Experimental evidence for competitive N–O and O–C bond homolysis in gasphase alkoxyamines

The extensive use of alkoxyamines in controlled radical polymerisation and polymer stabilisation is based on rapid cycling between the alkoxyamine (R1R2NO–R3) and a stable nitroxyl radical (R1R2NO•) via homolysis of the labile O–C bond. Competing homolysis of the alkoxyamine N–O bond has been predicted to occur for some substituents leading to production of aminyl and alkoxyl radicals. This intrinsic competition between the O–C and N–O bond homolysis processes has to this point been difficult to probe experimentally. Herein we examine the effect of local molecular structure on the competition between N–O and O–C bond cleavage in the gas phase by variable energy tandem mass spectrometry in a triple quadrupole mass spectrometer. A suite of cyclic alkoxyamines with remote carboxylic acid moieties (HOOC–R1R2NO–R3) were synthesised and subjected to negative ion electrospray ionisation to yield [M – H]− anions where the charge is remote from the alkoxyamine moiety. Collision-induced dissociation of these anions yield product ions resulting, almost exclusively, from homolysis of O–C and/or N–O bonds. The relative efficacy of N–O and O–C bond homolysis was examined for alkoxyamines incorporating different R3 substituents by varying the potential difference applied to the collision cell, and comparing dissociation thresholds of each product ion channel. For most R3 substituents, product ions from homolysis of the O–C bond are observed and product ions resulting from cleavage of the N–O bond are minor or absent. A limited number of examples were encountered however, where N–O homolysis is a competitive dissociation pathway because the O–C bond is stabilised by adjacent heteroatom(s) (e.g., R3 = CH2F). The dissociation threshold energies were compared for different alkoxyamine substituents (R3) and the relative ordering of these experimentally determined energies is shown to correlate with the bond dissociation free energies, calculated by ab initio methods. Understanding the structure-dependent relationship between these rival processes will assist in the design and selection of alkoxyamine motifs that selectively promote the desirable O–C homolysis pathway.

Sexual selection in true fruit flies (Diptera: Tephritidae) : transcriptome and experimental evidences for phytochemicals increasing male competitive ability

In male tephritid fruit flies of the genus Bactrocera, feeding on secondary plant compounds (sensu lato male lures = methyl eugenol, raspberry ketone and zingerone) increases male mating success. Ingested male lures alter the male pheromonal blend, normally making it more attractive to females and this is considered the primary mechanism for the enhanced mating success. However, the male lures raspberry ketone and zingerone are known, across a diverse range of other organisms, to be involved in increasing energy metabolism. If this also occurs in Bactrocera, then this may represent an additional benefit to males as courtship is metabolically expensive and lure feeding may increase a fly's short-term energy. We tested this hypothesis by performing comparative RNA-seq analysis between zingerone-fed and unfed males of Bactrocera tryoni. We also carried out behavioural assays with zingerone- and cuelure-fed males to test whether they became more active. RNA-seq analysis revealed, in zingerone-fed flies, up-regulation of 3183 genes with homologues transcripts to those known to regulate intermale aggression, pheromone synthesis, mating and accessory gland proteins, along with significant enrichment of several energy metabolic pathways and gene ontology terms. Behavioural assays show significant increases in locomotor activity, weight reduction and successful mating after mounting; all direct/indirect measures of increased activity. These results suggest that feeding on lures leads to complex physiological changes, which result in more competitive males. These results do not negate the pheromone effect, but do strongly suggest that the phytochemical-induced sexual selection is governed by both female preference and male competitive mechanisms.

Competitive advantage through safety compliance : smaller firm responses to changes in the Australian occupational health and safety regulatory context

Smaller firms are often viewed as resistant to regulation due to cost burdens. However, evidence indicates that for some compliance is beneficial under certain conditions. Drawing on data on attitudes and responses of smaller firm owner-managers to changes in Australia’s harmonising work health and safety context we report on smaller firms’ responses to these changes. Despite uncertainty due to incomplete harmonisation, many owner-managers viewed safety compliance as important and necessary to do business. Those with negative views still linked positive safety performance to business outcomes. We categorise smaller firms’ responses and in this sample most are Positive Responders. We suggest ways forward for policy-makers to support smaller firms in complying with occupational health and safety regulation.

