One-Electron Reduction of 2-Nitrotoluene, Nitrocyclopentane, and 1-Nitrobutane in Room Temperature Ionic Liquids: A Comparative Study of Butler–Volmer and Symmetric Marcus–Hush Theories Using Microdisk Electrodes

The voltammetry for the reduction of 2-nitrotoluene at a gold microdisk electrode is reported in two ionic liquids: trihexyltetradecylphosphonium tris(pentafluoroethyl)trifluorophosphate ([P-14,P-6,P-6,P-6][FAP]) and 1-ethyl-3-methylimidazolium bis[(trifluoromethyl)sulfonyl]imide ([Emim][NTf2]). The reduction of nitrocyclopentane (NCP) and 1-nitrobutane (BuN) was investigated using voltammetry at a gold microdisk electrode in the ionic liquid [P-14,P-6,P-6,P-6][FAP]. Simulated voltammograms, generated through the use of ButlerVolmer theory and symmetric MarcusHush theory, were compared to experimental data, with both theories parametrizing the data similarly well. An experimental value for the Marcusian parameter, 1 was also determined in all cases. For the reduction of 2-nitrotoluene, this was 0.5 +/- 0.1 eV in both solvents, while for NCP and BuN in [P-14,P-6,P-6,P-6][FAP], it was 2 +/- 0.1 and 5 +/- 0.1 eV, respectively. This is attributed to the localization of charge on the nitro group and the primary nitro alkyls increased interaction with the environment, resulting in a larger reorganization energy.

Application of Asymmetric Marcus-Hush Theory to Voltammetry in Room-Temperature Ionic Liquids

Asymmetric MarcusHush (AMH) theory is applied for the first time in ionic solvents to model the voltammetric reduction of oxygen in 1-butyl-1-methylpyrrolidinium bis-(trifluoromethylsulfonyl)-imide and of 2-nitrotoluene (2-NT), nitrocyclopentane (NCP), and 1-nitro-butane (BuN) in trihexyltetradecylphosphonium tris(pentafluoroethyl)trifluorophosphate on a gold microdisc electrode. An asymmetry parameter, gamma, was estimated for all systems as -0.4 for the reduction of oxygen and -0.05, 0.25, and 0 +/- 0.05 for the reductions of 2-NT, NCP, and BuN, respectively, which suggests equal force constants of reactants and products in the case of 2-NT and BuN and unequal force constants for oxygen and NCP where the force constants of the oxidized species are greater than the reduced species in the case of oxygen and less than the reduced species in the case of NCP. Previously measured values for a, the Butler-Volmer transfer coefficient, reflect this in each case. Where appreciable asymmetry occurs, AMH theory was seen to parametrize the experimental data better than either Butler-Volmer or symmetric Marcus-Hush theory, allowing additionally the extraction of reorganization energy. This is the first study to provide key physical insights into electrochemical systems in room-temperature ionic liquids using AMH theory, allowing elucidation of the reorganization energies and the relative force constants of the reactants and products in each reaction.

Double potential step chronoamperometry at microdisk electrodes: simulating the case of unequal diffusion coefficients

An efficient approach to the simulation of the double potential step chronoamperometry at a microdisk electrode based on an exponentially expanding time grid and conformal mapping of the space is presented. The dimensionless second potential step flux data are included as a function of the first potential step duration and the ratio of the diffusion coefficients of the reacting species allowing instant analysis of the experimental double potential step chronoamperograms without a need for simulation. The values of the diffusion coefficients are determined for several test systems and found to be in good agreement with existing literature data. (C) 2004 Elsevier B.V. All rights reserved.

Towards a cohesive, holistic view of top predation: a definition, synthesis and perspective

Research on the ecology of top predators - upper trophic level consumers that are relatively free from predation once they reach adult size - has provided regular contributions to general ecology and is a rapidly expanding and increasingly experimental, multidisciplinary and technological endeavour. Yet, an exponentially expanding literature coupled with rapid disintegration into specialized, disconnected subfields for study (e.g. vertebrate predators versus invertebrate predators, community ecology versus biological control etc.) increasingly means that we are losing a coherent, integrated understating of the role and importance of these species in ecosystems. This process of canalization is likely to hinder sharing of scientific discovery and continued progress, especially as there is a growing need to understand the generality of the top-down forcing, as demonstrated for some members of this group. Here, we propose ways to facilitate synthesis by promoting changes in mentality and awareness among specialists through increased debate and collaboration, conceptual reviews and a series of exemplary case studies. The strategy will rely on the collective contribution by all scientists in the field and will strive to consolidate and formalise top-order predation as a holistic, cohesive, cross-taxonomical field of research studying the ecology, evolution and behaviour of apex predators and their capability to exert top-down forcing on lower trophic levels. © 2014 The Authors.

