Carbon monoxide and isocyanide complexes of trivalent uranium metallocenes

The [Cp′3U] metallocenes contain substituted cyclopentadienyl ligands and UIII with f3 electron configuration. They are good π donors and bind π-accepting ligands (L) such as carbon monoxide and isocyanides to form the corresponding adducts [Cp′3U(L)] (see scheme). The π-donating capability of the [Cp′3U] fragments appears to be readily modulated by the substituents on the cyclopentadienyl ligand.

Poly[aqua([mu]3-2-hydroxy-5-nitrobenzoato-[kappa]3O1:O1':O2)rubidium]

In the structure of title compound [Rb2(C7H4NO2)2(H2O)2]n the centrosymmetric cyclic dimeric repeating unit comprises two irregular RbO4 complex centres bridged by the carboxylate groups of the 5-nitrosalicylate ligands. The coordination about each Rb is completed by a monodentate water molecule and a phenolic O donor which gives a bridging extension [Rb-O range 3.116(7)-3.135(5)A]. The two-dimensional polymeric structure is stabilized by intermolecular water O-H...O(carboxyl) hydrogen bonds and weak inter-ring pi--pi interactions [minimum ring centroid separation, 3.620(4)A].

Investigation to enhance high speed rail accessibility

High Speed Rail (HSR) is rapidly gaining popularity worldwide as a safe and efficient transport option for long-distance travel. Designed to win market shares from air transport, HSR systems optimise their productivity between increasing speeds and station spacing to offer high quality service and gain ridership. Recent studies have investigated the effects that the deployment of HSR infrastructure has on spatial distribution and the economic development of cities and regions. Findings appear mostly positive at higher geographical scales, where HSR links connect major urban centres several hundred kilometres apart and already well positioned within a national or international context. Also, at the urban level, studies have shown regeneration and concentration effects around HSR station areas with positive returns on city’s image and economy. However, doubts persist on the effects of HSR at an intermediate scale, where the accessibility trade off on station spacing limits access to many small and medium agglomerations. Thereby, their ability to participate in the development opportunities facilitated by HSR infrastructure is significantly reduced. The locational advantages deriving from transport improvements appear contrasting especially in regions that tend to have a polycentric structure, where cities may present greater accessibility disparities between those served by HSR and those left behind. This thesis fits in this context where intermediate and regional cities do not directly enjoy the presence of an HSR station while having an existing or planned proximate HSR corridor. With the aim of understanding whether there might be a solution to this apparent incongruity, the research investigates strategies to integrate HSR accessibility at the regional level. While current literature recommends to commit with ancillary investments to the uplift of station areas and the renewal of feeder systems, I hypothesised the interoperability between the HSR and the conventional networks to explore the possibilities offered by mixed traffic and infrastructure sharing. Thus, I developed a methodology to quantify the exchange of benefits deriving from this synergistic interaction. In this way, it was possible to understand which level of service quality offered by alternative transit strategies best facilitates the distribution of accessibility benefits for areas far from actual HSR stations. Therefore, strategies were selected for their type of service capable of regional extensions and urban penetrations, while incorporating a combination of specific advantages (e.g. speed, sub-urbanity, capacity, frequency and automation) in order to emulate HSR quality with increasingly efficient services. The North-eastern Italian macro region was selected as case study to ground the research offering concurrently a peripheral polycentric metropolitan form, the presence of a planned HSR corridor with some portions of HSR infrastructure implementation, and the project to develop a suburban rail service extended regionally. Results show significant distributive potential, in terms of network effects produced in relation with HSR, in increasing proportions for all the strategies considered: a regional metro rail strategy (abbreviated RMR), a regional high speed rail strategy (abbreviated RHSR), a regional light rail transit (abbreviated LRT) strategy, and a non-stopping continuous railway system (abbreviated CRS) strategy. The provision of additional tools to value HSR infrastructure against its accessibility benefits and their regional distribution through alternative strategies beyond the actual HSR stations, would have great implications, both politically and technically, in moving towards new dimensions of HSR evaluation and development.

