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.

Three Carrier Ambiguity Resolutions : Generalised problems, models and solutions

In this paper, the problems of three carrier phase ambiguity resolution (TCAR) and position estimation (PE) are generalized as real time GNSS data processing problems for a continuously observing network on large scale. In order to describe these problems, a general linear equation system is presented to uniform various geometry-free, geometry-based and geometry-constrained TCAR models, along with state transition questions between observation times. With this general formulation, generalized TCAR solutions are given to cover different real time GNSS data processing scenarios, and various simplified integer solutions, such as geometry-free rounding and geometry-based LAMBDA solutions with single and multiple-epoch measurements. In fact, various ambiguity resolution (AR) solutions differ in the floating ambiguity estimation and integer ambiguity search processes, but their theoretical equivalence remains under the same observational systems models and statistical assumptions. TCAR performance benefits as outlined from the data analyses in some recent literatures are reviewed, showing profound implications for the future GNSS development from both technology and application perspectives.

Theoretical critique of the work of art : co-producers in research

The ways in which the "traditional" tension between words and artwork can be perceived has huge implications for understanding the relationship between critical or theoretical interpretation, art and practice, and research. Within the practice-led PhD this can generate a strange sense of disjuncture for the artist-researcher particularly when engaged in writing the exegesis. This paper aims to explore this tension through an introductory investigation of the work of the philosopher Andrew Benjamin. For Benjamin criticism completes the work of art. Criticism is, with the artwork, at the centre of our experience and theoretical understanding of art – in this way the work of art and criticism are co-productive. The reality of this co-productivity can be seen in three related articles on the work of American painter Marcia Hafif. In each of these articles there are critical negotiations of just how the work of art operates as art and theoretically, within the field of art. This focus has important ramifications for the writing and reading of the exegesis within the practice-led research higher degree. By including art as a significant part of the research reporting process the artist-researcher is also staking a claim as to the critical value of their work. Rather than resisting the tension between word and artwork the practice-led artist-researcher need to embrace the co-productive nature of critical word and creative work to more completely articulate their practice and its significance as research. The ideal venue and opportunity for this is the exegesis.

Theoretical investigation of mechanisms of formation and interaction of nanoparticles

In this thesis an investigation into theoretical models for formation and interaction of nanoparticles is presented. The work presented includes a literature review of current models followed by a series of five chapters of original research. This thesis has been submitted in partial fulfilment of the requirements for the degree of doctor of philosophy by publication and therefore each of the five chapters consist of a peer-reviewed journal article. The thesis is then concluded with a discussion of what has been achieved during the PhD candidature, the potential applications for this research and ways in which the research could be extended in the future. In this thesis we explore stochastic models pertaining to the interaction and evolution mechanisms of nanoparticles. In particular, we explore in depth the stochastic evaporation of molecules due to thermal activation and its ultimate effect on nanoparticles sizes and concentrations. Secondly, we analyse the thermal vibrations of nanoparticles suspended in a fluid and subject to standing oscillating drag forces (as would occur in a standing sound wave) and finally on lattice surfaces in the presence of high heat gradients. We have described in this thesis a number of new models for the description of multicompartment networks joined by a multiple, stochastically evaporating, links. The primary motivation for this work is in the description of thermal fragmentation in which multiple molecules holding parts of a carbonaceous nanoparticle may evaporate. Ultimately, these models predict the rate at which the network or aggregate fragments into smaller networks/aggregates and with what aggregate size distribution. The models are highly analytic and describe the fragmentation of a link holding multiple bonds using Markov processes that best describe different physical situations and these processes have been analysed using a number of mathematical methods. The fragmentation of the network/aggregate is then predicted using combinatorial arguments. Whilst there is some scepticism in the scientific community pertaining to the proposed mechanism of thermal fragmentation,we have presented compelling evidence in this thesis supporting the currently proposed mechanism and shown that our models can accurately match experimental results. This was achieved using a realistic simulation of the fragmentation of the fractal carbonaceous aggregate structure using our models. Furthermore, in this thesis a method of manipulation using acoustic standing waves is investigated. In our investigation we analysed the effect of frequency and particle size on the ability for the particle to be manipulated by means of a standing acoustic wave. In our results, we report the existence of a critical frequency for a particular particle size. This frequency is inversely proportional to the Stokes time of the particle in the fluid. We also find that for large frequencies the subtle Brownian motion of even larger particles plays a significant role in the efficacy of the manipulation. This is due to the decreasing size of the boundary layer between acoustic nodes. Our model utilises a multiple time scale approach to calculating the long term effects of the standing acoustic field on the particles that are interacting with the sound. These effects are then combined with the effects of Brownian motion in order to obtain a complete mathematical description of the particle dynamics in such acoustic fields. Finally, in this thesis, we develop a numerical routine for the description of "thermal tweezers". Currently, the technique of thermal tweezers is predominantly theoretical however there has been a handful of successful experiments which demonstrate the effect it practise. Thermal tweezers is the name given to the way in which particles can be easily manipulated on a lattice surface by careful selection of a heat distribution over the surface. Typically, the theoretical simulations of the effect can be rather time consuming with supercomputer facilities processing data over days or even weeks. Our alternative numerical method for the simulation of particle distributions pertaining to the thermal tweezers effect use the Fokker-Planck equation to derive a quick numerical method for the calculation of the effective diffusion constant as a result of the lattice and the temperature. We then use this diffusion constant and solve the diffusion equation numerically using the finite volume method. This saves the algorithm from calculating many individual particle trajectories since it is describes the flow of the probability distribution of particles in a continuous manner. The alternative method that is outlined in this thesis can produce a larger quantity of accurate results on a household PC in a matter of hours which is much better than was previously achieveable.

