Experimental and theoretical studies of the redox potentials of cyclic nitroxides

The redox potentials of 25 cyclic nitroxides from four different structural classes (pyrrolidine, piperidine, isoindoline, and azaphenalene) were determined experimentally by cyclic voltammetry in acetonitrile, and also via high-level ab initio molecular orbital calculations. It is shown that the potentials are influenced by the type of ring system, ring substituents and/or groups surrounding the radical moiety. For the pyrrolidine, piperidine, and isoindolines there is excellent agreement (mean absolute deviation of 0.05 V) between the calculated and experimental oxidation potentials; for the azaphenalenes, however, there is an extraordinary discrepancy (mean absolute deviation of 0.60 V), implying that their one-electron oxidation might involve additional processes not considered in the theoretical calculations. This recently developed azaphenalene class of nitroxide represents a new variant of a nitroxide ring fused to an aromatic system and details of the synthesis of five derivatives involving differing aryl substitution are also presented.

A novel profluorescent dinitroxide for imaging polypropylene degradation

Free-radical processes underpin the thermo-oxidative degradation of polyolefins. Thus, to extend the lifetime of these polymers, stabilizers are generally added during processing to scavenge the free radicals formed as the polymer degrades. Nitroxide radical precursors, such as hindered amine stabilizers (HAS),1,2 are common polypropylene additives as the nitroxide moiety is a potent scavenger of polymer alkyl radicals (R¥). Oxidation of HAS by radicals formed during polypropylene degradation yields nitroxide radicals (RRNO¥), which rapidly trap the polymer degradation species to produce alkoxyamines, thus retarding oxidative polymer degradation. This increase in polymer stability is demonstrated by a lengthening of the “induction period” of the polymer (the time prior to a sharp rise in the oxidation of the polymer). Instrumental techniques such as chemiluminescence or infrared spectroscopy are somewhat limited in detecting changes in the polymer during the initial stages of degradation. Therefore, other methods for observing polymer degradation have been sought as the useful life of a polymer does not extend far beyond its “induction period”

Innovation

Innovation can be defined broadly to include the development and uptake of new technology, the introduction of new products, the utilisation of new market opportunities and the implementation of new business processes including new forms of work organisation or management structures and approaches. Innovation, or the commercial application of new knowledge, is of increasing importance to economic competitiveness given the growth in production and trade in high technology industries and knowledge intensive service sectors such as business services (Edquist, Hommen and McKelvey 2001). An important field of innovation in modern economies is associated with the rapid development and application of information and communications technologies (ICTs). ICTs constitute an increasing share of value added, growth and employment and also impact on employment and productivity in other industry sectors. The structural transformation of modern economies associated with ICTs has led to an increase in the importance of information and knowledge resources (rather than physical capital) as inputs or factors of production. Technology and product innovations are often given central attention in innovation research, however, organisational and managerial changes have been recognised as critical. Over the last two decades, understandings of the nature and process of innovation have advanced significantly. In the 1950s and 1960s, there was a view that innovation resulted from basic research, or in essence that scientific research acted as a 'push' for innovation. As such there was a great deal of emphasis on formal research and development, undertaken either by governments or research and development units within business organisations. Radical innovations involving new products and new technological trajectories were thought to derive from basic research (Freeman 1995).