The allocation of taxing rights of ship and aircraft leasing profits under Australia's tax treaties

The Australian Federal Commissioner of Taxation recently released Draft Taxation Ruling TR 2008/D3 with the stated purpose of clarifying ‘what profits derived from the leasing of ships or aircraft fall within the ship and aircraft articles of each of Australia’s tax treaties’. In particular, TR 2008/D3 explains the taxing rights over different types of leasing profits, such as a full basis lease in respect of any transport by a ship operated in international traffic and bareboat leases which are ancillary to the lessor transport operations of ships in international traffic. This article outlines the Commissioner’s views on the application of the standard ships and aircraft articles in the tax treaties to which it is a party as well as considering the major variations on the standard adoption. In doing so, guidance is provided as to the allocation of taxing rights of ship and aircraft leasing profits under Australia’s tax treaties.

Gold coating of silica and zinc oxide nanoparticles by the surface reduction of gold(I) chloride

The possibility of a surface inner sphere electron transfer mechanism leading to the coating of gold via the surface reduction of gold(I) chloride on metal and semi-metal oxide nanoparticles was investigated. Silica and zinc oxide nanoparticles are known to have very different surface chemistry, potentially leading to a new class of gold coated nanoparticles. Monodisperse silica nanoparticles were synthesised by the well known Stöber protocol in conjunction with sonication. The nanoparticle size was regulated solely by varying the amount of ammonia solution added. The presence of surface hydroxyl groups was investigated by liquid proton NMR. The resultant nanoparticle size was directly measured by the use of TEM. The synthesised silica nanoparticles were dispersed in acetonitrile (MeCN) and added to a bis acetonitrile gold(I) co-ordination complex [Au(MeCN)2]+ in MeCN. The silica hydroxyl groups were deprotonated in the presence of MeCN generating a formal negative charge on the siloxy groups. This allowed the [Au(MeCN)2]+ complex to undergo ligand exchange with the silica nanoparticles, which formed a surface co-ordination complex with reduction to gold(0), that proceeded by a surface inner sphere electron transfer mechanism. The residual [Au(MeCN)2]+ complex was allowed to react with water, disproportionating into gold(0) and gold(III) respectively, with gold(0) being added to the reduced gold already bound on the silica surface. The so-formed metallic gold seed surface was found to be suitable for the conventional reduction of gold(III) to gold(0) by ascorbic acid. This process generated a thin and uniform gold coating on the silica nanoparticles. This process was modified to include uniformly gold coated composite zinc oxide nanoparticles (Au@ZnO NPs) using surface co-ordination chemistry. AuCl dissolved in acetonitrile (MeCN) supplied chloride ions which were adsorbed onto ZnO NPs. The co-ordinated gold(I) was reduced on the ZnO surface to gold(0) by the inner sphere electron transfer mechanism. Addition of water disproportionated the remaining gold(I) to gold(0) and gold(III). Gold(0) bonded to gold(0) on the NP surface with gold(III) was reduced to gold(0) by ascorbic acid (ASC), which completed the gold coating process. This gold coating process of Au@ZnO NPs was modified to incorporate iodide instead of chloride. ZnO NPs were synthesised by the use of sodium oxide, zinc iodide and potassium iodide in refluxing basic ethanol with iodide controlling the presence of chemisorbed oxygen. These ZnO NPs were treated by the addition of gold(I) chloride dissolved in acetonitrile leaving chloride anions co-ordinated on the ZnO NP surface. This allowed acetonitrile ligands in the added [Au(MeCN)2]+ complex to surface exchange with adsorbed chloride from the dissolved AuCl on the ZnO NP surface. Gold(I) was then reduced by the surface inner sphere electron transfer mechanism. The presence of the reduced gold on the ZnO NPs allowed adsorption of iodide to generate a uniform deposition of gold onto the ZnO NP surface without the use of additional reducing agents or heat.