Ion trap simulations of quantum fields in an expanding universe

We propose an experiment in which the phonon excitation of ion(s) in a trap, with a trap frequency exponentially modulated at rate kappa, exhibits a thermal spectrum with an Unruh temperature given by k(B)T=h kappa. We discuss the similarities of this experiment to the response of detectors in a de Sitter universe and the usual Unruh effect for uniformly accelerated detectors. We demonstrate a new Unruh effect for detectors that respond to antinormally ordered moments using the ion's first blue sideband transition.

The MESH book : landscape / infrastructure

Resulting from a series of student-run 'Edge' conferences that have been held in Australia and New Zealand (beginning at RMIT in 1983), The Mesh Book is a collection of essays grouped into themes of Invisible Infrastructures (systems of belief), Immanent Infrastructures (natural systems) and Present Infrastructures (roads and services). Ranging from esoteric discussions to analytical case studies, the book assembles a broad spectrum of ideas on the landscape within the context of Australia and a contemporary study of place.

Taking a 'reality' check : expanding pre-service teachers' views on pedagogy and diversity

The outcomes of a two-pronged 'real-world' learning project, which aimed to expand the views of pre-service teachers about learning, pedagogy and diversity, will be discussed in this paper. Seventy-two fourth-year and 22 first-year students, enrolled in a Bachelor of Education degree in Queensland, Australia, were engaged in community sites outside of university lectures, and separate from their practicum. Using Butin's conceptual framework for service learning, we show evidence that this approach can enable pre-service teachers to see new realities about the dilemmas and ambiguities of performing as learners and as teachers. We contend that when such 'real-world' experiences have different foci at different times in their four-year degree, pre-service teachers have more opportunities to develop sophisticated understandings of pedagogy in diverse contexts for diverse learners.

Gateways placement in backbone wireless mesh networks

This paper presents a novel algorithm for the gateway placement problem in Backbone Wireless Mesh Networks (BWMNs). Different from existing algorithms, the new algorithm incrementally identifies gateways and assigns mesh routers to identified gateways. The new algorithm can guarantee to find a feasible gateway placement satisfying Quality-of-Service (QoS) constraints, including delay constraint, relay load constraint and gateway capacity constraint. Experimental results show that its performance is as good as that of the best of existing algorithms for the gateway placement problem. But, the new algorithm can be used for BWMNs that do not form one connected component, and it is easy to implement and use.

Printmaking as an expanding field in contemporary art practice : a case study of Japan, Australia and Thailand

This thesis proposes that contemporary printmaking, at its most significant, marks the present through reconstructing pasts and anticipating futures. It argues this through examples in the field, occurring in contexts beyond the Euramerican (Europe and North America). The arguments revolve around how the practice of a number of significant artists in Japan, Australia and Thailand has generated conceptual and formal innovations in printmaking that transcend local histories and conventions, whilst paradoxically, also building upon them and creating new meanings. The arguments do not portray the relations between contemporary and traditional art as necessarily antagonistic but rather, as productively dialectical. Furthermore, the case studies demonstrate that, in the 1980s and 1990s particularly, the studio practice of these printmakers was informed by other visual arts disciplines and reflected postmodern concerns. Departures from convention witnessed in these countries within the Asia-Pacific region shifted the field of the print into a heterogeneous and hybrid realm. The practitioners concerned (especially in Thailand) produced work that was more readily equated with performance and installation art than with printmaking per se. In Japan, the incursion of photography interrupted the decorative cast of printmaking and delivered it from a straightforward, craft-based aesthetic. In Australia, fixed notions of national identity were challenged by print practitioners through deliberate cultural rapprochements and technical contradictions (speaking across old and new languages).However time-honoured print methods were not jettisoned by any case study artists. Their re-alignment of the fundamental attributes of printmaking, in line with materialist formalism, is a core consideration of my arguments. The artists selected for in-depth analysis from these three countries are all innovators whose geographical circumstances and creative praxis drew on local traditions whilst absorbing international trends. In their radical revisionism, they acknowledged the specificity of history and place, conditions of contingency and forces of globalisation. The transformational nature of their work during the late twentieth century connects it to the postmodern ethos and to a broader artistic and cultural nexus than has hitherto been recognised in literature on the print. Emerging from former guild-based practices, they ambitiously conceived their work to be part of a continually evolving visual arts vocabulary. I argue in this thesis that artists from the Asia-Pacific region have historically broken with the hermetic and Euramerican focus that has generally characterised the field. Inadequate documentation and access to print activity outside the dominant centres of critical discourse imply that readings of postmodernism have been too limited in their scope of inquiry. Other locations offer complexities of artistic practice where re-alignments of customary boundaries are often the norm. By addressing innovative activity in Japan, Australia and Thailand, this thesis exposes the need for a more inclusive theoretical framework and wider global reach than currently exists for ‘printmaking’.

