Search

This qualitative dissertation conducted a critical discourse analysis of youth and adult discourses about the transition to high school. Despite being a well-researched field, studies of the transition to high school and interventions in the transition to high school do not prioritize youth perspectives. To remedy this shortcoming and examine youth discourses, I collected data from youth giving advice about beginning high school on TikTok. By conducting a critical discourse analysis of these videos and comparing discourses from school website data and school counseling textbooks, I developed findings that showcase the complexities of the transition to high school and call into question views based solely on academic measures. Youth and adult discourses agree that timeliness, organization, and self-knowledge are important for a successful transition. Youth discourses uniquely focus on advice to avoid relational violence and present an ambivalent view of friendship. Discourses of school tours that showcase amenities and serve as advertising for the school are uniquely adult. I used these findings to theorize the transition to high school as a curriculum and call for a vision of youth and adults co-creating the transition-as-curriculum. [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.]

Breadboarding is an essential part of Do-It-Yourself (DIY) electronic music. It is often used to investigate, test or refine a design prior to the construction of a finished instrument. It is part of a well-established design process that is often regarded as a stepping-stone or means to an end, and breadboard-based prototypes are generally not viewed as practical or complete instruments in their own right. Instead, they are viewed as fiddly and imprecise, with their intermittent connections and delicately mounted controls. Despite these, and other shortcomings, breadboard-based instruments have a number of features and affordances that make them worthy of exploration as legitimate musical instruments. Furthermore, the practice of breadboarding can be seen as an act of musical composition or performance. This thesis sets out to define and defend a domain that I will refer to as breadboard music. I will also present an appropriate framework or set of strategies, including the underpinning logic and philosophy behind them. The research undertaken is practice-related and uses empirical and iterative processes to derive new knowledge and understanding of breadboard music and DIY electronic music. I refer to the research as practice-related because it is both practice-based and practice-led; as well as presenting a framework developed through the practice of creative breadboarding, I will also present a series of original artefacts in the form of creative works. To conclude, I explore the limitations of black box devices and the importance of breadboarding and experimentation as a means to combat the shortcomings of such designs. I postulate that despite advancements in technology, breadboarding will continue to remain relevant as a creative musical practice.

Nucleation and growth of crystalline substances from solution is ubiquitous in the production of active pharmaceutical ingredients. However, a basic understanding of nucleation is still lacking after many years of study. One major problem in studies is due to the stochastic nature of nucleation, causing direct observation to be challenging. One possible solution to this is to use optical tweezers to promote nucleation localised to the tweezer focus. Although temporospatial influence and control over nucleation is achievable, some secondary considerations not usually part of the design of crystallisation processes must be considered, with a focus on optical properties with the aim of limiting laser induced heating. A preliminary study was conducted to allow crystal nucleation and growth experiments performed using the optical tweezer setup to be fully understood within context, examining nucleation and growth kinetics up to a scale of 3 mL on high throughput platforms. This study examined the effect of deuterated solvent and doping with spherical microparticles. The use of deuterated solvents resulted in the reduction of primary nucleation rates. Its impact on secondary nucleation and growth depended on the crystallising material. Doping with spherical microparticles was particle material dependent, with silica promoting nucleation and polystyrene's effect being system and solvent isotopologue dependent. Optical tweezers allow direct control over localised growth of macroscopic crystals with the effect being dependent upon the solvent isotopologue, when using low laser power. Higher laser power allows the time and position of nucleation to be controlled within certain conditions of supersaturation, laser power and relative location of the tweezing focus within the solution. As well as allowing the growth rates of crystals nucleated from bulk undersaturated solutions to be measured, suggesting the enhancement of the local solute concentration in the region surrounding the optical tweezing focus.