Competitive interactions of anti-carcinogens with serum albumin: A spectroscopic study of bendamustine and dexamethasone with the aid of chemometrics

Interactions between the anti-carcinogens, bendamustine (BDM) and dexamethasone (DXM), with bovine serum albumin (BSA) were investigated with the use of fluorescence and UV–vis spectroscopies under pseudo-physiological conditions (Tris–HCl buffer, pH 7.4). The static mechanism was responsible for the fluorescence quenching during the interactions; the binding formation constant of the BSA–BDM complex and the binding number were 5.14 × 105 L mol−1 and 1.0, respectively. Spectroscopic studies for the formation of BDM–BSA complex were interpreted with the use of multivariate curve resolution – alternating least squares (MCR–ALS), which supported the complex formation. The BSA samples treated with site markers (warfarin – site I and ibuprofen – site II) were reacted separately with BDM and DXM; while both anti-carcinogens bound to site I, the binding constants suggested that DXM formed a more stable complex. Relative concentration profiles and the fluorescence spectra associated with BDM, DXM and BSA, were recovered simultaneously from the full fluorescence excitation–emission data with the use of the parallel factor analysis (PARAFAC) method. The results confirmed that on addition of DXM to the BDM–BSA complex, the BDM was replaced and the DXM–BSA complex formed; free BDM was released. This finding may have consequences for the transport of these drugs during any anti-cancer treatment.

Treatment for gender dysphoria in children : the new legal, ethical and clinical landscape

- Gender dysphoria is a condition in which a child's subjectively felt identity and gender are not congruent with her or his biological sex. Because of this, the child suffers clinically significant distress or impairment in social functioning. - The Family Court of Australia has recently received an increasing number of applications seeking authorisation for the provision of hormones to treat gender dysphoria in children. - Some medical procedures and interventions performed on children are of such a grave nature that court authorisation must be obtained to render them lawful. These procedures are referred to as special medical procedures. - Hormonal therapy for the treatment of gender dysphoria in children is provided in two stages occurring years apart. Until recently, both stages of treatment were regarded by courts as special medical treatments, meaning court authorisation had to be provided for both stages. - In a significant recent development, courts have drawn a distinction between the two stages of treatment, permitting parents to consent to the first stage. In addition, it has been held that a child who is determined by a court to be Gillick competent can consent to stage 2 treatment. - The new legal developments concerning treatment for gender dysphoria are of ethical, clinical and practical importance to children and their families, and to medical practitioners treating children with gender dysphoria. Medical practitioners should benefit from an understanding of the recent developments in legal principles. This will ensure that they have up-to-date information about the circumstances under which treatment may be conducted with parental consent, and those in which they must seek court authorisation.

The competitive market for assurance engagements on greenhouse gas statements : is there a role for assurers from the accounting profession?

In response to current and increasing demand for assurance on greenhouse gas statements, the International Auditing and Assurance Standards Board (IAASB) released an exposure draft of a new assurance standard, ISAE 3410 'Assurance on a Greenhouse Gas Statement' (IFAC 2011), to provide comprehensive guidance on these types of greenhouse gas (GHG) assurance engagements. Internationally, approximately 50 percent of GHG statements are independently assured. The related assurance market is competitive, with the accounting profession and those outside the profession currently holding approximately equal shares. This paper highlights the characteristics of GHG assurance engagements that warrant multi-disciplinary teamwork, the unique and interdependent skill-sets that different practitioners bring to these engagements, and the market forces that create a demand for diverse providers.

Analysing governance of Australia's system of landscape-based greenhouse gas abatement

Healthy governance systems are key to delivering effective outcomes in any broad domain of natural resource management (NRM). One of Australia's emerging NRM governance domains is our national framework for greenhouse gas abatement (GGA), as delivered through a wide range of management practices in the Australian landscape. The emerging Landscape-Based GGA Domain represents an innovative governance space that straddles both the nation's broader NRM Policy and Delivery Domain and Australia's GGA Domain. As a point-in-time benchmark, we assess the health of this hybrid domain as it stood at the end of 2013. At that time, the domain was being progressed through the Australian government's Clean Energy Package and, more particularly, its Carbon Farming Initiative (CFI). While significant changes are currently under development by a new Australian government, this paper explores key areas of risk within the governance system underpinning this emerging hybrid domain at that point in time. We then map some potential reform or continuous improvement pathways required (from national to paddock scale) with the view to securing improved landscape outcomes over time through widespread GGA activities.