Hospital outpatient responses to potential driving impairment due to prescribed medications

Driving and using prescription medicines that have the potential to impair driving is an emerging research area. To date it is characterised by a limited (although growing) number of studies and methodological complexities that make generalisations about impairment due to medications difficult. Consistent evidence has been found for the impairing effects of hypnotics, sedative antidepressants and antihistamines, and narcotic analgesics, although it has been estimated that as many as nine medication classes have the potential to impair driving (Alvarez & del Rio, 2000; Walsh, de Gier, Christopherson, & Verstraete, 2004). There is also evidence for increased negative effects related to concomitant use of other medications and alcohol (Movig et al., 2004; Pringle, Ahern, Heller, Gold, & Brown, 2005). Statistics on the high levels of Australian prescription medication use suggest that consumer awareness of driving impairment due to medicines should be examined. One web-based study has found a low level of awareness, knowledge and risk perceptions among Australian drivers about the impairing effects of various medications on driving (Mallick, Johnston, Goren, & Kennedy, 2007). The lack of awareness and knowledge brings into question the effectiveness of the existing countermeasures. In Australia these consist of the use of ancillary warning labels administered under mandatory regulation and professional guidelines, advice to patients, and the use of Consumer Medicines Information (CMI) with medications that are known to cause impairment. The responsibility for the use of the warnings and related counsel to patients primarily lies with the pharmacist when dispensing relevant medication. A review by the Therapeutic Goods Administration (TGA) noted that in practice, advice to patients may not occur and that CMI is not always available (TGA, 2002). Researchers have also found that patients' recall of verbal counsel is very low (Houts, Bachrach, Witmer, Tringali, Bucher, & Localio, 1998). With healthcare observed as increasingly being provided in outpatient conditions (Davis et al., 2006; Vingilis & MacDonald, 2000), establishing the effectiveness of the warning labels as a countermeasure is especially important. There have been recent international developments in medication categorisation systems and associated medication warning labels. In 2005, France implemented a four-tier medication categorisation and warning system to improve patients' and health professionals' awareness and knowledge of related road safety issues (AFSSAPS, 2005). This warning system uses a pictogram and indicates the level of potential impairment in relation to driving performance through the use of colour and advice on the recommended behaviour to adopt towards driving. The comparable Australian system does not indicate the severity level of potential effects, and does not provide specific guidelines on the attitude or actions that the individual should adopt towards driving. It is reliant upon the patient to be vigilant in self-monitoring effects, to understand the potential ways in which they may be affected and how serious these effects may be, and to adopt the appropriate protective actions. This thesis investigates the responses of a sample of Australian hospital outpatients who receive appropriate labelling and counselling advice about potential driving impairment due to prescribed medicines. It aims to provide baseline data on the understanding and use of relevant medications by a Queensland public hospital outpatient sample recruited through the hospital pharmacy. It includes an exploration and comparison of the effect of the Australian and French medication warning systems on medication user knowledge, attitudes, beliefs and behaviour, and explores whether there are areas in which the Australian system may be improved by including any beneficial elements of the French system. A total of 358 outpatients were surveyed, and a follow-up telephone survey was conducted with a subgroup of consenting participants who were taking at least one medication that required an ancillary warning label about driving impairment. A complementary study of 75 French hospital outpatients was also conducted to further investigate the performance of the warnings. Not surprisingly, medication use among the Australian outpatient sample was high. The ancillary warning labels required to appear on medications that can impair driving were prevalent. A subgroup of participants was identified as being potentially at-risk of driving impaired, based on their reported recent use of medications requiring an ancillary warning label and level of driving activity. The sample reported previous behaviour and held future intentions that were consistent with warning label advice and health protective action. Participants did not express a particular need for being advised by a health professional regarding fitness to drive in relation to their medication. However, it was also apparent from the analysis that the participants would be significantly more likely to follow advice from a doctor than a pharmacist. High levels of knowledge in terms of general principles about effects of alcohol, illicit drugs and combinations of substances, and related health and crash risks were revealed. This may reflect a sample specific effect. Emphasis is placed in the professional guidelines for hospital pharmacists that make it essential that advisory labels are applied to medicines where applicable and that warning advice is given to all patients on medication which may affect driving (SHPA, 2006, p. 221). The research program applied selected theoretical constructs from Schwarzer's (1992) Health Action Process Approach, which has extended constructs from existing health theories such as the Theory of Planned Behavior (Ajzen, 1991) to better account for the intention-behaviour gap often observed when predicting behaviour. This was undertaken to explore the utility of the constructs in understanding and predicting compliance intentions and behaviour with the mandatory medication warning about driving impairment. This investigation revealed that