Small Business and entrepreneurship policy

There are two key approaches to entrepreneurship, each of which has different implications for small business policy (Danson 2002). The first conceives of entrepreneurship as an economic process and can be traced to the work of Joseph Schumpeter who developed the concept of creative destruction to describe the entrepreneurial process that led to the simultaneous elimination of old industries and activities and the creation of new activities through the commercial application of new ideas. While entrepreneurship as a process of creative destruction might include start up activity amongst small firms, it does not exclusively involve small firms as large firms may contribute to the entrepreneurial process through the generation of new knowledge and by assisting in financing the development of new ideas amongst small firms. Although innovation occurs in large as well as small firms, the literature on small enterprise innovation draws heavily on Schumpeter’s depiction of the central role of the entrepreneur in the process of creative destruction, whereby the economic system is transformed from within and new cycles in economic life emerge in which new industries and markets replace old industries and markets. Schumpeter argued that entrepreneurs drove the process of innovation and that innovation was a stimulus to economic development and involved the development of new products, processes, methods of production or new forms of commercial or financial organisation (Schumpeter 1911). At a time when technological development and structuraleconomic change are occurring at a rapid pace, small firm innovation is seen to be critically important because empirical evidence, although not undisputed, indicates that SMEs make an important contribution to radical innovations in new industries (Nooteboom 1994). The second view of entrepreneurship focuses on the individual entrepreneur more than the entrepreneurial process. The entrepreneur is depicted as an owner of small businesses, and is regarded as having particular personal characteristics such as self-reliance, individual initiative and self-motivation. Entrepreneurs are also considered to have a behavioural orientation towards the exploitation of new ideas and opportunities. They are the risk takers who are able to see an opportunity and pursue it commercially despite the uncertainty of rewards. The capacity to plan, manage and lead is also seen to be identifying characteristics of entrepreneurs. Different small business policy approaches arise from these different perspectives on entrepreneurship. Small business policy approaches that emphasise the process by which new ideas are generated and applied commercially arise from the first and broader view of entrepreneurship. Policies designed to generate a population of risk taking and self-motivated individuals with highly developed management and commercial skills are more in keeping with the second approach, which is focused on the individual entrepreneur rather than the entrepreneurial process.

The encapsulation of gold nanoparticles using RAFT, ATRP and miniemulsion polymerisation techniques

The investigation into the encapsulation of gold nanoparticles (AuNPs) by poly(methyl methacrylate) (PMMA) was undertaken. This was performed by three polymerisation techniques including: grafting PMMA synthesised by reversible addition-fragmentation chain transfer (RAFT) polymerisation to AuNPs, grafting PMMA synthesised by atom transfer radical polymerisation (ATRP) from the surface of functionalised AuNPs and by encapsulation of AuNPs within PMMA latexes produced through photo-initiated oil-in-water (o/w) miniemulsion polymerisation. The grafting of RAFT PMMA to AuNPs was performed by the addition of the RAFT functionalised PMMA to citrate stabilised AuNPs. This was conducted with a range of PMMA of varying molecular weight distribution (MWD) as either the dithioester or thiol end-group functionalities. The RAFT PMMA polymers were characterised by gel permeation chromatography (GPC), ultraviolet-visible (UV-vis), Fourier transform infrared-attenuated total reflectance (FTIR-ATR), Fourier transform Raman (FT-Raman) and proton nuclear magnetic resonance (1H NMR) spectroscopies. The attachment of PMMA to AuNPs showed a tendency for AuNPs to associate with the PMMA structures formed, though significant aggregation occurred. Interestingly, thiol functionalised end-group PMMA showed very little aggregation of AuNPs. The spherical polymer-AuNP structures did not vary in size with variations in PMMA MWD. The PMMA-AuNP structures were characterised using scanning electron microscopy (SEM), transition electron microscopy (TEM), energy dispersive X-ray analysis (EDAX) and UV-vis spectroscopy. The surface confined ATRP grafting of PMMA from initiator functionalised AuNPs was polymerised in both homogeneous and heterogeneous media. 11,11’- dithiobis[1-(2-bromo-2-methylpropionyloxy)undecane] (DSBr) was used as the surface-confined initiator and was synthesised in a three step procedure from mercaptoundecanol (MUD). All compounds were characterised by 1H NMR, FTIR-ATR and Raman spectroscopies. The grafting in homogeneous media resulted in amorphous PMMA with significant AuNP aggregation. Individually grafted AuNPs were difficult to separate and characterise, though SEM, TEM, EDAX and UV-vis spectroscopy was used. The heterogeneous polymerisation did not produce grafted AuNPs as characterised by SEM and EDAX. The encapsulation of AuNPs within PMMA latexes through the process of photoinitiated miniemulsion polymerisation was successfully achieved. Initially, photoinitiated miniemulsion polymerisation was conducted as a viable low temperature method of miniemulsion initiation. This proved successful producing a stable PMMA with good conversion efficiency and narrow particle size distribution (PSD). This is the first report of such a system. The photo-initiated technique was further optimised and AuNPs were included into the miniemulsion. AuNP encapsulation was very effective, producing reproducible AuNP encapsulated PMMA latexes. Again, this is the first reported case of this. The latexes were characterised by TEM, SEM, GPC, gravimetric analysis and dynamic light scattering (DLS).