The first 25 years of the Queensland Rugby Football League: Claims to legitimacy in annual reports

Despite the cultural importance of sporting organisations, little academic attention has been paid to the legitimising role of their annual reports. In this paper we examine the role of annual reports in establishing the legitimacy of a new organisation, the Queensland Rugby Football League (QRFL), founded in 1908. Contextualised with media reports from newspapers of the day, twelve annual reports from QRFL’s first 25 years are analysed and interpreted using insights from legitimacy theory. Through the presentation of audited financial statements and persuasive narrative accounts of its operations and success, QRFL made claims to pragmatic, moral and cognitive legitimacy as it sought to establish a niche as a new football code and organisation. This contextualised study situates the annual reports in their historical landscape, providing insights about how they contributed to QRFL’s efforts in overcoming the liability of newness in a competitive sports environment.

The evolving landscape of natural resource planning and governance in Australia

Australia’s governance of land and natural resources involves multiple polycentric domains of decision-making from global through to local levels. Although certainly complex, these arrangements have not necessarily translated into better decision-making or better environmental outcomes as evidenced by the growing concerns over the health and future of the Great Barrier Reef, (GBR). However within this system, arrangements for natural resource management (NRM) and reef water quality, which both use Australia’s integrated regional NRM model, have showed signs of improving decision-making and environmental outcomes in the GBR. In this paper we describe the latest evolutions in the governance and planning for natural resource use and management in Australia. We begin by reviewing the experience with first generation NRM as published in major audits and evaluations. As our primary interest is the health and future of the GBR, we then consider the impact of changes of second generation planning and governance outcomes in Queensland. We find that first generation plans, although developed under a relatively cohesive governance context, faced substantial problems in target setting, implementation, monitoring and review. Despite this, they were able to progress improvements in water quality in the Great Barrier Reef Regions. Second generation plans, currently being developed, face an even greater risk of failure due to the lack of bilateralism and cross-sectoral cooperation across the NRM governance system. The findings highlight the critical need to re-build and enhance the regional NRM model for NRM planning to have a positive impact on environmental outcomes in the GBR.

Representing places never visited: Landscape and the diasporic imagination

While landscape photography’s complicity with the colonial possession of new territory has been substantially discussed and well understood, this paper considers the role of the European landscape as the focus of diasporic desire. The interdisciplinary project, S2Q/Good Blood began as a social history map of Scandinavian and Nordic migration to Queensland in the nineteenth century, incorporating archival material from local collections with visual field trip data gathered in Denmark, Sweden, Norway and Finland. In 2011, some of this material found its way into the installation work, 'my mother is water, my father is wood'. What emerged from this experiment was an imaginary landscape, melding its loci through original photography and video footage in tandem with stock imagery and historical material. This juxtaposition reinforced the represented landscape as a narrative landscape and evidence of the performativity of belonging. This practitioner reflection utilizes Lynette Russell’s research into landscape archaeology to consider the significance of relationships with landscapes that are “not always empirically demonstrable.”

Cultural policy and Australia's national cultural heritage: Issues and challenges in the GLAM landscape

In 2012 the Australian Commonwealth government was scheduled to release the first dedicated policy for culture and the arts since the Keating government's Creative Nation (1994). Investing in a Creative Australia was to appear after a lengthy period of consultation between the Commonwealth government and all interested cultural sectors and organisations. When it eventuates, the policy will be of particular interest to those information professionals working in the GLAM (galleries, libraries, archives and museums) environment. GLAM is a cross-institutional field which seeks to find points of commonality among various cultural-heritage institutions, while still recognising their points of difference. Digitisation, collaboration and convergence are key themes and characteristics of the GLAM sector and its associated theoretical discipline. The GLAM movement has seen many institutions seeking to work together to create networks of practice that are beneficial to the cultural-heritage industry and sector. With a new Australian cultural policy imminent, it is timely to reflect on the issues and challenges that GLAM principles present to national cultural-heritage institutions by discussing their current practices. In doing so, it is possible to suggest productive ways forward for these institutions which could then be supported at a policy level by the Commonwealth government. Specifically, this paper examines four institutions: the National Gallery of Australia, the National Library of Australia, the National Archives of Australia and the National Museum of Australia. The paper reflects on their responses to the Commonwealth's 2011 Cultural Policy Discussion Paper. It argues that by encouraging and supporting collecting institutions to participate more fully in GLAM practices the Commonwealth government's cultural policy would enable far greater public access to, and participation in, Australia's cultural heritage. Furthermore, by considering these four institutions, the paper presents a discussion of the challenges and the opportunities that GLAM theoretical and disciplinary principles present to the cultural-heritage sector. Implications for Best Practice * GLAM is a developing field of theory and practice that encompasses many issues and challenges for practitioners in this area. * GLAM principles and practices are increasingly influencing the cultural-heritage sector. * Cultural policy is a key element in shaping the future of Australia's cultural-heritage sector and needs to incorporate GLAM principles.