Direct-fired supercritical carbon dioxide (sCO2) power cycles offer emissions-free electricity production from the combustion of fossil fuels. Chemical kinetic mechanisms are validated for combustion at lower pressures and much lower CO2 concentrations. The work critically investigates the ability of existing chemical kinetic mechanisms to simulate combustion under these conditions. This is done by investigating ignition delay time (IDT) data recorded using the shock tube experimental technique. The first key chapter of this Thesis details the development of a new High-Pressure Kinetic Shock Tube (HPST) at the University of Sheffield's (UoS) Translational Energy Research Centre (TERC). The HPST will be utilised for the research of high-pressure chemical kinetics. The project was delivered in the summer of 2022, with commissioning taking until the end of the year. The HPST will be used in a variety of research projects at the TERC from the combustion of supercritical CO2, ammonia, and synthetic aviation fuels. Chapter 3 details the development of a new chemical kinetic mechanism for modelling combustion in CO2. The University of Sheffield sCO2 mechanism (UoS sCO2) was developed based on IDT datasets of methane, hydrogen, and syngas. The UoS sCO2 Mechanism was developed and shown through a detailed qualitative analysis to be on average a better fit to the datasets measured for each of the three fuels. Chapters 4 and 5 focus on the validation of the UoS sCO2 2.0, the second iteration of the mechanism in collaboration with King Abdullah University of Science and Technology (KAUST). Eight IDT datasets for both hydrogen and syngas and ten for methane and methane hydrogen blends were recorded using the KAUST HighPressure Shock Tube between 20 and 40 bar. This data and subsequent modelling analysis are essential to the detailed understanding of the fundamentals of combustion in CO2.

Informed by a critical realist perspective and using a multiple case study methodology, this PhD study recruited, interviewed and analysed 12 cases of white South African (wSAn) learners in the post-apartheid era who reached a high proficiency in an indigenous African language (AfL) as a second or additional language (L2). The phenomenon of study, L2 AfL learning (L2AfLL) by wSAns, was characterised as a form of L2 indigenous language learning (L2ILL) by settler-descendants occurring in other post-colonial contexts like New Zealand and Kenya, among others. As an overall framing device, an investment metaphor was reconceptualised for the purposes of this study as the 'L2 Investment' framework - inspired, but divergent, from Norton's (1995) construct of investment and later investment model (with Darvin, 2015). Six core cases were selected and analysed in depth; in the cross-case analysis, these were complemented by a further six peripheral cases, in order to achieve a measure of analytic generalisation from the inclusion of limit cases (Campbell & Yin, 2018). Viewed through an L2 Investment frame, it was found that successful investment in L2AfLL occurred in cases with nominal access to AfLs in high school; ideal neurophysiology and prior human capital; and intrinsic motivation. For those who lacked such ideal personal conditions, guardian investment by parents was sufficient to catalyse investment behaviour, or the introduction of circumstantial necessity through moving to an AfL-dominant, rural area. All successful cases were found to have committed to a 'transgressive modality' of L2AfLL, in which class and spatial boundaries were overcome. This was undertaken either in isolation, or in addition to an academic modality (high school or university). Beyond a narrow focus on the conditions for and development of linguistic capital, fluency in an AfL was typically found to be leverageable for further social and symbolic capital, limited occupational gain, as well as what was termed zookairotic capital - e.g. emergent senses of rootedness, legitimacy, physical and psychological security, and joy. This emerged primarily for investors themselves, but also for most AfL-speaking interlocutors. Evidence was thus found for the value of multiple instances of symmetrical multilingualism (Orman, 2007), with implications for broader social welfare and nation-building.

The defence of plants against pathogen infection is a topical issue critical for maintaining food security in the face of climate change. Plants have evolved complex mechanisms to regulate gene expression, enabling transcriptional reprogramming in the face of threats like herbivores and infectious pathogens. Plant hormones are crucial signalling components which contribute to transcriptional reprogramming, and for stresses like herbivores and necrotrophic pathogens the hormone jasmonic acid plays a central role. Jasmonic acid perception occurs via the F-box protein Coronatine Insensitive 1 (COI1), which enables the targeted degradation of Jasmonate Zim Domain (JAZ) proteins, the focus of this work.

The β-barrel assembly complex (BAM), functions to fold outer membrane proteins (OMPs) into the outer membrane of diderm bacteria. High resolution structures of BAM exist in a variety of conformations, and in complex with OMP substrates that could represent folding intermediates. Despite this, the mechanism by which BAM folds its array of OMP substrates remains unresolved.

