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Current accepted theory for the calculation of gas flow through narrow openings, such as fractures in weapon casings during expansion, relies on the use of ideal nozzle flow theory being applicable throughout the fracture process. The thesis initially looked to determine the acceleration phase of fragments within expanding detonation gases; however, the scope narrowed to determine the applicability of the current gas flow model. The revised scope combines numerical and experimental research to investigate the flow Mach number within narrow openings, along with any influence of internal pressure, opening width or opening length. Numerical modelling conducted investigated internal pressures of 10 bar, 18 bar, 50 bar and 200 bar for opening diameters of 1 mm to 6 mm in 1 mm steps. Opening lengths of 5 mm, 10 mm and 20 mm were considered to determine any casing thickness effects. The modelling showed the internal pressure to have minimal effect on the flow, with the main driver being the opening diameter. In general, the flow stabilised at Mach numbers greater than unity for each case, returning Mach 1.2 for a diameter of 1 mm which increased to Mach 1.35 for diameters of 3 mm and above. The experimental investigation measured static and stagnation pressures within the flow through a 6 mm diameter opening requiring the design, construction, and calibration of a novel miniature pressure probe. Experimental pressures were limited by the probe response with tests conducted at 8 bar and 10 bar to study flow stability. Aerodynamic blockage effects were considered and detailed analysis of the experimental data is presented, using compressible flow theory and Rayleigh supersonic pitot theory. Supplementary numerical modelling could not definitively determine detached bow shock presence within the experimental set up used, so uncertainties in the final analyses were calculated for inappropriate use of either theory. The most conservative approach was to use compressible flow theory as this underestimated the flow Mach number should a bow shock exist. Experimentally, the flow was approximately Mach 1.15 which gives reasonable agreement with the numerical modelling; both returning low supersonic flow. Finally, two alternative model hypotheses are presented; however, neither was developed into a working model due to experimental limitations.

Attitudes towards sexual offenders have been widely studied in forensic psychology and criminology research over the past 25 years. At present, however, studies examining these views are predominantly descriptive in nature. That is, self-report questionnaire measures are typically distributed to different groups (e.g., general public samples, and members of different occupational categories), with the resultant between-groups differences being reported in research papers. While these studies have provided some interesting findings, the results gained from them fail to inform researchers about the psychological mechanisms that underpin views about this offending population. The overarching aim of this thesis was to begin to fill this knowledge gap. That is, a range of studies were designed to use robust experimental methods, within validated theoretical paradigms, in order to examine some of the potential constructs that influence people’s attitudes towards sexual offenders. Chapter 1 presents a review of the current state of the field in relation to attitudes towards sexual offenders, with gaps in current knowledge being identified. In Chapter 2, the theoretical framework within which the empirical aspects of the thesis operate is set out. Key constructs in this section include dual-process cognition, and our reliance on implicit (i.e., non-conscious) mental processes when making decisions. Chapter 3 builds upon criticisms of one measure of attitudes towards sexual offenders in order to reconceptualise its use into one of an outcome measure. This is then used throughout Chapters 4, 5, and 6 as a measure of sentencing and risk judgements, in order to examine the effects of various experimental manipulations. Studies presented in Chapter 4 found that heuristic-based processes based around the principles of availability appear to influence decision-making about sexual offenders at the macro (political) level, but not at the micro (individual) level. Instead, individual participants’ attitudes and judgements about sexual offenders were dependent on different primes relating to the representativeness (Chapter 5) and affect (Chapter 6) heuristics. Chapter 7 offers a discussion of the empirical findings presented at earlier points of the thesis, and outlines opportunities to develop further work into the heuristic-based nature of attitudes towards sexual offenders. The work contained within this thesis is original, in that well-validated theoretical models are used to begin to examine the psychological mechanisms that may underpin attitudes iii towards sexual offenders. The apparent dual-process nature of such views calls into question some previously-expressed calls within the literature that presenting fact-based information about sexual offenders may lead to improvements in societal attitudes. Instead, it may be that more indirect and emotional methods may be required to achieve such aims. Towards the end of the thesis, clear opportunities for further work are set out, as are some of the potential implications of this research.

Particulate solutions exhibit many interesting and varied behaviours when driven out of equilibrium. Not least of which is their ability to form elaborate and intricate patterns when subject to gravity driven flow in the confined space between a substrate and the fluid-air interface of a thin film. The present work presents results of investigations into some of the key physical pro- cesses within the fluid, that are thought to lead to the formation of patterns. These were performed using a range of simplified models and numerical simulations. The cen- tral theme of the work is a simplified two fluid model of the particle-laden fluid itself, the results of which reveal a novel pattern formation process, entirely distinct from the conventional instability driven process normally associated with patterning. This process involves the decay of fluctuations in the particle volume fraction in one direction while fluctuations in the other persist. Ultimately, however, it was found, using both simulations and analytical stability analysis, that the physical processes encompassed by this simple model are not sufficient to increase the intensity of the patterns. As well as considering additions to the model; two more, in depth, studies of physical processes at the microscopic level, thought to be potentially important to the formation of patterns, were also carried out. These consisted of the formulation of a simple, analytical, constitutive relation and a particle scale simulation including full many body hydrody- namic interactions. These highlighted the importance of memory effects and, long range, hydrodynamic interactions as potentially important processes by which band patterns may grow and increase in intensity. The whole issue of patterning on a surface also leads to the question of how these, two dimensional, patterns should be characterised and, to this end, a number of novel methods for calculating the complexity are also discussed.