Faith's knowledge : papers exploring the theory and application of theological epistemology

This thesis locates the origins of modern secular knowledge in late medieval theology. Problems with modern and postmodern knowledge which arise from these theological origins are then tackled theologically, and the manner in which secular ways of understanding knowledge are embedded in specific university, political and hospital contexts are then described and evaluated from a post-secular theological standpoint. The theoretical component of this thesis looks at knowledge itself and finds that without faith there can be no knowledge. The applied component of this thesis does two things. Firstly it explores how our conception of knowledge shapes the assumptions, operational norms, belief frames and tacit values of some characteristically modern and secular institutions. Secondly the applied component evaluates those contexts from the theologically premised conception of knowledge which was argued for in the theoretical component of this thesis.

Political theory and theoretical physics

This paper explains, somewhat along a Simmelian line, that political theory may produce practical and universal theories like those developed in theoretical physics. The reasoning behind this paper is to show that the Element of Democracy Theory may be true by way of comparing it to Einstein’s Special Relativity – specifically concerning the parameters of symmetry, unification, simplicity, and utility. These parameters are what make a theory in physics as meeting them not only fits with current knowledge, but also produces paths towards testing (application). As the Element of Democracy Theory meets these same parameters, it could settle the debate concerning the definition of democracy. This will be shown firstly by discussing why no one has yet achieved a universal definition of democracy; secondly by explaining the parameters chosen (as in why these and not others confirm or scuttle theories); and thirdly by comparing how Special Relativity and the Element of Democracy match the parameters.

Political theory and theoretical physics [Revised]

This paper explains, somewhat along a Simmelian line, that political theory may produce practical and universal theories like those developed in theoretical physics. The reasoning behind this paper is to show that the Element of Democracy Theory may be true by way of comparing it to Einstein’s Special Relativity – specifically concerning the parameters of symmetry, unification, simplicity, and utility. These parameters are what make a theory in physics as meeting them not only fits with current knowledge, but also produces paths towards testing (application). As the Element of Democracy Theory meets these same parameters, it could settle the debate concerning the definition of democracy. This will be shown firstly by discussing why no one has yet achieved a universal definition of democracy; secondly by explaining the parameters chosen (as in why these and not others confirm or scuttle theories); and thirdly by comparing how Special Relativity and the Element of Democracy match the parameters.