Nosocomial infections (those that are hospital-acquired) lead to patient morbidity and mortality, and are further complicated by the growing problem of antimicrobial resistance. Wastewater plumbing systems (WPS) are bacterial reservoirs and vehicles for bacterial transmission. Sink traps form a barrier between users and the WPS, but breaches can lead to contamination and have been implicated in outbreaks of infections. This project sought to address the need for a novel antimicrobial nanocoating to reduce bacterial colonisation and biofilm formation in sink traps. A nanocoating was developed by embedding silver nanoparticles in a matrix of commercially-available and low-cost pipe cement, applied to unplasticised polyvinyl chloride. Material characterisation and nanotopography imaging revealed that roughness was increased by surface grinding, with nanotopography images showing the troughs produced, and high silver stability was evident with very low dissolution under controlled dialysis experiment conditions. Culture-dependent and -independent techniques were used to characterise the bacteria present in hospital sink traps, revealing certain dominant genera such as Citrobacter, Pseudomonas and Serratia. Sequencing of 16S rDNA from sink traps has previously been an under-reported area. A bacterial isolate of interest, Cupriavidus pauculus MF1, was further investigated and found to be multidrug-resistant with biofilm formation comparable to Pseudomonas aeruginosa. Whole genome sequencing, producing a hybrid assembly of short- and long-reads, allowed annotation of a number of antibiotic and metal resistance and virulence factor genes of interest, supporting the suggestion that awareness should be increased for this and other opportunistic pathogens in hospital sink traps. Silver nanocoatings demonstrated potent antiplanktonic and antibiofilm activity against the nosocomial pathogens Pseudomonas aeruginosa, Acinetobacter baumannii and Enterococcus faecalis. Novel, more realistic experimental conditions were developed, first using a hospital sink trap community to colonise a benchtop model sink trap system. Antibiofilm activity was evident over long time periods, up to 11 days, but waned by day 25. Placement of silver nanocoated specimens in real-world sink traps in two university buildings provided little overall evidence of a consistent antibiofilm effect. Follow-up in vitro experiments using hospital and university building sink trap communities confirmed that the silver nanocoating was active against those same polymicrobial communities. It is possible that certain realistic environmental conditions mask the surface of nanocoatings and limit their activity, with relevance to antimicrobial nanocoating development in plumbing systems and other environments. The results indicate that there can be significant discord between in vitro and in situ experiments, emphasising the need for novel antimicrobial nanocoatings to be evaluated in real-world settings.

Reversibly switchable fluorescent proteins (RSFPs) switch between a highly and weakly fluorescent state upon photoexcitation. This switching is known to be driven by reversible photoisomerisation and a change in protonation state of the chromophore. However, the exact sequence of events after optical excitation is unclear. In this thesis, time-resolved crystallography and vibrational spectroscopy are used to study the ultrafast dynamics of a new RSFP. Time-resolved serial femtosecond crystallography (TR-SFX) is used to probe the trans/cis reaction and reveals ultrafast sub-Angstrom motions of the chromophore and surrounding hydrogen bonding network. The addition of a stokes pulse (shown to dump the excited state population) increases these displacements and allows assignment of the light-induced signals to a vibrationally excited electronic ground state structure instead of an excited state structure. Temperature analysis of the steady-state switching rates resolves an intermediate ground-state structure using conventional crystallography which supports the TR-SFX assignments. Ultrafast pump-probe vibrational spectroscopy confirms that excited state photoisomerisation occurs (~70 ps), proceeded by rearrangement of a nearby arginine residue (~7 ps) with deprotonation (trans-neutral/cis-anion) occurring between 2 ns - 1 ms. An additional dump pulse is then shown to repress product formation and reforms the ground state, further supporting the structural observations of the pump-dump-probe crystallography measurements. These results improve our understanding of photoswitching in RSFPs and have important implications for structural assignments in future TR-SFX experiments. Time-resolved serial synchrotron crystallography (TR-SSX) is an accessible and emerging technique for studying protein dynamics on millisecond timescales. Here, the trans/cis isomerisation of an RSFP is probed at 10 ms with a range of pump intensities to demonstrate precise control of the cis-state formation yields. The population transfer is resolved crystallographically using quantitative analysis of the occupancy, showing excellent agreement with optical flash-photolysis measurements. The issue of X-ray induced heating, which leads to partial thermal recovery, is also addressed. A temperature increase of 82-112 K is extracted for the fixed-target sample delivery used, which should be accounted for in all future TR-SSX experiments. Finally, the effect of pH on the protonation step is investigated by studying a RSFP mutant with a destabilised ground state conformation. Structural and spectroscopic evidence is presented for a new class of reaction at low pH, involving a cis-neutral/trans-cation isomerisation, in contrasts to the typical cis-anion/trans-neutral reaction at neutral pH. These steady-state observations expand our understanding of acid/base equilibria in the photoreactions of RSFPs.