This thesis presents results concerning canonical extensions of bounded lattices and natural dualities for quasivarieties of default bilattices. Part I is dedicated to canonical extensions, while Part II focuses on natural duality for default bilattices. A canonical extension of a lattice-based algebra consists of a completion of the underlying lattice and extensions of the additional operations to the completion. Canonical extensions find rich application in providing an algebraic method for obtaining relational semantics for non-classical logics. Part I gives a new construction of the canonical extension of a bounded lattice. The construction is done via successive applications of functors and thus provides an elegant exposition of the fact that the canonical extension is functorial. Many existing constructions are described via representation and duality theorems. We demonstrate precisely how our new formulation relates to existing constructions as well as proving new results about complete lattices constructed from graphs. Part I ends with an analysis of the untopologised structures used in two methods of construction of canonical extensions of bounded lattices: the untopologised graphs used in our new construction, and the so-called `intermediate structure'. We provide sufficient conditions for the intermediate structure to be a lattice and, for the case of finite lattices, identify when the dual graph is not a minimal representation of the lattice. Part II applies techniques from natural duality theory to obtain dualities for quasivarieties of bilattices used in default logic. Bilattices are doubly-ordered algebraic structures which find application in reasoning about inconsistent and incomplete information. This account is the first attempt to provide dualities or representations when there is little interaction required between the two orders. Our investigations begin by using computer programs to calculate dualities for specific examples, before using purely theoretical techniques to obtain dualities for more general cases. The results obtained are extremely revealing, demonstrating how one of the lattice orders from the original algebra is encoded in the dual structure. We conclude Part II by describing a new class of default bilattices. These provide an alternative way of interpreting contradictory information. We obtain dualities for two newly-described quasivarieties and provide insights into how these dual structures relate to previously described classes of dual structures for bilattices.

Carbon nanotubes (CNT) are a new form of industrially relevant nano-scale particle and are seen as the cutting edge of the burgeoning nanotechnology revolution which promises to impact on all our lives. Due to high length to diameter ratio, CNT are perhaps the most well known of a growing collection of high aspect ratio nanoparticles (HARN). However the production and use of carbon nanotubes has presented an interesting toxicological question based on its structure and raised the question ‘are carbon nanotubes like asbestos?’. Few people are unaware of the devastating global pandemic of diseases caused by asbestos and similarities in needle-like shape between asbestos and nanotubes have raised fears that nanotubes may mimic asbestos-type disease. The purpose of this study was to investigate this link, based on the wealth of information known about the toxic effects of certain forms of fibre on the respiratory system. From this we hope to identify those carbon nanotubes which are hazardous whilst not prejudicing the use of those industrially relevant materials which can be used safely. Within fibre toxicology there exists a central paradigm which outlines the main properties a fibrous particle must possess if it is to exert pathogenic effects in the body. This paradigm outlines the importance of length, thinness and biopersistence to a fibre and an absence of one or more of these attributes results in a loss of pathogenicity. We took this paradigm and, using suitable asbestos and non-asbestos controls, applied it various morphological forms of carbon nanotubes using an in vivo model. The resultant data demonstrates for the first time that asbestos-like pathogenic behaviour associated with carbon nanotubes is closely linked to the morphology of the nanotubes and their aggregates. Specifically our results showed that CNT which possessed a long, straight length were highly inflammogenic and fibrogenic within the peritoneal cavity of mice; a model sensitive to the pathogenic effects of fibres. As well as length, the importance of biopersistence in the pathogenesis of fibrous particles has been known for many years and is a central attribute affecting the pathogenicity of fibres. Amphibole asbestos is known to be durable, a commercially exploited attribute and as such is biopersistent in the lung which is a key feature of its pathogenicity. Glass fibre on the other hand is bio-soluble, and whilst long and inhalable, does not cause significant disease due to its lack of biopersistence. Based on the grapheme structure of CNT which impart exceptional strength and rigidity and the chemical inertness of carbon we would hypothesis that CNT would be biopersistent and therefore fulfil another of the criteria of the fibre pathogenicity paradigm (FPP). Our aim therefore has been to establish the durability of CNT against fibrous particles of known durability using a synthetic solution maintained at a pH to simulate the lung environment. Using a range of 4 CNT and using both durable and non-durable fibres such as amphibole asbestos and glass fibre to bench mark our result; we demonstrated that 3 of the 4 CNT tested displayed exceptional durability whilst the fourth lost approximately 30% of its mass during the experiment with concomitant reduction in pathogenicity. As well as length and biopersistence, the surface of a particle has been shown to contribute to the overall toxicity of a particle and in certain circumstances, such as that of quartz, the surface of the particle can be the biologically active component. In the case of carbon nanotubes, surface functionalisation is commonly used for various endpoints including the addition of various tags and labels for tracking. As such our further aim was to investigate the relationship between the length-dependent pathogenicity of a fibre sample and the surface of the fibre. By using different forms of functional groups attached to the surface of a pathogenic carbon nanotube we aim to critically test if the level of inflammation and fibrosis triggered in vivo can be altered by simple alteration of the surface. Our results showed that surface modification of CNT could alter the inflammogenic and fibrogenic effects of CNT which may have important implications when considering the hazard assessment of functionalised HARN. As CNT are not the only form of fibrous nanomaterial and within this project we also attempted to determine the applicability of the FPP to further high aspect ratio nanomaterials. In order to do this we set out to determine the generality of this hypothesis by asking whether nickel nanowires, a radically different form of HARN to CNT, show length-dependent pathogenicity. Nickel oxide nanowires synthesised to be predominantly long (>20 μm) act similarly to amphibole asbestos in showing the ability to elicit strong inflammation in the mouse peritoneal model in a dose dependent manner; inflammation was not seen with the short (<5 μm) nanowires. In summation, the results from this study are the first to show that long HARN can indeed behave like asbestos when in contact with the sensitive mesothelium. This study suggests a potential link between inhalation exposure to long nanotubes and asbestos-related disease, especially mesothelioma and as such this may have immediate implications across many disciplines if care is to be taken to avoid a long term legacy of harm.

