Visible light enhanced oxidant free dehydrogenation of aromatic alcohols using Au-Pd alloy nanoparticle catalysts

We find that visible light irradiation of gold–palladium alloy nanoparticles supported on photocatalytically inert ZrO2 significantly enhances their catalytic activity for oxidant-free dehydrogenation of aromatic alcohols to the corresponding aldehydes at ambient temperatures. Dehydrogenation is also the dominant process in the selective oxidation of the alcohols to the corresponding aldehydes with molecular oxygen. The alloy nanoparticles strongly absorb light and exhibit superior catalytic and photocatalytic activity when compared to either pure palladium or gold nanoparticles. Analysis with a free electron gas model for the bulk alloy structure reveals that the alloying increases the surface charge heterogeneity on the alloy particle surface, which enhances the interaction between the alcohol molecules and the metal NPs. The increased surface charge heterogeneity of the alloy particles is confirmed with density function theory applied to small alloy clusters. Optimal catalytic activity was observed with a Au : Pd molar ratio of 1 : 186, which is in good agreement with the theoretical analysis. The rate-determining step of the dehydrogenation is hydrogen abstraction. The conduction electrons of the nanoparticles are photo-excited by the incident light giving them the necessary energy to be injected into the adsorbed alcohol molecules, promoting the hydrogen abstraction. The strong chemical adsorption of alcohol molecules facilitates this electron transfer. The results show that the alloy nanoparticles efficiently couple thermal and photonic energy sources to drive the dehydrogenation. These findings provide useful insight into the design of catalysts that utilize light for various organic syntheses at ambient temperatures.

Medical free-text to concept mapping as an information retrieval problem

Concept mapping involves determining relevant concepts from a free-text input, where concepts are defined in an external reference ontology. This is an important process that underpins many applications for clinical information reporting, derivation of phenotypic descriptions, and a number of state-of-the-art medical information retrieval methods. Concept mapping can be cast into an information retrieval (IR) problem: free-text mentions are treated as queries and concepts from a reference ontology as the documents to be indexed and retrieved. This paper presents an empirical investigation applying general-purpose IR techniques for concept mapping in the medical domain. A dataset used for evaluating medical information extraction is adapted to measure the effectiveness of the considered IR approaches. Standard IR approaches used here are contrasted with the effectiveness of two established benchmark methods specifically developed for medical concept mapping. The empirical findings show that the IR approaches are comparable with one benchmark method but well below the best benchmark.

Multipurpose nanoporous alumina-carbon nanowall bi-dimensional nano-hybrid platform via catalyzed and catalyst-free plasma CVD

Simple, rapid, plasma-assisted synthesis of large-area arrays of vertically-aligned carbon nanowalls on highly-porous, transparent bare and gold-coated alumina membranes with the two pore sizes is reported. It is demonstrated that the complex patterns of vertically aligned nanowalls can nucleate and form different morphologies in the low-temperature plasmas. The process is stable, and the twofold change in the gas flow (10 and 20 sccm) does not noticeably influence the morphology of the nanowall pattern. Application of a thin (5 nm) gold layer to nanoporous membrane prior to the nanowall growth allows controlling the network morphology.

The role of digital screens in urban life: New opportunities for placemaking

Large digital screens are becoming prevalent across today’s cities dispersing into everyday urban spaces such as public squares and cultural precincts. Examples, such as Federation Square, demonstrate the opportunities for using digital screens to create a sense of place and to add long-term social, cultural and economic value for citizens, who live and work in those precincts. However, the challenge of implementing digital screens in new urban developments is to ensure they respond appropriately to the physical and sociocultural environment in which they are placed. Considering the increasing rate at which digital screens are being embedded into public spaces, it is surprising that the programs running on these screens still seem to be stuck in the cinematic model. The availability of advanced networking and interaction technologies offers opportunities for information access that goes beyond free-to-air television and advertising. This chapter revisits the history and current state of digital screens in urban life and discusses a series of research studies that involve digital screens as interface between citizens and the city. Instead of focusing on technological concerns, the chapter presents a holistic analysis of these studies, with the aim to move towards a more comprehensive understanding of the sociocultural potential of this new media platform, and how the digital content is linked with the spatial quality of the physical space, as well as the place and role of digital screens within the smart city movement.