the theoretical constructs related to intention and planning to avoid driving if an effect from the medication was noticed were useful. Not all the theoretical model constructs that had been demonstrated to be significant predictors in previous research on different health behaviours were significant in the present analyses. Positive outcome expectancies from avoiding driving were found to be important influences on forming the intention to avoid driving if an effect due to medication was noticed. In turn, intention was found to be a significant predictor of planning. Other selected theoretical constructs failed to predict compliance with the Australian warning label advice. It is possible that the limited predictive power of a number of constructs including risk perceptions is due to the small sample size obtained at follow up on which the evaluation is based. Alternately, it is possible that the theoretical constructs failed to sufficiently account for issues of particular relevance to the driving situation. The responses of the Australian hospital outpatient sample towards the Australian and French medication warning labels, which differed according to visual characteristics and warning message, were examined. In addition, a complementary study with a sample of French hospital outpatients was undertaken in order to allow general comparisons concerning the performance of the warnings. While a large amount of research exists concerning warning effectiveness, there is little research that has specifically investigated medication warnings relating to driving impairment. General established principles concerning factors that have been demonstrated to enhance warning noticeability and behavioural compliance have been extrapolated and investigated in the present study. The extent to which there is a need for education and improved health messages on this issue was a core issue of investigation in this thesis. Among the Australian sample, the size of the warning label and text, and red colour were the most visually important characteristics. The pictogram used in the French labels was also rated highly, and was salient for a large proportion of the sample. According to the study of French hospital outpatients, the pictogram was perceived to be the most important visual characteristic. Overall, the findings suggest that the Australian approach of using a combination of visual characteristics was important for the majority of the sample but that the use of a pictogram could enhance effects. A high rate of warning recall was found overall and a further important finding was that higher warning label recall was associated with increased number of medication classes taken. These results suggest that increased vigilance and care are associated with the number of medications taken and the associated repetition of the warning message. Significantly higher levels of risk perception were found for the French Level 3 (highest severity) label compared with the comparable mandatory Australian ancillary Label 1 warning. Participants' intentions related to the warning labels indicated that they would be more cautious while taking potentially impairing medication displaying the French Level 3 label compared with the Australian Label 1. These are potentially important findings for the Australian context regarding the current driving impairment warnings about displayed on medication. The findings raise other important implications for the Australian labelling context. An underlying factor may be the differences in the wording of the warning messages that appear on the Australian and French labels. The French label explicitly states "do not drive" while the Australian label states "if affected, do not drive", and the difference in responses may reflect that less severity is perceived where the situation involves the consumer's self-assessment of their impairment. The differences in the assignment of responsibility by the Australian (the consumer assesses and decides) and French (the doctor assesses and decides) approaches for the decision to drive while taking medication raises the core question of who is most able to assess driving impairment due to medication: the consumer, or the health professional? There are pros and cons related to knowledge, expertise and practicalities with either option. However, if the safety of the consumer is the primary aim, then the trend towards stronger risk perceptions and more consistent and cautious behavioural intentions in relation to the French label suggests that this approach may be more beneficial for consumer safety. The observations from the follow-up survey, although based on a small sample size and descriptive in nature, revealed that just over half of the sample recalled seeing a warning label about driving impairment on at least one of their medications. The majority of these respondents reported compliance with the warning advice. However, the results indicated variation in responses concerning alcohol intake and modifying the dose of medication or driving habits so that they could continue to drive, which suggests that the warning advice may not be having the desired impact. The findings of this research have implications for current countermeasures in this area. These have included enhancing the role that prescribing doctors have in providing warnings and advice to patients about the impact that their medication can have on driving, increasing consumer perceptions of the authority of pharmacists on this issue, and the reinforcement of the warning message. More broadly, it is suggested that there would be benefit in a wider dissemination of research-based information on increased crash risk and systematic monitoring and publicity about the representation of medications in crashes resulting in injuries and fatalities. Suggestions for future research concern the continued investigation of the effects of medications and interactions with existing medical conditions and other substances on driving skills, effects of variations in warning label design, individual behaviours and characteristics (particularly among those groups who are dependent upon prescription medication) and validation of consumer self-assessment of impairment.