Drug-induced liver injury (DILI) is the most frequent cause for withdrawal of approved drugs and attrition of drug development. Although the cellular mechanisms of DILI leading to overt tissue and organ damage are still not fully defined, model hepatotoxins such as acetaminophen (paracetamol; AP AP) have been used in animal models to provide important insight into the relationship between chemical structure, drug metabolism and cellular response. The overall extent of APAP injury is thought to be dependent on the activation of cell-cell signalling pathways, in particular between hepatocytes and cells of the innate immune system. However, the extent of the role of the innate immune and inflammatory response in the modulation of liver injury remains poorly defined, with conflicting evidence in the literature. The work presented in this thesis has used model hepatotoxins AP AP and galactosamine (GaIN) and the innate immune stimulator lipopolysaccharide (LPS) as tools to explore the mechanism of inflammation associated with DILl with the aim to further understand the various inflammatory pathways during DILl and their contribution to the progression ofliver injury. Male C57BLl6 mice were used to investigate the inflammatory response associated with AP AP, GaIN and LPS exposure. Inflammation was measured as serum levels of TNF -u, IL-6 and IL- 1β by ELlSA and neutrophil infiltration as assessed by histological analysis. Hepatotoxicity in the AP AP model was characterised by a dose and time-dependent increase in serum ALT and was confirmed by histological analysis (O-lOOOmg/kg; 0-24hr). Significant elevations in levels of TNF -α, IL-6 and IL-l β were observed in the serum of mice following APAP overdose (530mg/kg; 0-24hr). Overnight fasting of mice led to a greater hepatotoxic and inflammatory response compared to non-fasted mice post AP AP treatment. The LPS model was characterised by having no hepatotoxicity, as serum ALT activity remained at control levels (control - 41.37±8.45U/l; LPS - 50.57±5.56U/I; 5mg/kg; 24hr) and having a potent inflammatory response as determined by cytokine release (TNF-α 513.13±50.15pg/ml; IL-6 - 1201.12±157.20pg/ml; IL-lβ - 227.08±39.93pg/ml; 5mg/kg; 24hr) and neutrophil infiltration. The GaIN model was characterised by mild hepatotoxicity (ALT activity 875.30±144.81U/l; 800mg/kg; 24hr) and a mild inflammatory response, with increase in cytokines (TNF-α - 56.44±5.68pg/ml; IL-6 - 63.22±8.41pg/ml; IL-lβ- 40.72±3.64pg/ml; 800mg/kg; 24hr) and neutrophil infiltration. Concurrent administration of suppressors of either metabolism (DMSO), or the innate immune response (aspirin, ethyl pyruvate and anti-HMGBl antibody) was also investigated. DMSO inhibited APAP metabolism, whereas aspirin had no effect on AP AP toxicity or the inflammatory response. Delayed administration of ethyl pyruvate reduced toxicity and serum HMGB 1 content post APAP. Expression of RAGE mRNA over a 24hr time course was measured in whole livers of fasted and fed mice treated with APAP by RT-PCR. Full-length (flRAGE), endogenous secretory (esRAGE) and total (tRAGE) isoforms of RAGE increased in fed mice between l hr and 3hr. Fasted mice showed a more prolonged increase in expression of all 3 isoforms of RAGE, culminating in a peak increase at 5hr. Western blot analysis determined that there were no changes in RAGE protein expression in whole liver over a 24hr period of AP AP iv exposure. In situ hybridisation revealed a nuclear accumulation of RAGE mRNA III hepatocytes following AP AP exposure. In summary, the studies described in this thesis have provided further evidence for the role of inflammation during DILl by using and developing a variety of in vivo models. These models assessed both basic and novel mechanisms of inflammation, such as cytokine release, hepatic neutrophil infiltration and RAGE expression, and tested potential therapeutic inhibitors such as aspirin and EP.

