase expression have been previously associated with a variety of diseases and conditions. Salivary alpha-amylase is subject to a high diversity of post-translational modifications, including physiological proteolysis in the oral cavity. Here we developed methodology for rapid sample preparation and non-targeted LC-ESI-MS/MS analysis of saliva from healthy subjects and observed an extreme diversity of alpha-amylase proteolytic isoforms. Our results emphasize the importance of consideration of post-translational events such as proteolysis in proteomic studies, biomarker discovery and validation, particularly in saliva. (C) 2012 Elsevier B.V. All rights reserved.

The development of virtual leaf surface models for interactive agrichemical spray applications

This project constructed virtual plant leaf surfaces from digitised data sets for use in droplet spray models. Digitisation techniques for obtaining data sets for cotton, chenopodium and wheat leaves are discussed and novel algorithms for the reconstruction of the leaves from these three plant species are developed. The reconstructed leaf surfaces are included into agricultural droplet spray models to investigate the effect of the nozzle and spray formulation combination on the proportion of spray retained by the plant. A numerical study of the post-impaction motion of large droplets that have formed on the leaf surface is also considered.

The origin of a large (>3km) maar volcano by coalescence of multiple shallow craters: Lake Purrumbete maar, southeastern Australia

Lake Purrumbete maar is located in the intraplate, monogenetic Newer Volcanics Province in southeastern Australia. The extremely large crater of 3000. m in diameter formed on an intersection of two fault lines and comprises at least three coalesced vents. The evolution of these vents is controlled by the interaction of the tectonic setting and the properties of both hard and soft rock aquifers. Lithics in the maar deposits originate from country rock formations less than 300. m deep, indicating that the large size of the crater cannot only be the result of the downwards migration of the explosion foci in a single vent. Vertical crater walls and primary inward dipping beds evidence that the original size of the crater has been largely preserved. Detailed mapping of the facies distributions, the direction of transport of base surges and pyroclastic flows, and the distribution of ballistic block fields, form the basis for the reconstruction of the complex eruption history,which is characterised by alternations of the eruption style between relatively dry and wet phreatomagmatic conditions, and migration of the vent location along tectonic structures. Three temporally separated eruption phases are recognised, each starting at the same crater located directly at the intersection of two local fault lines. Activity then moved quickly to different locations. A significant volcanic hiatus between two of the three phases shows that the magmatic system was reactivated. The enlargement of especially the main crater by both lateral and vertical growth led to the interception of the individual craters and the formation of the large circular crater. Lake Purrumbete maar is an excellent example of how complicated the evolution of large, seemingly simple, circular maar volcanoes can be, and raises the question if these systems are actually monogenetic.

Reconstruction of a multi-vent kimberlite eruption from deposit and host rock characteristics: Jericho kimberlite, Nunavut, Canada

The Jericho kimberlite (173.1. ±. 1.3. Ma) is a small (~. 130. ×. 70. m), multi-vent system that preserves products from deep (>. 1. km?) portions of kimberlite vents. Pit mapping, drill core examination, petrographic study, image analysis of olivine crystals (grain size distributions and shape studies), and compositional and mineralogical studies, are used to reconstruct processes from near-surface magma ascent to kimberlite emplacement and alteration. The Jericho kimberlite formed by multiple eruptions through an Archean granodiorite batholith that was overlain by mid-Devonian limestones ~. 1. km in thickness. Kimberlite magma ascended through granodiorite basement by dyke propagation but ascended through limestone, at least in part, by locally brecciating the host rocks. After the first explosive breakthrough to surface, vent deepening and widening occurred by the erosive forces of the waxing phase of the eruption, by gravitationally induced failures as portions of the vent margins slid into the vent and, in the deeper portions of the vent (>. 1. km), by scaling, as thin slabs burst from the walls into the vent. At currently exposed levels, coherent kimberlite (CK) dykes (<. 40. cm thick) are found to the north and south of the vent complex and represent the earliest preserved in-situ products of Jericho magmatism. Timing of CK emplacement on the eastern side of the vent complex is unclear; some thick CK (15-20. m) may have been emplaced after the central vent was formed. Explosive eruptive products are preserved in four partially overlapping vents that are roughly aligned along strike with the coherent kimberlite dyke. The volcaniclastic kimberlite (VK) facies are massive and poorly sorted, with matrix- to clast-supported textures. The VK facies fragmented by dry, volatile-driven processes and were emplaced by eruption column collapse back into the volcanic vents. The first explosive products, poorly preserved because of partial destruction by later eruptions, are found in the central-east vent and were formed by eruption column collapse after the vent was largely cleared of country rock debris. The next active vent was either the north or south vent. Collapse of the eruption column, linked to a vent widening episode, resulted in coeval avalanching of pipe margin walls into the north vent, forming interstratified lenses of country rock-rich boulder breccias in finer-grained volcaniclastic kimberlite. South vent kimberlite has similar characteristics to kimberlite of the north vent and likely formed by similar processes. The final eruptive phase formed olivine-rich and moderately sorted deposits of the central vent. Better sorting is attributed to recycling of kimberlite debris by multiple eruptions through the unconsolidated volcaniclastic pile and associated collapse events. Post-emplacement alteration varies in intensity, but in all cases, has overprinted the primary groundmass and matrix, in CK and VK, respectively. Erosion has since removed all limestone cover.

