Azo-linked corner porphyrin systems: synthesis, crystal structures and spectroscopic investigation

1,2-Bis[10,15-di(3,5-di-tert-butyl)phenylporphyrinatonickel(II)-5-yl]diazene was synthesised via copper catalysed coupling of aminated nickel(II) 5,10-diarylporphyrin (“corner porphyrin”) and its X-ray crystal structure was determined. Two different crystals yielded different structures, one with the free meso positions in a trans-like orientation, and the other with a cis-like disposition. The free meso positions of the obtained dimer have been further functionalised while the synthesis of a zinc analogue has so far been unsuccessful. The X-ray crystal structure of the dinitro derivative of the dinickel(II) azoporphyrin was determined, and the structure showed a cis-like disposition of the nitro groups.

Performance measurement and continuous improvement : are they linked to manufacturing strategy?

To maintain or achieve competitiveness and profitability, a manufacturing firm or enterprise must respond to a range of challenges, including rapid improvements in technology; declining employment and output; globalisation of markets and environmental requirements. In addition, substantial changes in government policy have had important impacts in many countries, as have the increasing levels of global trade. Manufacturing enterprises need to have a clear understanding of what their customers want and why customers purchase their products rather than purchase from their competitors. They need to fully understand the aims of the business in terms of its customers, market segments, product attributes, geographical markets and performance. Continuous Improvement (CI) methods have become widely adopted and regarded as providing an important component of increased company competitiveness. This article examines the extent to which continuous improvement activities have contributed to the different areas of business performance.

Monitoring animal behaviour and environmental interactions : GPS collars and satellite remote sensing within a satellite remote sensing context

Remote monitoring of animal behaviour in the environment can assist in managing both the animal and its environmental impact. GPS collars which record animal locations with high temporal frequency allow researchers to monitor both animal behaviour and interactions with the environment. These ground-based sensors can be combined with remotely-sensed satellite images to understand animal-landscape interactions. The key to combining these technologies is communication methods such as wireless sensor networks (WSNs). We explore this concept using a case-study from an extensive cattle enterprise in northern Australia and demonstrate the potential for combining GPS collars and satellite images in a WSN to monitor behavioural preferences and social behaviour of cattle.

Monitoring animal behaviour and environmental interactions using wireless sensor networks, GPS collars and satellite remote sensing

Remote monitoring of animal behaviour in the environment can assist in managing both the animal and its environmental impact. GPS collars which record animal locations with high temporal frequency allow researchers to monitor both animal behaviour and interactions with the environment. These ground-based sensors can be combined with remotely-sensed satellite images to understand animal-landscape interactions. The key to combining these technologies is communication methods such as wireless sensor networks (WSNs). We explore this concept using a case-study from an extensive cattle enterprise in northern Australia and demonstrate the potential for combining GPS collars and satellite images in a WSN to monitor behavioural preferences and social behaviour of cattle.

Azo- and butadiyne-linked 5,10-diarylporphyrins

Porphyrins are one of Nature’s essential building blocks that play an important role in several biological systems including oxygen transport, photosynthesis, and enzymes. Their capacity to absorb visible light, facilitate oxidation and reduction, and act as energy- and electron-transfer agents, in particular when several are held closely together, is of interest to chemists who seek to mimic Nature and to make and use these compounds in order to synthesise novel advanced materials. During this project 26 new 5,10-diarylsubstituted porphyrin monomers, 10 dimers, and 1 tetramer were synthesised. The spectroscopic and structural properties of these compounds were investigated using 1D/2D 1H NMR, UV/visible, ATR-IR and Raman spectroscopy, mass spectrometry, X-ray crystallography, electrochemistry and gel permeation chromatography. Nitration, amination, bromination and alkynylation of only one as well as both of the meso positions of the porphyrin monomers have resulted in the expansion of the synthetic possibilities for the 5,10-diarylsubstituted porphyrins. The development of these new porphyrin monomers has led to the successful synthesis of new azo- and butadiyne-linked dimers. The functionalisation of these compounds was investigated, in particular nitration, amination, and bromination. The synthesised dimers containing the azo bridge have absorption spectra that show a large split in the Soret bands and intense Q-bands that have been significantly redshifted. The butadiyne dimers also have intense, red-shifted Q-bands but smaller Soret band splittings. Crystal structures of two new azoporphyrins have been acquired and compared to the azoporphyrin previously synthesised from 5,10,15- triarylsubstituted porphyrin monomers. A completely new cyclic porphyrin oligomer (CPO) was synthesised comprising four porphyrin monomers linked by azo and butadiyne bridges. This is the first cyclic tetramer that has both the azo and butadiyne linking groups. The absorption spectrum of the tetramer exhibits a large Soret split making it more similar to the azo- dimers than the butadiyne-linked dimers. The spectroscopic characteristics of the synthesised tetramer have been compared to the characteristics of other cyclic porphyrin tetramers. The collected data indicate that the new synthesised cyclic tetramer has a more efficient ð-overlap and a better ground state electronic communication between the porphyrin rings.