These studies were aimed at identifying potential surrogate compounds for dermal absorption of bioactive agents in vitro using flow through and static cell diffusion systems, and also to generate novel data on the effects of application vehicle on chemical absorption following low level exposure. For protection and risk assessment purposes, the influence of ‘everyday’ clothing, and skin surface decontamination on dermal chemical absorption was also assessed. The model compounds (caffeine and benzoic acid), and the surrogate compounds (chlorpyrifos, dichlorvos and phorate) were generally found to be poor marker chemicals for comparison with HD absorption through human and pig skin in vitro. However, benzoic acid absorption from a finite dose in IPA more closely matched the absorption profile of HD applied as a finite dose in IPA. Dichlorvos absorption was greatest from all vehicles compared with chlorpyrifos and HD absorption in vitro. Dermal absorption of chlorpyrifos was enhanced when applied in PG compared with absorption from IPA or IPM. No differences were observed between absorption of neat HD and HD in IPA in terms of percentage of applied dose absorbed at 24 hours. Absorption of HD through full thickness pig skin more closely matched absorption through full thickness human skin, split thickness pig skin overestimated absorption of HD in vitro in comparison. ‘Everyday’ clothing (cotton shirt) significantly reduced absorption of dichlorvos, chlorpyrifos and HD through human skin. Chemicals were applied to clothed skin in IPA to mimic finite exposure, and left in contact for 30 minutes (dichlorvos), 4 hours (chlorpyrifos), and 1 hour (HD). For all chemicals, removal of clothing followed by immediate skin surface decontamination with 0.5% (v/v) soap solution further reduced absorption compared with removal of clothing alone. Despite these differences not being significant, in terms or civilian exposure, it would be recommended to remove clothing and decontaminate as early as possible postexposure to minimise the potential for dermal absorption and localised toxicity within the skin. In conclusion, the organophosphate compounds used in these studies (chlorpyrifos and dichlorvos) could potentially be useful surrogates for organophosphate agents such as VX or sarin, however, further work is needed to make these comparisons. The vehicle in which a chemical is applied to the skin can have a profound effect on dermal absorption, and this knowledge is important for risk assessment for exposure to a range of chemicals. Cotton shirt material significantly reduced dermal absorption of all chemicals used compared with 24 hour exposure. Despite this clothing not being designed for protective purposes, this may have a significant impact for reducing dermal absorption and toxicity in vivo as a result of chemical exposure. Further investigation is needed to assess absorption of a wider range of chemicals and application vehicles for risk assessment purposes, and to identify chemicals that more closely mimic dermal absorption of bioactive agents in vitro for extrapolation to in vivo exposure scenarios

Cortical and trabecular bone characteristics can be used to make predictions regarding previous loading regimes and developmental milestones which a bone has encountered. This has led to the suggestion that in the adult pelvis, bone patterning is related to the remodeling forces generated during bipedal locomotion. However, during the neonatal period the pelvic complex is non-load bearing, therefore, structural organisation of the ilium cannot reflect direct stance related forces. This study considers the cortical and trabecular bone structure in the ilium of the fetal and newborn infant, a structural configuration which until now has remained largely neglected in the literature. Only recently, with the advent of imaging modalities, has a greater insight and understanding of previously unexplored human bone structural composition and developing bone structure been made possible. In this study, multiple imaging techniques were applied to establish the optimal modality for application to the assessment of bone microstructure. Plain plate macroradiography and micro-computed tomography were identified as the gold standard imaging modalities for bone structural analysis for respective qualitative and quantitative assessment. These techniques were applied to gain a perspective of bone form from a sample of fetal and neonatal ilia selected from the Scheuer collection of juvenile remains. Initially, qualitative analysis highlighted consistent and well-defined patterns of cortical and trabecular bone organisation within the fetal and neonatal ilium, which corresponded with previously recognised regions in the adult that have been attributed directly to forces associated with bipedal locomotion. This was highly unexpected as the early developmental ilium is non-load bearing. Subsequently, quantification of the neonatal cortical and trabecular structure reinforced radiographic observations by identifying regions of significant architectural arrangement. Further investigation of this precocious patterning led to a revised proposal for the mode of growth in the human ilium during the neonatal developmental period. Analysis revealed statistically significant differences in regional trabecular characteristics and cortical thicknesses which have formed the basis of a proposed growth model for the ilium. The presence of ‘progressive growth regions’ and ‘restricted growth regions’ which appear to relate to metaphyseal and non-metaphyseal borders of the ilium have been demonstrated. Analysis of the early iliac bone pattern is important for understanding the relationship between trabecular bone patterning and cortical bone structure during the earliest stages of development in response to the specific functional forces acting during this period. It is suggested that the seemingly organised rudimentary scaffold observed in the early developmental ilium may be attributable to early ossification patterning, non-weight bearing anatomical interactions or even to a predetermined genetic blueprint. It must also be postulated that whilst the observed patterning may be indicative of a predetermined inherent template, early non-load bearing locomotive influences may subsequently be superimposed upon this scaffolding and perhaps reinforced and likely remodelled at a later age. Ultimately, the analysis of this fundamental primary pattern has core implications for understanding the earliest changes in iliac trabecular architecture and provides a baseline insight into future ontogenetic development and bipedal capabilities. Finally, the structural data and statistical analysis presented challenge the current concept of implied centrifugal ossification within the human ilium and present evidence of an alternative pattern of ossification that is largely dictated and controlled by basic anatomical principles.