Empirical insights into the development of a service-oriented enterprise architecture

Organisations use Enterprise Architecture (EA) to reduce organisational complexity, improve communication, align business and information technology (IT), and drive organisational change. Due to the dynamic nature of environmental and organisational factors, EA descriptions need to change over time to keep providing value for its stakeholders. Emerging business and IT trends, such as Service-Oriented Architecture (SOA), may impact EA frameworks, methodologies, governance and tools. However, the phenomenon of EA evolution is still poorly understood. Using Archer's morphogenetic theory as a foundation, this research conceptualises three analytical phases of EA evolution in organisations, namely conditioning, interaction and elaboration. Based on a case study with a government agency, this paper provides new empirically and theoretically grounded insights into EA evolution, in particular in relation to the introduction of SOA, and describes relevant generative mechanisms affecting EA evolution. By doing so, it builds a foundation to further examine the impact of other IT trends such as mobile or cloud-based solutions on EA evolution. At a practical level, the research delivers a model that can be used to guide professionals to manage EA and continually evolve it.

Researching Theories of Modernity & the Subject-Critique of contemporary architecture under ideological capitalism-and Fascism & Modern Architecture

In this symposium I will discuss my work on three parallel projects I have been working on since 2010: Theories of Modernity & the Subject-Critique of contemporary architecture under ideological capitalism-and Fascism & Modern Architecture

Synthesis of a multimodal molecular imaging probe based on a hyperbranched polymer architecture

Molecular imaging is utilised in modern medicine to aid in the diagnosis and treatment of disease by allowing its spatiotemporal state to be examined in vivo. This study focuses on the development of novel multimodal molecular imaging agents based on hyperbranched polymers that combine the complementary capabilities of optical fluorescence imaging and positron emission tomography-computed tomography (PET/CT) into one construct. RAFT-mediated polymerisation was used to prepare two hydrophilic hyperbranched polymers that were differentiated by their size and level of branching. The multiple functional end-groups facilitated covalent attachment of both near infrared fluorescent dyes for optical imaging, as well as a copper chelator allowing binding of 64Cu as a PET radio nuclei. In vivo multimodal imaging of mice using PET/CT and planar optical imaging was first used to assess the biodistribution of the polymeric materials and it was shown that the larger and more branched polymer had a significantly longer circulation time. The larger constructs were also shown to exhibit enhanced accumulation in solid tumours in a murine B16 melanoma model. Importantly, it was demonstrated that the PET modality gave rise to high sensitivity immediately after injection of the agent, while the optical modality facilitated extended longitudinal studies, thus highlighting how the complementary capabilities of the molecular imaging agents can be useful for studying various diseases, including cancer.

'Free' surfactant in gastric aspirates and bronchoalveolar lavage in children with and without reflux oesophagitis

Aim: Dipalmitoylphosphatidycholine (DPPC) is the characteristic and main constituent of surfactant. Adsorption of surfactant to epithelial surfaces may be important in the masking of receptors. The aims of the study were to (i) compare the quantity of free DPPC in the airways and gastric aspirates of children with gastroesophageal reflux disease (GORD) to those without and (ii) describe the association between free DPPC levels with airway cellular profile and capsaicin cough sensitivity. Methods: Children aged <14 years were defined as 'coughers' if a history of cough in association with their GORD symptoms was elicited before gastric aspirates and nonbronchoscopic bronchoalveolar lavage (BAL) were obtained during elective flexible upper gastrointestinal endoscopy. GORD was defined as histological presence of reflux oesophagitis. Spirometry and capsaicin cough-sensitivity test was carried out in children aged >6 years before the endoscopy. Results: Median age of the 68 children was 9 years (interquartile range (IQR) 7.2). Median DPPC level in BAL of children with cough (72.7 μg/mL) was similar to noncoughers (88.5). There was also no significant difference in DPPC levels in both BAL and gastric aspirates of children classified according to presence of GORD. There was no correlation between DPPC levels and cellular counts or capsaicin cough-sensitivity outcome measures. Conclusion: We conclude that free DPPC levels in the airways and gastric aspirate is not influenced by presence of cough or GORD defined by histological presence of reflux oesophagitis. Whether quantification of adsorbed surfactant differs in these groups remain unknown. Free DPPC is unlikely to have a role in masking of airway receptors. © 2006 Royal Australasian College of Physicians.

