[2.2]Paracyclophane as a Target of the Organic Solid State: Emergent Properties via Supramolecular Construction

In this account, we review the synthesis of [2.2]paracyclophanes in the organic solid state. Reactions in crystalline solids provide a means to obtain molecules with high degrees of stereocontrol that can also be unattainable in solution. We show that [2.2]paracyclophanes form in the solid state stereospecifically and in quantitative yield via intermolecular [2+2] double photodimerization reactions. The double cycloaddition that affords a paracyclophane in the solid state does not readily occur in solution. Small molecules in the form of hydrogen-bond-donor templates can provide access to [2.2]paracyclophanes in a solid by design. A [2.2]paracyclophane obtained using a hydrogen-bond template is shown to exhibit attractive optical properties and has been employed as a building block of a metal-organic framework (MOF).     

Distinguishing between green building occupants’ reasoned and unplanned behaviours

Several frameworks incorporate social and psychological elements of environmentally significant behaviour, and most assume cognitive and deliberate decision-making. Household energy consumption behaviours, however, span a spectrum from reasoned and deliberate to unplanned and automatic. The aim of this paper is to advance knowledge of reasoned and unplanned behaviours in the context of pro-environmental action. Using results of a survey administered to occupants of an urban residential green building, this study explores five household consumption behaviours and tests the hypothesis that unplanned behaviours will be poorly predicted by a reasoned, values-based behavioural framework. Using path analyses, variables in a values-based framework are used to predict surveyed behaviours. Findings indicate that behaviours hypothesized to be unplanned were not well predicted by the values-based framework. The framework successfully predicted what was hypothesized to be a fully reasoned behaviour. Three potential reasons are discussed for the lack of prediction of some behaviours. A deeper understanding of how unplanned, automatic or habitual behaviours intervene in conservation intentions can help policy-makers and building designers better respond to influences of occupant behaviour on building performance.     

Hydrogel/bioactive glass composites for bone regeneration applications: Synthesis and characterisation

Due to the deficiencies of current commercially available biological bone grafts, alternative bone graft substitutes have come to the forefront of tissue engineering in recent times. The main challenge for scientists in manufacturing bone graft substitutes is to obtain a scaffold that has sufficient mechanical strength and bioactive properties to promote formation of new tissue. The ability to synthesise hydrogel based composite scaffolds using photopolymerisation has been demonstrated in this study. The prepared hydrogel based composites were characterised using techniques including Fourier Transform Infrared Spectroscopy (FTIR), X-ray diffraction (XRD), scanning electron microscopy (SEM), Energy-dispersive X-ray spectrometry (EDX), rheological studies and compression testing. In addition, gel fraction, differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), porosity and swelling studies of the composites were carried out. It was found that these novel hydrogel bioglass composite formulations did not display the inherent brittleness that is typically associated with bioactive glass based bone graft materials and exhibited enhanced biomechanical properties compared to the polyethylene glycol hydrogel scaffolds along. Together, the combination of enhanced mechanical properties and the deposition of apatite on the surface of these hydrogel based composites make them an ideal candidate as bone graft substitutes in cancellous bone defects or low load bearing applications.     

Crude oil aggregation by microscopy and dynamic light scattering

This research is focused on establishing a methodology to evaluate the aggregation state of Mexican crude oil solutions from two different sources and SARA compositions, by using Dynamic Light Scattering (DLS). Different crude oil concentrations were established and monitored through time in order to determine their effects on the aggregation state. DLS results indicate that the aggregation state of the studied solutions is influenced by crude oil composition, specifically by the amount of resins. Particle size and elemental analysis of the aggregates were performed by Scanning Electron Microscopy (SEM) and Energy Dispersive X-ray Spectroscopy (EDX), respectively. Results from these techniques reveal particulated low-porosity smooth surfaces due to the presence of resin, as well as the determination of the characteristic elements found in asphaltenes. High-Resolution Transmission Electron Microscopy (HTEM) indicated the presence of asphaltene aggregates constituted by nanometric particles and asphaltene stacking as well as ultrafine nanocrystalline-oriented structures.     