Sound is an important part of the human experience and provides valuable information about the world around us. Auditory human-computer interfaces do not have the same richness of expression and variety as audio in the world, and it has been said that this is primarily due to a lack of reasonable design tools for audio interfaces. There are a number of good guidelines for audio design and a strong psychoacoustic understanding of how sounds are interpreted. There are also a number of sound manipulation techniques developed for computer music. This research takes these ideas as the basis for an audio interface design system. A proof-of-concept of this system has been developed in order to explore the design possibilities allowed by the new system. The core of this novel audio design system is the timbre space. This provides a multi-dimensional representation of a sound. Each sound is represented as a path in the timbre space and this path can be manipulated geometrically. Several timbre spaces are compared to determine which amongst them is the best one for audio interface design. The various transformations available in the timbre space are discussed and the perceptual relevance of two novel transformations are explored by encoding "urgency" as a design parameter. This research demonstrates that the timbre space is a viable option for audio interface design and provides novel features that are not found in current audio design systems. A number of problems with the approach and some suggested solutions are discussed. The timbre space opens up new possibilities for audio designers to explore combinations of sounds and sound design based on perceptual cues rather than synthesiser parameters.

The purpose of this study was to determine if the student-to-administrator ratio in a school was related to student achievement as well as to examine the duties a principal delegated to others to determine if a pattern existed between principals of high and low performing high schools in regard to duties kept versus duties delegated. While the results of this study did not find one overall recommendation for a student-to-administrator ratio, it did determine that there are certain duties principals of high achieving schools did not delegate as compared to principals of schools with lower achievement. This study also produced a comprehensive description of the 51 duties of a high school principal and provides a recommendation for which duties may be most valuable for the principal to keep and which duties could be delegated to other personnel. [The dissertation citations contained here are published with the permission of ProQuest LLC. Further reproduction is prohibited without permission. Copies of dissertations may be obtained by Telephone (800) 1-800-521-0600. Web page: http://www.proquest.com/en-US/products/dissertations/individuals.shtml.]

The purpose of this study was to examine the influence of various intensity levels of athletic participation on academic and leadership performance in a selective institution. For the purpose of this study a retrospective analysis of existing admissions and student performance data was conducted. The continuous dependent variables were academic and leadership performance scores. The categorical independent variables were the three intensity levels of athletic participation (high commitment athletes, moderate commitment athletes, general population students), gender and race. The subjects for this study included 4977 of the 4998 students that graduated from a selective institution from 1992 through 1996. Results of this study provide evidence that participation in college athletics did not hinder student academic performance in a selective institution. Even athletes that participated in high commitment athletics were found to reach their academic potential in this setting. These findings are attributed to the institutional policies that allowed athletes to remain integrated within the student body as a whole. It remains unclear; however, which policies had the greatest impact on the academic success of athletes in this investigation. In a separate analysis, athletic participation was found to negatively influence high commitment athlete's leadership performance scores in a selective institution. Given the scarcity of published research examining the influence of athletic participation on leadership development, the findings of this investigation may form the foundation upon which future studies will build upon. The implications for this study provide insight for future research and allow for the advancement of current theory on the complex role of intercollegiate athletics and its influence on the academic and leadership performance of college students. [The dissertation citations contained here are published with the permission of ProQuest LLC. Further reproduction is prohibited without permission. Copies of dissertations may be obtained by Telephone (800) 1-800-521-0600. Web page: http://www.proquest.com/en-US/products/dissertations/individuals.shtml.]