Experimental and theoretical investigation of ligand effects on the synthesis of ZnO nanoparticles

ZnO nanoparticles with highly controllable particle sizes(less than 10 nm) were synthesized using organic capping ligands in Zn(Ac)2 ethanolic solution. The molecular structure of the ligands was found to have significant influence on the particle size. The multi-functional molecule tris(hydroxymethyl)-aminomethane (THMA) favoured smaller particle distributions compared with ligands possessing long hydrocarbon chains that are more frequently employed. The adsorption of capping ligands on ZnnOn crystal nuclei (where n = 4 or 18 molecular clusters of(0001) ZnO surfaces) was modelled by ab initio methods at the density functional theory (DFT) level. For the molecules examined, chemisorption proceeded via the formation of Zn...O, Zn...N, or Zn...S chemical bonds between the ligands and active Zn2+ sites on ZnO surfaces. The DFT results indicated that THMA binds more strongly to the ZnO surface than other ligands, suggesting that this molecule is very effective at stabilizing ZnO nanoparticle surfaces. This study, therefore, provides new insight into the correlation between the molecular structure of capping ligands and the morphology of metal oxide nanostructures formed in their presence.

Two-dimensional coordination polymers in rubidium and caesium complexes with orthanilic acid

The crystal structures of the rubidium and caesium complexes with 2-aminobenzenesulfonic acid (orthanilic acid), [Rb4(C6H6NO3S)4(H2O)]n (1) and [Cs(C6H6NO3S)]n (2) and have been determined at 200 K. Complex 1 has a repeating unit comprising four independent and different Rb coordination centres, (RbO8), (RbO7), (RbN2O4) and (RbO10), each having irregular stereochemistry and involving a number of bidentate chelate sulfonate-O,O’-metal and bridging interactions, giving a two-dimensional polymeric layered structure. Anhydrous complex 2 is also polymeric with the irregular (CsO7) coordination polyhedron comprising six sulfonate oxygen donors from three separate bidentate chelate sulfonate ligands and one monodentate bridging sulfonate oxygen, giving a two-dimensional layered structure.

Early users of fertility treatment with hormones and IVF : women who live in major cities and have private health insurance

Objective: To identify early users (women aged <34 years) of fertility treatment with hormones and in vitro fertilisation (IVF). Methods: A cross-sectional survey of infertile women from fertility clinics (n=59) and from the community (Australian Longitudinal Study on Women's Health participants) who had (n=121) or had not (n=110) used hormones/IVF as treatment for infertility. Associations between socio-demographic, reproductive and lifestyle factors, medical conditions and recurrent symptoms and using treatment (or not) were analysed using multivariable logistic regression. Results: Among infertile women who had used treatment (community vs clinic), women from clinics had lower odds of living outside major cities, using hormones only, i.e., not IVF, or recurrent headaches/migraines, severe tiredness, or stiff/painful joints; and higher odds of recent diagnoses of urinary tract infection or anxiety disorder. Compared to infertile women who had not used treatment, women from clinics had lower odds of living outside major cities, recurrent allergies or severe tiredness; and higher odds of having private health insurance for hospital or ancillary services, recent diagnosis of polycystic ovary syndrome or recurrent constipation. Conclusions: Compared to infertile women in the community, living in major cities and having private health insurance are associated with early use of treatment for infertility at specialist clinics by women aged <34 years. Implications: These results provided evidence of inequity of services for infertile women.