Reading the environment : narrative constructions of ecological subjectivities in Australian children's literature

Ways in which humans engage with the environment have always provided a rich source of material for writers and illustrators of Australian children's literature. Currently, readers are confronted with a multiplicity of complex, competing and/or complementing networks of ideas, theories and emotions that provide narratives about human engagement with the environment at a particular historical moment. This study, entitled Reading the Environment: Narrative Constructions of Ecological Subjectivities in Australian Children's Literature, examines how a representative sample of Australian texts (19 picture books and 4 novels for children and young adults published between 1995 and 2006) constructs fictional ecological subjects in the texts, and offers readers ecological subject positions inscribed with contemporary environmental ideologies. The conceptual framework developed in this study identifies three ideologically grounded positions that humans may assume when engaging with the environment. None of these positions clearly exists independently of any other, nor are they internally homogeneous. Nevertheless they can be categorised as: (i) human dominion over the environment with little regard for environmental degradation (unrestrained anthropocentrism); (ii) human consideration for the environment driven by understandings that humans need the environment to survive (restrained anthropocentrism); and (iii) human deference towards the environment guided by understandings that humans are no more important than the environment (ecocentrism). iv The transdisciplinary methodological approach to textual analysis used in this thesis draws on ecocriticism, narrative theories, visual semiotics, ecofeminism and postcolonialism to discuss the difficulties and contradictions in the construction of the positions offered. Each chapter of textual analysis focuses on the construction of subjectivities in relation to one of the positions identified in the conceptual framework. Chapter 5 is concerned with how texts highlight the negative consequences of human dominion over the environment, or, in the words of this study, living with ecocatastrophe. Chapter 6 examines representations of restrained anthropocentrism in its contemporary form, that is, sustainability. Chapter 7 examines representations of ecocentrism, a radical position with inherent difficulties of representation. According to the analysis undertaken, the focus texts convey the subtleties and complexities of human engagement with the environment and advocate ways of viewing and responding to contemporary unease about the environment. The study concludes that these ways of viewing and responding conform to and/or challenge dominant socio-cultural and political-economic opinions regarding the environment. This study, the first extended work of its kind, makes an original contribution to ecocritical study of Australian children's literature. By undertaking a comprehensive analysis of how texts for children represent human engagement with the environment at a time when important environmental concerns pose significant threats to human existence, I hope to contribute new knowledge to an area of children's literature research that to date has been significantly under-represented.

Exploration and exploitation : the interplay between knowledge and continuous innovation

In rapidly changing environments, organisations require dynamic capabilities to integrate, build and reconfigure resources and competencies to achieve continuous innovation. Although tangible resources are important to promoting the firm’s ability to act, capabilities fundamentally rest in the knowledge created and accumulated by the firm through human capital, organisational routines, processes, practices and norms. The exploration for new ideas, technologies and knowledge – to one side – and – on the other one – the exploitation of existing and new knowledge is essential for continuous innovation. Firms need to decide how best to allocate their scarce resources for both activities and at the same time build dynamic capabilities to keep up with changing market conditions. This in turn, is influenced by the absorptive capacity of the firm to assimilate knowledge. This paper presents a case study that investigates the sources of knowledge in an engineering firm in Australia, and how it is organised and processed. As information pervades the firm from both internal and external sources, individuals integrate knowledge using both exploration and exploitation approaches. The findings illustrate that absorptive capacity can encourage greater leverage for exploration potential leading to radical innovation; and reconfiguring exploitable knowledge for incremental improvements. This study provides an insight for managers in quest of improving knowledge strategies and continuous innovation. It also makes significant theoretical contributions to the literature through extending the concepts of

Challenging cohesion

Cohesion as a term connotes attraction, unity, and commonness amongst discrete entities. Considering cohesion as a concept is timely with the recent rise of network culture, which comes with both subtle and radical changes in how people connect with, position themselves in relation to, and understand other constituents of society (cf. Varnelis; Castells; Jenkins et al.). Such dis- and inter-connections signify an imminent and immanent epistemological challenge we must confront: how can we understand inherently multi-faceted subjects, components of which are in constant transformation? For researchers, disciplinary complexity is one of the main implications of this situation. While disciplinary integration may be an effective or vital component in pursuit of knowledge (cf. Nicolescu) it may also impart significant conceptual and pragmatic conflicts. What are possible ways to coalesce multiple dimensions of reality that can lead to conceptually cohesive and useful knowledge production? This issue of M/C Journal attempts to answer this question by looking at different perspectives on the notion of cohesion across topical and disciplinary boundaries.