Fusing shrinking and expanding active contour models for robust IRIS segmentation

The performance of iris recognition systems is significantly affected by the segmentation accuracy, especially in non- ideal iris images. This paper proposes an improved method to localise non-circular iris images quickly and accurately. Shrinking and expanding active contour methods are consolidated when localising inner and outer iris boundaries. First, the pupil region is roughly estimated based on histogram thresholding and morphological operations. There- after, a shrinking active contour model is used to precisely locate the inner iris boundary. Finally, the estimated inner iris boundary is used as an initial contour for an expanding active contour scheme to find the outer iris boundary. The proposed scheme is robust in finding exact the iris boundaries of non-circular and off-angle irises. In addition, occlusions of the iris images from eyelids and eyelashes are automatically excluded from the detected iris region. Experimental results on CASIA v3.0 iris databases indicate the accuracy of proposed technique.

A point interpolation method with locally smoothed strain field (PIM-LS2) for mechanics problems using triangular mesh

A point interpolation method with locally smoothed strain field (PIM-LS2) is developed for mechanics problems using a triangular background mesh. In the PIM-LS2, the strain within each sub-cell of a nodal domain is assumed to be the average strain over the adjacent sub-cells of the neighboring element sharing the same field node. We prove theoretically that the energy norm of the smoothed strain field in PIM-LS2 is equivalent to that of the compatible strain field, and then prove that the solution of the PIM- LS2 converges to the exact solution of the original strong form. Furthermore, the softening effects of PIM-LS2 to system and the effects of the number of sub-cells that participated in the smoothing operation on the convergence of PIM-LS2 are investigated. Intensive numerical studies verify the convergence, softening effects and bound properties of the PIM-LS2, and show that the very ‘‘tight’’ lower and upper bound solutions can be obtained using PIM-LS2.

Expanding ethical vistas of IT professionals

In this paper we argue for an experientially grounded view of IT professionals’ ethical formation and support. We propose that for such formation and support to be effectual, it should challenge professionals’ conceptualisations of their field and of ethics, and it should do so with the aim of changing their experience. To this end, we present a Model of Ethical IT, which is based on an examination of the nature of ethics and on empirical findings concerning IT professionals’ experience of ethics. We argue that for IT professionals to be enabled to become more ethical in their practice: the purpose of IT must be primarily understood to be user-oriented; the nature of professional ethics must be primarily understood to be other-centred; and the goal of ethics education must be understood as primarily promoting a change in awareness.

The expanding roles of the ghrelin-gene derived peptide obestatin in health and disease

Obestatin is a 23 amino acid, ghrelin gene-derived peptide hormone produced in the stomach and a range of other tissues throughout the body. While it was initially reported that obestatin opposed the actions of ghrelin with regards to appetite and food intake, it is now clear that obestatin is not an endogenous ghrelin antagonist of ghrelin, but it is a multi-functional peptide hormone in its own right. In this review we will discuss the controversies associated with the discovery of obestatin and explore emerging central and peripheral roles of obestatin, roles in adipogenesis, pancreatic homeostasis and cancer.