In vitro and in vivo studies on protease-activated receptor-2

Protease-activated receptor-2 (PAR2) is a G protein coupled receptor (GPCR) that is activated by proteolytic cleavage of its amino terminal domain by trypsin-like serine proteases. Cleavage of this receptor exposes a neoepitope, termed the tethered ligand (TL), which binds intramolecularly within the receptor to stimulate signal transduction via coupled G proteins. PAR2-mediated signal transduction is also experimentally stimulated by hexapeptides (agonist peptides; APs) that are homologous to the TL sequence. Due to the irreversible nature of PAR2 proteolysis, downstream signal transduction is tightly regulated. Following activation, PAR2 is rapidly uncoupled from downstream signalling by the post-translational modifications phosphorylation and ubiquination which facilitate interactions with â- arrestin. This scaffolding protein couples PAR2 to the internalisation machinery initiating its desensitisation and trafficking through the early and late endosomes followed by receptor degradation. PAR2 is widely expressed in mammalian tissues with key roles for this receptor in cardiovascular, respiratory, nervous and musculoskeletal systems. This receptor has also been linked to pathological states with aberrant expression and signalling noted in several cancers. In prostate cancer, PAR2 signalling induces migration and proliferation of tumour derived cell lines, while elevated receptor expression has been noted in malignant tissues. Importantly, a role for this receptor has also been suggested in prostate cancer bone metastasis as coexpression of PAR2 and a proteolytic activator has been demonstrated by immunohistochemical analysis. Based on these data, the primary focus of this project has been on two aspects of PAR2 biology. The first is characterisation of cellular mechanisms that regulate PAR2 signalling and trafficking. The second aspect is the role of this receptor in prostate cancer bone metastasis. In addition, to permit these studies, it was first necessary to evaluate the specificity of the commercially available anti-PAR2 antibodies SAM11, C17, N19 and H99. The evaluation of the four commercially available antibodies was assessed using four techniques: immunoprecipitation; Western blot analysis; immunofluorescence; and flow cytometry. These approaches demonstrated that three of the antibodies efficiently detect ectopically expressed PAR2 by each of these techniques. A significant finding from this study was that N19 was the only antibody able to specifically detect N-glycosylated endogenous PAR2 by Western blot analysis. This analysis was performed on lysates from prostate cancer derived cell lines and tissue derived from wildtype and PAR2 knockout mice. Importantly, further evaluation demonstrated that this antibody also efficiently detects endogenous PAR2 at the cell surface by flow cytometry. The anti-PAR2 antibody N19 was used to explore the in vitro role of palmitoylation, the post-translational addition of palmitate, in PAR2 signalling, trafficking, cell surface expression and desensitization. Significantly, use of the palmitoylation inhibitor 2-bromopalmitate indicated that palmitate addition is important in trafficking of PAR2 endogenously expressed by prostate cancer cell lines. This was supported by palmitate labelling experiments using two approaches which showed that PAR2 stably expressed by CHO cells is palmitoylated and that palmitoylation occurs on cysteine 361. Another key finding from this study is that palmitoylation is required for optimal PAR2 signalling as Ca2+ flux assays indicated that in response to trypsin agonism, palmitoylation deficient PAR2 is ~9 fold less potent than wildtype receptor with a reduction of about 33% in the maximum signal induced via the mutant receptor. Confocal microscopy, flow cytometry and cell surface biotinylation analyses demonstrated that palmitoylation is required for efficient cell surface expression of PAR2. Importantly, this study also identified that palmitoylation of this receptor within the Golgi apparatus is required for efficient agonist-induced rab11amediated trafficking of PAR2 to the cell surface. Interestingly, palmitoylation is also required for receptor desensitization, as agonist-induced â-arrestin recruitment and receptor degradation were markedly reduced in CHO-PAR2-C361A cells compared with CHO-PAR2 cells. Collectively, these data provide new insights on the life cycle of PAR2 and demonstrate that palmitoylation is critical for efficient signalling, trafficking, cell surface localization and degradation of this receptor. This project also evaluated PAR2 residues involved in ligand docking. Although the extracellular loop (ECL)2 of PAR2 is known to be required for agonist-induced signal transduction, the binding pocket for receptor agonists remains to be determined. In silico homology modelling, based on a crystal structure for the prototypical GPCR rhodopsin, and ligand docking were performed to identify PAR2 transmembrane (TM) amino acids potentially involved in agonist binding. These methods identified 12 candidate residues that were mutated to examine the binding site of the PAR2 TL, revealed by trypsin cleavage, as well as of the soluble ligands 2f-LIGRLO-NH2 and GB110, which are both structurally based on the AP SLIGRLNH2. Ligand binding was evaluated from the impact of the mutated residues on PAR2-mediated calcium mobilisation. An important finding from these experiments was that mutation of residues Y156 and Y326 significantly reduced 2f-LIGRLO-NH2 and GB110 agonist activity. L307 was also important for GB110 activity. Intriguingly, mutation of PAR2 residues did not alter trypsin-induced signalling to the same extent as for the soluble agonists. The reason for this difference remains to be further examined by in silico and in vitro experimentation and, potentially, crystal structure studies. However, these findings identified the importance of TM domains in PAR2 ligand docking and will enhance the design of both PAR2 agonists and potentially agents to inhibit signalling (antagonists). The potential importance of PAR2 in prostate cancer bone metastasis was examined using a mouse model. In patients, prostate cancer bone metastases cause bone growth by disrupting bone homeostasis. In an attempt to mimic prostate cancer growth in bone, PAR2 responsive 22Rv1 prostate cancer cells, which form mixed osteoblastic and osteolytic lesions, were injected into the proximal aspect of mouse tibiae. A role for PAR2 was assessed by treating these mice with the recently developed PAR2 antagonist GB88. As controls, animals bearing intra-tibial tumours were also treated with vehicle (olive oil) or the prostate cancer chemotherapeutic docetaxel. The effect of these treatments on bone was examined radiographically and by micro-CT. Consistent with previous studies, 22Rv1 tumours caused osteoblastic periosteal spicule formation and concurrent osteolytic bone loss. Significantly, blockade of PAR2 signalling reduced the osteoblastic and osteolytic phenotype of 22Rv1 tumours in bone. No bone defects were detected in mice treated with docetaxel. These qualitative data will be followed in the future by quantitative micro-CT analysis as well as histology and histomorphometry analysis of already collected tissues. Nonetheless, these preliminary experiments highlight a potential role for PAR2 in prostate cancer growth in bone. In summary, in vitro studies have defined mechanisms regulating PAR2 activation, downstream signalling and trafficking and in vivo studies point to a potential role for this receptor in prostate cancer bone metastasis. The outcomes of this project are that a greater understanding of the biology of PAR2 may lead to the development of strategies to modulate the function of this receptor in disease.