Crossing the language and cultural divide : the challenges of educating Asian law students in a globalising world

In 2004, there were sweeping, radical changes made to the underlying legal framework regulating life in China. This reflected such things as the incorporation of basic international human rights standards into domestic law - not only in China but in countries worldwide which highlights the increasingly global nature of many important legal issues. China is not immune from this development of cross pollination of legal processes. This has led to an increase in the internationalisation of legal education and the rapid rise in the number of overseas students who undertake at least part of their university studies in a foreign country. Academics need to develop cross-cultural sensitivity in teaching these overseas students; there are important reasons why the educative process needs to meet the different set of needs presented by international students who come to study in Australia. This teaching note sets out the experiences of two particular situations, the teaching of Business Law to Asian students and an innovative Australian postgraduate program taught in Mandarin.

Studies of the radiation chemistry and grafting of a fluoropolymer

The radiation chemistry and the grafting of a fluoropolymer, poly(tetrafluoroethylene-coperfluoropropyl vinyl ether) (PFA), was investigated with the aim of developing a highly stable grafted support for use in solid phase organic chemistry (SPOC). A radiation-induced grafting method was used whereby the PFA was exposed to ionizing radiation to form free radicals capable of initiating graft copolymerization of styrene. To fully investigate this process, both the radiation chemistry of PFA and the grafting of styrene to PFA were examined. Radiation alone was found to have a detrimental effect on PFA when irradiated at 303 K. This was evident from the loss in the mechanical properties due to chain scission reactions. This meant that when radiation was used for the grafting reactions, the total radiation dose needed to be kept as low as possible. The radicals produced when PFA was exposed to radiation were examined using electron spin resonance spectroscopy. Both main-chain (–CF2–C.F–CF2-) and end-chain (–CF2–C.F2) radicals were identified. The stability of the majority of the main-chain radicals when the polymer was heated above the glass transition temperature suggested that they were present mainly in the crystalline regions of the polymer, while the end-chain radicals were predominately located in the amorphous regions. The radical yield at 77 K was lower than the radical yield at 303 K suggesting that cage recombination at low temperatures inhibited free radicals from stabilizing. High-speed MAS 19F NMR was used to identify the non-volatile products after irradiation of PFA over a wide temperature range. The major products observed over the irradiation temperature 303 to 633 K included new saturated chain ends, short fluoromethyl side chains in both the amorphous and crystalline regions, and long branch points. The proportion of the radiolytic products shifted from mainly chain scission products at low irradiation temperatures to extensive branching at higher irradiation temperatures. Calculations of G values revealed that net crosslinking only occurred when PFA was irradiated in the melt. Minor products after irradiation at elevated temperatures included internal and terminal double bonds and CF3 groups adjacent to double bonds. The volatile products after irradiation at 303 K included tetrafluoromethane (CF4) and oxygen-containing species from loss of the perfluoropropyl ether side chains of PFA as identified by mass spectrometry and FTIR spectroscopy. The chemical changes induced by radiation exposure were accompanied by changes in the thermal properties of the polymer. Changes in the crystallinity and thermal stability of PFA after irradiation were examined using DSC and TGA techniques. The equilibrium melting temperature of untreated PFA was 599 K as determined using a method of extrapolation of the melting temperatures of imperfectly formed crystals. After low temperature irradiation, radiation- induced crystallization was prevalent due to scission of strained tie molecules, loss of perfluoropropyl ether side chains, and lowering of the molecular weight which promoted chain alignment and hence higher crystallinity. After irradiation at high temperatures, the presence of short and long branches hindered crystallization, lowering the overall crystallinity. The thermal stability of the PFA decreased with increasing radiation dose and temperature due to the introduction of defect groups. Styrene was graft copolymerized to PFA using -radiation as the initiation source with the aim of preparing a graft copolymer suitable as a support for SPOC. Various grafting conditions were studied, such as the total dose, dose rate, solvent effects and addition of nitroxides to create “living” graft chains. The effect of dose rate was examined when grafting styrene vapour to PFA using the simultaneous grafting method. The initial rate of grafting was found to be independent of the dose rate which implied that the reaction was diffusion controlled. When the styrene was dissolved in various solvents for the grafting reaction, the graft yield was strongly dependent of the type and concentration of the solvent used. The greatest graft yield was observed when the solvent swelled the grafted layers and the substrate. Microprobe Raman spectroscopy was used to map the penetration of the graft into the substrate. The grafted layer was found to contain both poly(styrene) (PS) and PFA and became thicker with increasing radiation dose and graft yield which showed that grafting began at the surface and progressively penetrated the substrate as the grafted layer was swollen. The molecular weight of the grafted PS was estimated by measuring the molecular weight of the non-covalently bonded homopolymer formed in the grafted layers using SEC. The molecular weight of the occluded homopolymer was an order of magnitude greater than the free homopolymer formed in the surrounding solution suggesting that the high viscosity in the grafted regions led to long PS grafts. When a nitroxide mediated free radical polymerization was used, grafting occurred within the substrate and not on the surface due to diffusion of styrene into the substrate at the high temperatures needed for the reaction to proceed. Loading tests were used to measure the capacity of the PS graft to be functionialized with aminomethyl groups then further derivatized. These loading tests showed that samples grafted in a solution of styrene and methanol had superior loading capacity over samples graft using other solvents due to the shallow penetration and hence better accessibility of the graft when methanol was used as a solvent.