Small firm growth

We review and discuss the literature on small firm growth with an intention to provide a useful vantage point for new research studies regarding this important phenomenon. We first discuss conceptual and methodological issues that represent critical choices for those who research growth and which make it challenging to compare results from previous studies. The substantial review of past research is organized into four sections representing two smaller and two larger literatures. The first of the latter focuses on internal and external drivers of small firm growth. Here we find that much has been learnt and that many valuable generalizations can be made. However, we also conclude that more research of the same kind is unlikely to yield much. While interactive and non-linear effects may be worth pursuing it is unlikely that any new and important growth drivers or strong, linear main effects would be found. The second large literature deals with organizational life-cycles or stages of development. While deservedly criticized for unwarranted determinism and weak empirics this type of approach addresses problems of high practical and also theoretical relevance, and should not be shunned by researchers. We argue that with a change in the fundamental assumptions and improved empirical design, research on the organizational and managerial consequences of growth is an important line of inquiry. With this, we overlap with one of the smaller literatures, namely studies focusing on the effects of growth. We argue that studies too often assume that growth equals success. We advocate instead the use of growth as an intermediary variable that influences more fundamental goals in ways that should be carefully examined rather than assumed. The second small literature distinguishes between different modes or forms of growth, including, e.g., organic vs. acquisition-based growth, and international expansion. We note that modes of growth is an important topic that has been under studied in the growth literature, whereas in other branches of research aspects of it may have been studied intensely, but not primarily from a growth perspective. In the final section we elaborate on ways forward for research on small firm growth. We point at rich opportunities for researchers who look beyond drivers of growth, where growth is viewed as a homogenous phenomenon assumed to unambiguously reflect success, and instead focus on growth as a process and a multi-dimensional phenomenon, as well as on how growth relates to more fundamental outcomes.

Explaining usage of process modeling grammars : comparing three theoretical models in the study of two grammars

Our objective was to determine the factors that lead users to continue working with process modeling grammars after their initial adoption. We examined the explanatory power of three theoretical models of IT usage by applying them to two popular process modeling grammars. We found that a hybrid model of technology acceptance and expectation-confirmation best explained user intentions to continue using the grammars. We examined differences in the model results, and used them to provide three contributions. First, the study confirmed the applicability of IT usage models to the domain of process modeling. Second, we discovered that differences in continued usage intentions depended on the grammar type instead of the user characteristics. Third, we suggest implications and practice.

The coming

Through an exploration of representations of metamorphosis and the creation of a body of written work, this thesis uses a critical examination of theoretical approaches to metamorphosis in combination with textual analysis of representations of metamorphosis and creative practice as research to arrive at the beginnings of an ethic of writing. The creative work, The Coming, consists of a collection of short fiction, The Coming, and two collections of poetry, Orison and Milagros. The exegesis, Transhuman Change: towards an ethic of writing, explores theories about metamorphosis as a figure for writing, as a trope, and as a motif for exploring identity to contextualise the analysis of representations of metamorphosis from which the ethic is developed. With reference to the psychosexual development theory of Jacques Lacan and Elaine Scarry’s philosophy of the body, pain, language and creativity, the exegesis examines existing approaches to metamorphosis and uses supplementary textual analysis of influential representations of metamorphosis from Ovid to Pygmalion, X-Men and Extreme Makeover to explore assumptions about the body, language, the self, gender in western culture. The limitations of the performance of representations of metamorphosis as a figure for the self’s survival of death are considered in the light of voice as metonym for self to propose an ethic which valorises life. The experience of sex and the construction of gender in representations of metamorphosis are considered in the light of Lacan’s theory of desire and Scarry’s theory of the body and language to propose an ethic of representing gender ironically. The motif of the faithless lover and the Pygmalion myth are considered in the light of the (m)other’s role in language to propose an ethic in which indeterminacy constitutes the condition for being aware of oneself among selves. Each of the three proposals is discussed in relation to the short fiction, memoir and poems produced in the course of this research to test their limits and possibilities as the foundation of an emerging ethic of writing.