An intelligent network control system for plug-in electric vehicles and the associate communication mechanism

The development of an intelligent plug-in electric vehicle (PEV) network is an important research topic in the smart grid environment. An intelligent PEV network enables a flexible control of PEV charging and discharging activities and hence PEVs can be utilized as ancillary service providers in the power system concerned. Given this background, an intelligent PEV network architecture is first developed, and followed by detailed designs of its application layers, including the charging and discharging controlling system, mobility and roaming management, as well as communication mechanisms associated. The presented architecture leverages the philosophy in mobile communication network buildup

Self-assembled hyperbranched polymer - gold nanoparticle hybrids : understanding the effect of polymer coverage on assembly size and SERS performance

In the past few years, remarkable progress has been made in unveiling novel and unique optical properties of strongly coupled plasmonic nanostructures. However, application of such plasmonic nanostructures in biomedicine remains challenging due to the lack of facile and robust assembly methods for producing stable nanostructures. Previous attempts to achieve plasmonic nano-assemblies using molecular ligands were limited due to the lack of flexibility that could be exercised in forming them. Here, we report the utilization of tailor-made hyperbranched polymers (HBP) as linkers to assemble gold nanoparticles (NPs) into nano-assemblies. The ease and flexibility in tuning the particle size and number of branch ends of a HBP makes it an ideal candidate as a linker, as opposed to DNA, small organic molecules and linear or dendrimeric polymers. We report a strong correlation of polymer (HBP) concentration with the size of the hybrid nano-assemblies and “hot-spot” density. We have shown that such solutions of stable HBP-gold nano-assemblies can be barcoded with various Raman tags to provide improved surface-enhanced Raman scattering (SERS) compared with non-aggregated NP systems. These Raman barcoded hybrid nano-assemblies, with further optimization of NP shape, size and “hot-spot” density, may find application as diagnostic tools in nanomedicine.