Biceps femoris architecture and strength in athletes with a prior ACL reconstruction

Purpose To determine if limbs with a history of anterior cruciate ligament (ACL) injury reconstructed from the semitendinosus (ST) display different biceps femoris long head (BFlh) architecture and eccentric strength, assessed during the Nordic hamstring exercise, compared to the contralateral uninjured limb. Methods The architectural characteristics of the BFlh were assessed at rest and at 25% of a maximal voluntary isometric contraction (MVIC) in the control (n=52) and previous ACL injury group (n=15) using two-dimensional ultrasonography. Eccentric knee-flexor strength was assessed during the Nordic hamstring exercise. Results Fascicle length was shorter (p=0.001; d range: 0.90 to 1.31) and pennation angle (p range: 0.001 to 0.006: d range: 0.87 to 0.93) was greater in the BFlh of the ACL injured limb when compared to the contralateral uninjured limb at rest and during 25% of MVIC. Eccentric strength was significantly lower in the ACL injured limb than the contralateral uninjured limb (-13.7%; -42.9N; 95% CI = -78.7 to -7.2; p=0.021; d=0.51). Fascicle length, MVIC and eccentric strength were not different between the left and right limb in the control group. Conclusions Limbs with a history of ACL injury reconstructed from the ST have shorter fascicles and greater pennation angles in the BFlh compared to the contralateral uninjured side. Eccentric strength during the Nordic hamstring exercise of the ACL injured limb is significantly lower than the contralateral side. These findings have implications for ACL rehabilitation and hamstring injury prevention practices which should consider altered architectural characteristics.

Microstructural characterization of ultrafine-grain interstitial-free steel by X-ray diffraction line profile analysis

This paper highlights the microstructural features of commercially available interstitial free (IF) steel specimens deformed by equal channel angular pressing (ECAP) up to four passes following the route A. The microstructure of the samples was studied by different techniques of X-ray diffraction peak profile analysis as a function of strain (epsilon). It was found that the crystallite size is reduced substantially already at epsilon=2.3 and it does not change significantly during further deformation. At the same time, the dislocation density increases gradually up to epsilon=4.6. The dislocation densities estimated from X-ray diffraction study are found to correlate very well with the experimentally obtained yield strength of the samples.

Singularity-free path planning for the Stewart platform manipulator

This paper addresses the problem of singularity-free path planning for the six-degree-of-freedom parallel manipulator known as the Stewart platform manipulator. Unlike serial manipulators, the Stewart platform possesses singular configurations within the workspace where the manipulator is uncontrollable. An algorithm has been developed to construct continuous paths within the workspace of the manipulator by avoiding singularities and ill-conditioning. Given two end-poses of the manipulator, the algorithm finds out safe (well-conditioned) via points and plans a continuous path from the initial pose to the final one. When the two end-poses belong to different branches and no singularity-free path is possible, the algorithm indicates the impossibility of a valid path. A numerical example has also been presented as illustration of the path planning strategy.

Label-free isolation of a prostate cancer cell among blood cells and the single-cell measurement of drug accumulation using an integrated microfluidic chip

Circulating tumor cells (CTCs) are found in the blood of patients with cancer. Although these cells are rare, they can provide useful information for chemotherapy. However, isolation of these rare cells from blood is technically challenging because they are small in numbers. An integrated microfluidic chip, dubbed as CTC chip, was designed and fabricated for conducting tumor cell isolation. As CTCs usually show multidrug resistance (MDR), the effect of MDR inhibitors on chemotherapeutic drug accumulation in the isolated single tumor cell is measured. As a model of CTC isolation, human prostate tumor cells were mixed with mouse blood cells and the labelfree isolation of the tumor cells was conducted based on cell size difference. The major advantages of the CTC chip are the ability for fast cell isolation, followed by multiple rounds of single-cell measurements, suggesting a potential assay for detecting the drug responses based on the liquid biopsy of cancer patients.

Architecture, the body and authority in performance

This is a theoretical investigation seeking to learn more about architecture by looking at architectural practice through another discipline. In this research architecture is investigated by examining its relationship with bodies through performance and theatre set design. This thesis aims to build on existing architectural theory, in which an absence of discourse on the body has been identified, by analysing representations of architecture and the body in performance. The research specifically examines the relationship between the body, architecture and authority in performance through the analysis of several performance works.

Unsteady free convection flow in the stagnation-point region of a rotating sphere

The unsteady free convection boundary-layer flow in the forward stagnation-point region of a sphere, which is rotating with time-dependent angular velocity in an ambient fluid, has been studied. Both constant wall temperature and constant hear flux conditions have been considered. The non-linear coupled parabolic partial differential equations governing the flow have been solved numerically using an implicit finite-difference scheme. The skin friction and the heat transfer are enhanced by the buoyancy force. The effect of the buoyancy force is found to be more pronounced for smaller Prandtl numbers than for larger Prandtl numbers. For a given buoyancy force, the heat transfer increases with an increase in Prandtl number, but the skin friction decreases.