An ESR study of irradiated poly(tetrafluoroethylene-co-perfluoropropyl vinyl ether) (PFA)

Poly(tetrafluoroethylene-co-perfluoropropyl vinyl ether) (PFA) with 2 mol% perfluoropropyl vinyl ether (PPVE) was exposed to γ-irradiation in vacuum at both 77 K and room temperature and the ESR spectra recorded. Both the main chain, CF2–C.F–CF2, and end chain, CF2C.F2 radicals were identified at both temperatures and their thermal stabilities measured. No radicals unique to the radiolytic cleavage at the PPVE units were observed at room temperature, either due to the low concentration of the comonomer or β-scission to form a chain end radical and a non-radical species. G-values for radical formation at room temperature and 77 K were found to be 0.93 and 0.16, respectively.

A naturalistic inquiry of registered nurses' perspectives and expectations of psychodynamic therapeutic care in acute psychiatric inpatient facilities

Within contemporary inpatient mental health nursing practice, the psychodynamic model of care considered previously to be central to the nurse-patient relationship now seems a radical concept. It appears to exist only within primary care facilities and public health care practice settings. This naturalistic inquiry aimed to explicate mental health nurses' perspectives and expectations of providing psychodynamic therapeutic care in acute inpatient psychiatric facilities. Ten registered nurses working in acute inpatient mental health facilities were interviewed. Five themes emerged: a career for life, relating in a psychodynamic manner, swimming against the current, adopting a position of difference, and hopeful expectancy.

Effect of poly(acrylic acid) end-group functionality on inhibition of calcium oxalate crystal growth

A number of series of poly(acrylic acids) (PAA) of differing end-groups and molecular weights prepared using atom transfer radical polymerization were used as inhibitors for the crystallization of calcium oxalate at 23 and 80°C. As measured by turbidimetry and conductivity and as expected from previous reports, all PAA series were most effective for inhibition of crystallization at molecular weights of 1500–4000. However, the extent of inhibition was in general strongly dependent on the hydrophobicity and molecular weight of the end-group. These results may be explicable in terms of adsorption/desorption of PAA to growth sites on crystallites. The overall effectiveness of the series didn't follow a simple trend with end-group hydrophobicity, suggesting self-assembly behavior or a balance between adsorption and desorption rates to crystallite surfaces may be critical in the mechanism of inhibition of calcium oxalate crystallization.