Monoclonal antibodies which recognise tumour associated antigens provide a means of targeting radionuclides selectively to tumour cells. Work has been directed towards the synthesis of functionalised macrocyclic ligands to bind indium(III) [( 111)In:- γ-emitter] and gallium(III) [( 67)Ga:- γ-emitter] for use in radioimmunoscintigraphy and silver(I) [( 111)Ag:- β-emitter] for use in radioimmunotherapy. Macrocyclic ligands have been selected to bind the respective radionuclides rapidly, under mild conditions, to form complexes which are kinetically inert in vivo. Four tribasic hexadentate macrocyclic ligands (9, 10, 11 and 12-membered rings) have been synthesised to bind indium and gallium. Comparison of the rate of ( 111)In uptake under mild conditions at low concentration (10-100 µM) revealed that the nine-membered triaza-triacid was the most effective. The X-ray crystal structures of the indium and gallium complexes of the [9]-N(_3)-triacid have been determined. A C-functionalised derivative of the [9]-N(_3)-triacid has been synthesised by two routes, both starting from (2S)-Lysine. The syntheses of two N-functionalised derivatives of the [9]-N(_3)-triacid are also described. Antibody linkage has been effected (in collaborative work with Celltech Ltd.) by reacting the functionalised macrocycle with a heterobifunctional linker molecule (maleimide ester) followed by incubation with the antibody (previously treated with 2-iminothiolane).Three new nitrogen and sulphur donor macrocyclic ligands have been synthesised to bind silver(I) and the 1:1 silver complexes have been isolated as crystalline solids and characterised by FAB mass spectrometry and ( 1)H nmr. Silver(I) complexes of two of the ligands have been characterised by X-ray crystallographic analysis. The stability constants (log K(_s), MeOH) for the silver(1) complexes of the[18]-membered N(_4)S(_2) and N(_4)S(_2)Me(_4) macrocyclic ligands (14.1 and 14.6respectively) are the highest recorded for monocyclic ligands.

This report outlines the development process for Junctions, an original, mini-drama podcast that explores racial bias in the context of everyday interaction. The report consists of three sections – The Podcast, Pilot Episode, and Future Episodes – each of which speaks to a different aspect of the program’s framework. It also includes nearly all of the planning documents I created during pre-production, production, and post-production.

This thesis focuses on United States civil-military relations during the first decade of the twenty-first century. It examines interactions between principal-level civilian and top-tier military leadership during three strategic decision-making moments. Each case involves examples of subjective civilian control. The author's goal is to investigate and then categorize the processes that were used, assessing how variables influenced the nature of subjective control. Qualitative process tracing is the primary methodology. The author focuses on available sources from myriad avenues including but not limited to journalism, memoirs, primary documents, and social science literature. Case study analysis identifies numerous variables. Presidential leadership and process organization were found to be the most influential, spanning from engaged to "delegatory" and orderly to ad-hoc, respectively. Correlations are identified between the variables. Then, theories from established literature are reviewed and applied when possible. Research finds that subjective civil-military relations became increasingly moderate and theoretically "pure" over each case, chronologically. The author uses his analysis to create new typologies of subjective civil-military control, focusing on the relationships between presidential leadership and process organization. The resulting typologies are intended to assist political scientists' identification and categorization of varying civil-military relationships on the subjective end of Huntington's spectrum.

This work is a broad historical survey of Christianity's presence in the geographic region of modern day Israel and Palestine. It focuses on Christian communities' perceived identities, treatment by their neighbors, and current status. Particular focus is paid to perceived memory/identity of recent generations; Ottoman rule, British mandate, and modern Israeli-Palestinian geopolitics are examined most deeply. Qualitative interviews with Christians living in the West Bank, Jerusalem, and northern Israel complement the work.

Global energy consumption is projected to double from its 1990 level by 2030. Although rechargeable lithium-ion batteries have powered mobile computing and telecommunications for two decades, their energy density is inadequate to meet rising demands for grid storage, and falls short of DOE targets for electric vehicles and the needs of new electronic devices. As a result, the lithium-sulfur (Li-S) system has emerged as a leading “Beyond Lithium Ion” candidate. Simultaneously, the impetus for a comprehensive “Internet of Things” that interactively monitors and controls energy use, infrastructure, and human health has been consistently hampered by a lack of batteries that are small, thin, flexible, implantable, high-energy density, and cheaply manufactured to power the multitude of required devices. This dissertation addresses three aspects of these dilemmas. First, an elastic, conductive, and electroactive polymer nanocomposite comprising polypyrrole and polyurethane (PPyPU) is developed to serve as a binder for flexible Li-S cathodes. After fifty flex/bend cycles, the cathodes provide high capacity with essentially no capacity-fade for 100 cycles at high sulfur loadings. The electroactive PPy in the binder is believed to stabilize dissolved polysulfides, while the elastic PU accommodates the significant sulfur expansion which is known to compromise Li-S cathode integrity during charge/discharge. Second, a process is presented for producing extrusion-printed carbon nanotube-based electrodes for Li-S cathodes. Although printing provides a high-throughput, inexpensive, top-down, “green” alternative to industrial microfabrication, it has been infrequently applied to batteries, and the few reports of printed batteries were based on low energy-density materials. Therefore, multiwall carbon nanotube inks are formulated for printing microelectrodes to be utilized as electrodeposition scaffolds for high-loading Li/polysulfide catholytes. The resulting lithium-sulfur cathodes are shown to meet industrial benchmarks for portable and wearable electronics. In concert, sulfur-infused single-wall carbon nanotubes (S@SWNT) are used for inkjet-printed thin-film cathodes as proof-of-concept for integrated, printing-based nanomanufacturing. Third, an electroactive bio-nanocomposite comprising purely endogenous materials (dopamine and hyaluronic acid) is synthesized and characterized in vitro as a potentially implantable energy-storage material. The dopamine-hyaluronic acid (DAHA) hydrogel composite can be electropolymerized to create a pseudocapacitive biopolymer, p(DAHA), that exhibits catechol−quinone interconversion, high pseudocapacitance and discharge capacity, and stable, long-term electroactivity for 400 cycles. These characteristics predispose it for bioelectronic energy storage, i.e., as a supercapacitor or, when coupled with an implantable Ag/AgCl electrode, a biobattery with an operating voltage of ∼0.85 V.