Avalanches on a conical bead pile: scaling with tuning parameters

Uniform spherical beads were used to explore the scaling behavior of a granular system near its critical angle of repose on a conical 3D bead pile. We found two tuning parameters that could take the system to a critical point. The existence of those tuning parameters violates the fundamental assumption of self-organized criticality, which proposed that complex dynamical systems self-organize to a critical point without need for tuning. Our avalanche size distributions were well described by a simple power-law, as is characteristic of a critical point, with the power τ = 1.5 when dropping beads slowly onto the apex of a bead pile from a small height. However, we could also move the system from the critical point using either of two tuning parameters: the height from which the beads fell onto the top of the pile or the region over which the beads struck the pile. As the drop height increased, the system did not reach the critical point yet the resulting distributions were independent of the bead mass, coefficient of friction, or coefficient of restitution. All our apex-dropping distributions for any type of bead (glass, stainless steel, zirconium) showed universality by scaling onto a common curve with τ = 1.5 and σ =?1.0, where 1/σ is the power of the tuning parameter. From independent calculations using the moments of the distribution, we find values for τ = 1.6 ± 0.1 and σ =?0.91 ± 0.15. When beads were dropped across the surface of the pile instead of solely on the apex, then the system also moved from the critical point and again the avalanche size distributions fell on a common curve when scaled similarly using the same values of τ and σ. We also observed that an hcp structure on the base of the pile caused an emergent structure in the pile that had six faces with some fcc or hcp structure; this structure did not affect the distribution of avalanche sizes.     

Making and negotiating value: design and collaboration with community led groups

ABSTRACT

Value in collaborative design research and practice can be understood fundamentally as relationships, materials, processes, contexts, and outcomes that are subjects of and for negotiation. We argue for conceptions of value that move beyond traditional ‘outcomes’ based measurements to reimagine and rearticulate value itself as co-created, emerging from negotiation, relationality and immersion in specific contexts. These understandings of value, we argue, are not rooted in or always knowable through designers’ experiences, even as designers participate in creating them. Using case studies from our research we suggest that value in design collaboration emerges as a question: value to whom, and to what end? We propose that addressing these questions ethically through co-design requires actively engaged, grounded work with collaborators based in three principles: being present for the work, participant making, and co-creating capacity for collaborators to ‘go off and do their thing’.     

Broadband and knowledge intensive firm clusters: Essential link or auxiliary connection?

This study evaluates the relationship between the spatial distribution of broadband providers and the presence of knowledge intensive firm clusters in US counties. Results highlight this relationship is heterogeneous and localized. In some places, broadband appears to be an essential link that enables knowledge firms to strategically locate in lower cost counties and in close proximity to major knowledge centres. In other places, the availability of broadband Internet connections are unable the negative externalities associated with locations in more remote areas of the country. From a policy perspective, this suggests that broadband should be viewed as a key component, but not the only component, of comprehensive local economic development plans.     

Images of native Americans

Abstract

This interesting volume explores the photographic environment and output of four Anglo women who had extended photographic relationships with Native American people: Kate Cory, an artist and collector who lived with the Hopi people for many years; Mary Shaffer; who travelled amongst the Stoney and Metis of Alberta, Canada; Jane Gay, who assisted ethnographer Alice Fletcher and documented land allotment and the effects of the Dawes Act on the Nez Percé people; Grace Nicholson, who set up commercial enterprises trading in art and cultural objects. None of the women was primarily a photographer. Their photographic work was always an adjunct to other purposes, to record encounters commercial, artistic or ethnographic, but at the same time the work functioned as a key articulation of their relationships with Native peoples. All four women, in their different ways, looked to Native American peoples as a way of defining and experiencing their own identities and spirituality and all four shared a commitment to and engagement with these peoples.