Revisiting the debate about public service media exceptionalism

The development of public service broadcasters (PSBs) in the 20th century was framed around debates about its difference compared to commercial broadcasting. These debates navigated between two poles. One concerned the relationship between non‐commercial sources of funding and the role played by statutory Charters as guarantors of the independence of PSBs. The other concerned the relationship between PSBs being both a complementary and a comprehensive service, although there are tensions inherent in this duality. In the 21st century, as reconfigured public service media organisations (PSMs) operate across multiple platforms in a convergent media environment, how are these debates changing, if at all? Is the case for PSM “exceptionalism” changed with Web‐based services, catch‐up TV, podcasting, ancillary product sales, and commissioning of programs from external sources in order to operate in highly diversified cross‐media environments? Do the traditional assumptions about non‐commercialism still hold as the basis for different forms of PSM governance and accountability? This paper will consider the question of PSM exceptionalism in the context of three reviews into Australian media that took place over 2011‐2012: the Convergence Review undertaken through the Department of Broadband, Communications and the Digital Economy; the National Classification Scheme Review undertaken by the Australian Law Reform Commission; and the Independent Media Inquiry that considered the future of news and journalism.

Evaluation of Eph receptor and ephrin expression within the human cornea and limbus

Eph receptor tyrosine kinases and their ligands, the ephrins, regulate the development and maintenance of multiple organs but little is known about their potential role within the cornea. The purpose of this study was to perform a thorough investigation of Eph/ephrin expression within the human cornea including the limbal stem cell niche. Initially, immunohistochemistry was performed on human donor eyes to determine the spatial distribution of Eph receptors and ephrins in the cornea and limbus. Patterns of Eph/ephrin gene expression in (1) immortalised human corneal endothelial (B4G12) or corneal epithelial (HCE-T) cell lines, and (2) primary cultures of epithelial or stromal cells established from the corneal limbus of cadaveric eye tissue were then assessed by reverse transcription (RT) PCR. Limbal epithelial or stromal cells from primary cultures were also assessed for evidence of Eph/ephrin-reactivity by immunofluorescence. Immunoreactivity for ephrinA1 and EphB4 was detected in the corneal endothelium of donor eyes. EphB4 was also consistently detected in the limbal and corneal epithelium and in cells located in the stroma of the peripheral cornea. Expression of multiple Eph/ephrin genes was detected in immortalised corneal epithelial and endothelial cell lines. Evidence of Eph/ephrin gene expression was also demonstrated in primary cultures of human limbal stromal (EphB4, B6; ephrinA5) and epithelial cells (EphA1, A2; ephrinA5, B2) using both RT-PCR and immunofluorescence. The expression of Eph receptors and ephrins within the human cornea and limbus is much wider than previously appreciated and suggests multiple potential roles for these molecules in the maintenance of normal corneal architecture.

Private health insurance status and utilisation of dental services in Australia

This article focuses on the relationship between private insurance status and dental service utilisation in Australia using data between 1995 and 2001. This article employs joint maximum likelihood to estimate models of time since last dental visit treating private ancillary health insurance (PAHI) as endogenous. The sensitivity of results to the choice between two different but related types of instrumental variables is examined. We find robust evidence in both 1995 and 2001 that individuals with a PAHI policy make significantly more frequent dental consultations relative to those without such coverage. A comparison of the 1995 and 2001 results, however, suggests that there has been an increasing role of PAHI in terms of the frequency of dental consultations over time. This seems intuitive given the trends in the price of unsubsidised private dental consultations. In terms of policy, our results suggest that while government measures to increase private health insurance coverage in Australia has been successful to a significant degree, it may have come at some cost in terms of socio-economic inequality as the privately insured are provided much better access to care and financial protection.