Sexually transmissible infections (STIs) are responsible for considerable morbidity and even mortality. In 2012, STIs resulted in 100 million lost disability-adjusted life years and human immunodeficiency syndrome (HIV) was the sixth leading cause of death in the world. In this thesis, mathematical models are applied to Chlamydia, gonorrhoea and HIV at in-host, population and global levels to understand pathogen and immune system interaction, spread of infection through populations, and effectiveness of control strategies. At the in-host level, a mathematical model tracking cell and chlamydiae counts in mice predicts that the chlamydial load at equilibrium is independent of the inoculum. Experimental data are shown to be consistent with this prediction. The model is used to identify the rate of replenishment of healthy cells as having a large impact on the equilibrium level, highlighting the importance of cell availability to Chlamydia dynamics. At the population level, a mathematical model of gonorrhoea is used to simulate the potential impact of vaccines. A vaccine of 50% efficacy that is protective for 20 years, administered before sexual debut, is predicted to reduce gonorrhoea prevalence in the population by over 90% after 20 years. A novel mathematical model is developed to simulate Chlamydia in declining koala populations, and is used to predict that it would be most effective to vaccinate females aged 1-2 years. Targeting these koalas and vaccinating around 10% of the population each year using a vaccine of 75% average efficacy is expected to reverse population decline in 5 years. At the global level, public health strategies are often informed by model-based costeffectiveness analyses. A systematic review is conducted of the cost-effectiveness literature for HIV interventions in regions with concentrated epidemics. Interventions that target key affected populations are found to be most cost-effective. Data on HIV spending for twelve countries shows that in eight more than 30% of spending goes to general population and non-targeted programs, suggesting that HIV resource allocation is not consistent with cost-effectiveness evidence. The findings in this thesis, from the in-host scale to the global scale, will inform vaccine development and resource allocation for STIs.

The distribution and abundance of coral reef fishes is undoubtedly affected by a variety of factors. While much previous research into dispersal success of reef fishes has focused on species' ability to survive for long periods in the pelagic larval stage, this alone cannot explain biogeographic patterns. Consequently, a novel approach was developed to examine another potentially important factor contributing to dispersal ability: the number of offspring propagules produced at a source location. A large scale data collection effort was undertaken around islands of the Central and Western Pacific to facilitate testing of this hypothesis. Since direct measurement of larval output on this scale is not possible, a proxy for larval output--adult population density--was used as the predictive variable in models used to identify factors underlying dispersal patterns. In situ visual sampling was conducted over seven years on 38 islands across the Pacific. Over 750 species and 300,000 individual fish were identified and sampled along 700 transects. Analysis was focused on the large biogeographic barrier separating Johnston Atoll and the Hawaiian Archipelago from the rest of the study islands. The regions most likely to be sources of fish larvae reaching the Johnston-Hawaii system were sampled using robust, standardized, quantitative fish census methods. Methodological precautions were taken to ensure that the types of population estimates used in the analyses were robust in space and over time. Novel statistical methods were developed to evaluate the strength of ecological data and two types were identified as suitably robust and reliable; numeric density from belt-transect surveys and presence-absence records from large search area roving diver surveys. Biomass estimates and presence-absence data from belt transects were deemed inadequate or inappropriate for these analyses. Highly significant results of regression models confirmed a relationship between adult population density and long distance dispersal in 3 of 5 fish families included in the analysis. This finding is novel and offers a significant new approach to the study of the biogeography of marine species.