Provincialising Perth? Satellite television and the Chinese communities in Western Australia

This paper explores the tensions between the security that access to satellite television programming from mainland China lends its 'new migrants' (xin yimin) and the vulnerability the consumption of 'foreign' media leaves them open to in Perth. The indiscreet 2-3 metre satellite dishes are an increasingly common sight in Perth's suburban backyards and on first glance, their presence might be (mis)interpreted as attempts to turn Perth into the China's next province. However, it is our argument these attempts to manage multiple belongings can be better understood within a context of conditions. These include Perth's geographical and metaphoric distance from the metropolitan centres of Sydney and Melbourne; the intense media scrutiny of China in recent times; the rapid closeness and synchronicity between China and Perth for reasons of trade, the dynamics of China's media environment and the mainland Chinese's care for and regard for themselves as mobile, global citizens of contemporary society.

Signal authentication and integrity schemes for next generation global navigation satellite systems

This paper describes a number of techniques for GNSS navigation message authentication. A detailed analysis of the security facilitated by navigation message authentication is given. The analysis takes into consideration the risk of critical applications that rely on GPS including transportation, finance and telecommunication networks. We propose a number of cryptographic authentication schemes for navigation data authentication. These authentication schemes provide authenticity and integrity of the navigation data to the receiver. Through software simulation, the performance of the schemes is quantified. The use of software simulation enables the collection of authentication performance data of different data channels, and the impact of various schemes on the infrastructure and receiver. Navigation message authentication schemes have been simulated at the proposed data rates of Galileo and GPS services, for which the resulting performance data is presented. This paper concludes by making recommendations for optimal implementation of navigation message authentication for Galileo and next generation GPS systems.

Photo-cross-linked poly(D,L-lactide)-based networks. Structural characterization by HR-MAS NMR spectroscopy and hydrolytic degradation behavior

To date, biodegradable networks and particularly their kinetic chain lengths have been characterized by analysis of their degradation products in solution. We characterize the network itself by NMR analysis in the solvent-swollen state under magic angle spinning conditions. The networks were prepared by photoinitiated cross-linking of poly(dl-lactide)−dimethacrylate macromers (5 kg/mol) in the presence of an unreactive diluent. Using diffusion filtering and 2D correlation spectroscopy techniques, all network components are identified. By quantification of network-bound photoinitiator fragments, an average kinetic chain length of 9 ± 2 methacrylate units is determined. The PDLLA macromer solution was also used with a dye to prepare computer-designed structures by stereolithography. For these networks structures, the average kinetic chain length is 24 ± 4 methacrylate units. In all cases the calculated molecular weights of the polymethacrylate chains after degradation are maximally 8.8 kg/mol, which is far below the threshold for renal clearance. Upon incubation in phosphate buffered saline at 37 °C, the networks show a similar mass loss profile in time as linear high-molecular-weight PDLLA (HMW PDLLA). The mechanical properties are preserved longer for the PDLLA networks than for HMW PDLLA. The initial tensile strength of 47 ± 2 MPa does not decrease significantly for the first 15 weeks, while HMW PDLLA lost 85 ± 5% of its strength within 5 weeks. The physical properties, kinetic chain length, and degradation profile of these photo-cross-linked PDLLA networks make them most suited materials for orthopedic applications and use in (bone) tissue engineering.

Paving for diverse pathways : using industry-linked learning to support Performing Arts students in their transition to protean careers

Statistics presented in Australia Council reports such as Don’t Give Up Your Day Job (2003), and Artswork: A Report On Australians Working in the Arts 1 and 2 (1997, 2005), and in other studies on destinations for Performing Arts graduates, demonstrate the diversity of post-graduation pathways for our students, the prevalence of protean careers, and the challenges in developing a sense of professional identity in a context where a portfolio of work across performance making, producing, administration and teaching can make it difficult for young artists to establish career status and capital in conventional terms (cf. Dawn Bennett, “Academy and the Real World: Developing Realistic Notions of Career in the Performing Arts”, Arts & Humanities in Higher Education, 8.3, 2009). In this panel, academics from around Australia will consider the ways in which Drama, Theatre and Performance Studies as a discipline is deploying a variety of practical, professional and work-integrated teaching and learning activities – including performance-making projects, industry projects, industry placements and student-initiated projects – to connect students with the networks, industries and professional pathways that will support their progression into their career. The panellists include Bree Hadley (Queensland University of Technology), Meredith Rogers (La Trobe University), Janys Hayes (Woolongong University) and Teresa Izzard (Curtin University). The panelists will present insights into the activities they have found successful, and address a range of questions, including: How do we introduce students to performance-making and / or producing models they will be able to employ in their future practice, particularly in light of the increasingly limited funds, time and resources available to support students’ participation in full-scale productions under the stewardship of professional artists?; How and when do we introduce students to industry networks?; How do we cater for graduates who will work as performers, writers, directors or administrators in the non-subsidised sector, the subsidised sector, community arts and education?; How do we category cater for graduates who will go on to pursue their work in a practice-as-research context in a Higher Degree?; How do we assist graduates in developing a professional identity? How do we assist graduates in developing physical, professional and personal resilience?; How do we retain our connections with graduates as part of their life-long learning?; Do practices and processes need to differ for city or regionally based / theoretically or practically based degree programs?; How do our teaching and learning activities align with emergent policy and industrial frameworks such as the shift to the “Producer Model” in Performing Arts funding, or the new mentorship, project, production and enterprise development opportunities under the Australia Council for the Arts’ new Opportunities for Young and Emerging Artists policy framework?