A hidden Markov model and relative entropy rate approach to vision-based dim target detection for UAV sense-and-avoid

Uninhabited aerial vehicles (UAVs) are a cutting-edge technology that is at the forefront of aviation/aerospace research and development worldwide. Many consider their current military and defence applications as just a token of their enormous potential. Unlocking and fully exploiting this potential will see UAVs in a multitude of civilian applications and routinely operating alongside piloted aircraft. The key to realising the full potential of UAVs lies in addressing a host of regulatory, public relation, and technological challenges never encountered be- fore. Aircraft collision avoidance is considered to be one of the most important issues to be addressed, given its safety critical nature. The collision avoidance problem can be roughly organised into three areas: 1) Sense; 2) Detect; and 3) Avoid. Sensing is concerned with obtaining accurate and reliable information about other aircraft in the air; detection involves identifying potential collision threats based on available information; avoidance deals with the formulation and execution of appropriate manoeuvres to maintain safe separation. This thesis tackles the detection aspect of collision avoidance, via the development of a target detection algorithm that is capable of real-time operation onboard a UAV platform. One of the key challenges of the detection problem is the need to provide early warning. This translates to detecting potential threats whilst they are still far away, when their presence is likely to be obscured and hidden by noise. Another important consideration is the choice of sensors to capture target information, which has implications for the design and practical implementation of the detection algorithm. The main contributions of the thesis are: 1) the proposal of a dim target detection algorithm combining image morphology and hidden Markov model (HMM) filtering approaches; 2) the novel use of relative entropy rate (RER) concepts for HMM filter design; 3) the characterisation of algorithm detection performance based on simulated data as well as real in-flight target image data; and 4) the demonstration of the proposed algorithm's capacity for real-time target detection. We also consider the extension of HMM filtering techniques and the application of RER concepts for target heading angle estimation. In this thesis we propose a computer-vision based detection solution, due to the commercial-off-the-shelf (COTS) availability of camera hardware and the hardware's relatively low cost, power, and size requirements. The proposed target detection algorithm adopts a two-stage processing paradigm that begins with an image enhancement pre-processing stage followed by a track-before-detect (TBD) temporal processing stage that has been shown to be effective in dim target detection. We compare the performance of two candidate morphological filters for the image pre-processing stage, and propose a multiple hidden Markov model (MHMM) filter for the TBD temporal processing stage. The role of the morphological pre-processing stage is to exploit the spatial features of potential collision threats, while the MHMM filter serves to exploit the temporal characteristics or dynamics. The problem of optimising our proposed MHMM filter has been examined in detail. Our investigation has produced a novel design process for the MHMM filter that exploits information theory and entropy related concepts. The filter design process is posed as a mini-max optimisation problem based on a joint RER cost criterion. We provide proof that this joint RER cost criterion provides a bound on the conditional mean estimate (CME) performance of our MHMM filter, and this in turn establishes a strong theoretical basis connecting our filter design process to filter performance. Through this connection we can intelligently compare and optimise candidate filter models at the design stage, rather than having to resort to time consuming Monte Carlo simulations to gauge the relative performance of candidate designs. Moreover, the underlying entropy concepts are not constrained to any particular model type. This suggests that the RER concepts established here may be generalised to provide a useful design criterion for multiple model filtering approaches outside the class of HMM filters. In this thesis we also evaluate the performance of our proposed target detection algorithm under realistic operation conditions, and give consideration to the practical deployment of the detection algorithm onboard a UAV platform. Two fixed-wing UAVs were engaged to recreate various collision-course scenarios to capture highly realistic vision (from an onboard camera perspective) of the moments leading up to a collision. Based on this collected data, our proposed detection approach was able to detect targets out to distances ranging from about 400m to 900m. These distances, (with some assumptions about closing speeds and aircraft trajectories) translate to an advanced warning ahead of impact that approaches the 12.5 second response time recommended for human pilots. Furthermore, readily available graphic processing unit (GPU) based hardware is exploited for its parallel computing capabilities to demonstrate the practical feasibility of the proposed target detection algorithm. A prototype hardware-in- the-loop system has been found to be capable of achieving data processing rates sufficient for real-time operation. There is also scope for further improvement in performance through code optimisations. Overall, our proposed image-based target detection algorithm offers UAVs a cost-effective real-time target detection capability that is a step forward in ad- dressing the collision avoidance issue that is currently one of the most significant obstacles preventing widespread civilian applications of uninhabited aircraft. We also highlight that the algorithm development process has led to the discovery of a powerful multiple HMM filtering approach and a novel RER-based multiple filter design process. The utility of our multiple HMM filtering approach and RER concepts, however, extend beyond the target detection problem. This is demonstrated by our application of HMM filters and RER concepts to a heading angle estimation problem.