Ubiquitous computing describes computing technologies that are designed to be embedded in tools and in our environment, providing computational support for user interaction and service delivery. Intelligent environments are context-aware computing environments that deliver services using ubiquitous computing technologies. These environments provide users with services tailored to the users’ preferences and the current state of the environment. The development and implementation of these environments is challenging due to their potential ability to gather information on the environment’s occupants and context. The information collection, when combined with advanced data-mining techniques, has unprecedented potential to invade users’ privacy. The invasion of privacy is a significant concern to users, and must be addressed before intelligent environments can gain widespread acceptance. The use of ubiquitous computing technologies also poses unique challenges for service delivery and network security. By definition, ubiquitous computing describes computing that has faded into the background, allowing users to use the services and technologies as easily as they would more tangible physical objects. This integration into our world raises the question that if a service is inconspicuous enough to blend into the background, how can we allow users to identify previously unused services? Information security within intelligent environments is complicated by the physical availability of much of the environment’s hardware (which leaves it vulnerable to being tampered with). These privacy and security concerns raise the need for a ubiquitous computing infrastructure that will allow private interaction and the effective delivery of personalised and identity-restricted services. Owing to the large variety of services they could provide, it has been suggested that intelligent environments will one day cover most of our daily lives (for example our homes, offices, public transport networks or shopping centres). This requires a common approach be taken to users’ interaction with intelligent environments, and suggests a shared infrastructure will be required to support users’ interactions with different environments. User privacy requirements necessitate that this infrastructure be independently operated from the intelligent environments (and its service providers). Further privacy and interaction requirements highlight the need for user-controlled identity management structures and anonymous environmental interaction.

Participation in whitewater kayaking is growing faster than any other outdoor recreational pursuit. With increases in participation, an increase in the number of injuries associated with whitewater kayaking may also become apparent. Overuse injuries are the most prevalent type of injury found in whitewater kayakers. Due the large range of motion and forces that occur through the shoulder while kayaking, the most common injury location is the shoulder. Little scientific inquiry has been performed assessing the kinematics of kayaking and the musculoskeletal attributes of these athletes. Sixteen whitewater kayakers with shoulder pain and sixteen whitewater kayakers without shoulder pain participated in this study. Each subject underwent kinematic and electromyographic analysis of the forward kayak stroke. Additionally, participants underwent clinical examination of shoulder injury, clinical assessment of shoulder and torso range of motion, posterior shoulder tightness assessment, isokinetic strength testing at the shoulder, and a scapular kinematic evaluation during a standardized humeral elevation task.The most common type of injury found was related to overuse. Statistical comparisons occurred between the involved and uninvolved limb in the shoulder pain group and between the involved and uninvolved and matching shoulders in the control group, respectively. Significant differences were found between in involved and uninvolved shoulder for shoulder internal rotation and abduction range of motion. Additional differences were found for these variables between the involved shoulder in the pain group and the matching shoulder in the control group. Kayakers with shoulder pain present with decreased shoulder range of motion on their involved shoulder. Assessment of the specific types of injuries seen in whitewater kayakers should be further evaluated. Additionally, the role of increasing range of motion through injury prevention programs in whitewater kayakers with shoulder pain should be investigated.

A fundamental task of algebraists is to classify algebraic structures. For example, the classification of finite groups has been widely studied and has benefited from the use of computational tools. Advances in computer power have allowed researchers to attack problems never possible before. In this dissertation, algorithms for noncommutative algebra, when ab is not necessarily equal to ba, are examined with practical implementations in mind. Different encodings of associative algebras and modules are also considered. To effectively analyze these algorithms and encodings, the encoding neutral analysis framework is introduced. This framework builds on the ideas used in the arithmetic complexity framework defined by Winograd. Results in this dissertation fall into three categories: analysis of algorithms, experimental results, and novel algorithms. Known algorithms for calculating the Jacobson radical and Wedderburn decomposition of associative algebras are reviewed and analyzed. The algorithms are compared experimentally and a recommendation for algorithms to use in computer algebra systems is given based on the results. A new algorithm for constructing the Drinfel'd double of finite dimensional Hopf algebras is presented. The performance of the algorithm is analyzed and experiments are performed to demonstrate its practicality. The performance of the algorithm is elaborated upon for the special case of group algebras and shown to be very efficient. The MeatAxe algorithm for determining whether a module contains a proper submodule is reviewed. Implementation issues for the MeatAxe in an encoding neutral environment are discussed. A new algorithm for constructing endomorphism rings of modules defined over path algebras is presented. This algorithm is shown to have better performance than previously used algorithms. Finally, a linear time algorithm, to determine whether a quotient of a path algebra, with a known Gröbner basis, is finite or infinite dimensional is described. This algorithm is based on the Aho-Corasick pattern matching automata. The resulting automata is used to efficiently determine the dimension of the algebra, enumerate a basis for the algebra, and reduce elements to normal forms.

Guidelines to an understanding of visitor centres and how they impose and are imposed upon by the landscape. This dissertation is principally directed to Landscape Architects and those involved in the design and implementation of visitor centres in relation to the landscape. Its emphasis is on fostering an understanding of visitor centres and their relationship to the landscape rather than providing hard and fast practical solutions, in which, needless to say, landscape professionals should be well versed. This dissertation is divided into five basic parts, and although distinct, are closely interconnected. Part one: An introduction outlining aims, defining the problem and the visitor centre. Part two: A philosophic view of attitudes to visitor centres in the past and present, and how they affect our perception of the landscape. Part three: A look at the practical application of how an understanding of the visitor centre affects design at ground level. Part four; Case studies - Two case studies examining how two visitor centres have been related to the landscape. Part five: A look to the future and the implications involved. Also a conclusion and a summary of resources.