Separable spatiotemporal priors for convex reconstruction of time-varying 3D point clouds

Reconstructing 3D motion data is highly under-constrained due to several common sources of data loss during measurement, such as projection, occlusion, or miscorrespondence. We present a statistical model of 3D motion data, based on the Kronecker structure of the spatiotemporal covariance of natural motion, as a prior on 3D motion. This prior is expressed as a matrix normal distribution, composed of separable and compact row and column covariances. We relate the marginals of the distribution to the shape, trajectory, and shape-trajectory models of prior art. When the marginal shape distribution is not available from training data, we show how placing a hierarchical prior over shapes results in a convex MAP solution in terms of the trace-norm. The matrix normal distribution, fit to a single sequence, outperforms state-of-the-art methods at reconstructing 3D motion data in the presence of significant data loss, while providing covariance estimates of the imputed points.

Scopophobia/Scopophilia: electric light and the anxiety of the gaze in postwar American architecture

In the years of reconstruction and economic boom that followed the Second World War, the domestic sphere encountered new expectations regarding social behaviour, modes of living, and forms of dwelling. This book brings together an international group of scholars from architecture, design, urban planning, and interior design to reappraise mid-twentieth century modern life, offering a timely reassessment of culture and the economic and political effects on civilian life. This collection contains essays that examine the material of art, objects, and spaces in the context of practices of dwelling over the long span of the postwar period. It asks what role material objects, interior spaces, and architecture played in quelling or fanning the anxieties of modernism’s ordinary denizens, and how this role informs their legacy today. Table of Contents [Book] Introduction Robin Schuldenfrei Part 1: Psychological Constructions: Anxiety of Isolation and Exposure 1. Taking Comfort in the Age of Anxiety: Eero Saarinen’s Womb Chair Cammie McAtee 2. The Future is Possibly Past: The Anxious Spaces of Gaetano Pesce Jane Pavitt 3. Scopophobia/Scopophilia: Electric Light and the Anxiety of the Gaze in American Postwar Domestic Architecture Margaret Petty Part 2: Ideological Objects: Design and Representation 4. The Allegory of the Socialist Lifestyle: The Czechoslovak Pavilion at the Brussels Expo, its Gold Medal and the Politburo Ana Miljacki 5. Assimilating Unease: Moholy-Nagy and the Wartime-Postwar Bauhaus in Chicago Robin Schuldenfrei 6. The Anxieties of Autonomy: Peter Eisenman from Cambridge to House VI Sean Keller Part 3: Societies of Consumers: Materialist Ideologies and Postwar Goods 7. "But a home is not a laboratory": The Anxieties of Designing for the Socialist Home in the German Democratic Republic 1950—1965 Katharina Pfützner 8. Architect-designed Interiors for a Culturally Progressive Upper-Middle Class: The Implicit Political Presence of Knoll International in Belgium Fredie Floré 9. Domestic Environment: Italian Neo-Avant-Garde Design and the Politics of Post-Materialism Mary Louise Lobsinger Part 4: Class Concerns and Conflict: Dwelling and Politics 10. Dirt and Disorder: Taste and Anxiety in the Working Class Home Christine Atha 11. Upper West Side Stories: Race, Liberalism, and Narratives of Urban Renewal in Postwar New York Jennifer Hock 12. Pawns or Prophets? Postwar Architects and Utopian Designs for Southern Italy Anne Parmly Toxey. Coda: From Homelessness to Homelessness David Crowley