The question of what makes a text 'literary' has been philosophically evergreen, stretching back to Aristotle's Poetics and weathering every critical approach through the modern era. Since the 1970s, researchers in the field of Empirical Studies in Literature (ESL) have tried to determine whether literary processing is principally text-directed (the formalist position) or reader-directed (the conventionalist position), based on observations of actual readers. Given the widespread characterisation of reading as intensely subjective, we might expect to see a huge diversity of response-yet major studies in ESL have reported results in favour of the formalist position. In expanding its sample beyond undergraduates, this survey-based study of Japanese poetry in English translation gives diversity of response a greater chance to emerge, and produces evidence suggesting that the case for the formalist position is not as strong as previously thought. Moreover, this thesis engages with recent work in Translation Studies to account for the translated-ness of its stimulus texts. Recognising translation as an important litmus test for understanding 'literariness,' this thesis operationalises a major contemporary theory of translation for the first time: Venuti's ([1995] 2008) theory of foreignisation. Against its proponent's objections, I make the case for the amenability of this theory to empirical testing, laying the groundwork for further study. Building on Eco (1990), I advance a useful new concept (intentio translatoris) to schematise the dynamics of reader response in Venuti's theory and explain the shifting criteria by which he describes translations as foreignising. Following an in-depth comparison between Russian Formalism and Venuti's foreignisation, I conclude that the latter theory does not totally escape the instrumental model it rejects. I do this to challenge unspoken assumptions about the translator as source of invariance, and to encourage a reassessment of the role of intentio lectoris in reading literature in translation.

An agitated tube reactor (ATR) has been converted from a commercially available flow chemistry reactor into a working solvent extraction contactor. It has been determined that the ATR has potential to be an industrial option for solvent extraction. Mass transfer coefficients have been calculated for a wide range of agitation frequencies and residence times using Cu(II) extraction by extractant Mextral® 84H. Mass transfer has then been compared to a Taylor-Couette Disc Contactor, and a novel design, presented in this work, called a D-cell contactor. Varying liquid volume by including an air phase has been shown to improve mass transfer within the ATR. The motion of liquid in the tube at each volume has also been monitored and compared against power per volume and droplet diameter calculations. In most operational parameters, liquid in the ATR is found to bypass agitation, therefore not achieving the expected extraction equilibrium. The volume of unmixed liquid is determined and a mass transfer coefficient for the mixed liquid is calculated. Based on the current design, optimum parameters are found when a tube is half filled and subject to an agitation frequency of 5 Hz. With these operational conditions, the ATR is shown to mix 95% of the fluid and reaches equilibrium within approximately 160 s. The viability of the ATR as a solvent extractor has been compared against a Taylor-Couette Disc Contactor and a Pulsed Column. It is seen that at 5 Hz, with 50% fill fraction, that the ATR produces a comparable mass transfer coefficient to a pulsed column correlation, as well as other mass transfer coefficients in literature.

Over the years, the expectations of public safety dispatchers have expanded considerably to include responsibilities that go beyond the traditional role of a dispatcher. People often associate the role of a dispatcher as being the first point of contact for someone experiencing an emergency and needing assistance. This study sought to assess the perception of the training effectiveness of the Public Safety Dispatch Academy using the first two levels of Kirkpatrick's Evaluation Model. Kentucky requires all full-time, public safety dispatchers attain certification from the Kentucky Law Enforcement Council (KLEC). Information was obtained the scores of written examinations during the training academy, and two questionnaires gauging student reaction to training before and after the academy. It was hypothesized dispatch academy students with a positive perception of training will experience higher scores on the written academic examinations than those with lower perceptions. It was also hypothesized students with positive perceptions of training will experience an overall higher average of learning than students with a negative perception of training. Survey results and examination scores from nine academies held over a 14-month period were reviewed and determined a modest level of learning occurred during the academy. Results indicate the students in the academy have an increase of learning as measured by written exam scores and their own perception of skill. Students who indicated the academy did not meet their training expectations still had significant increase in score from pretest to post. Students who answered they disagreed or strongly disagreed the academy prepared them for the job as a dispatcher still had an average 23.6-point increase in learning, just two-tenths less from those who agreed or strongly agreed. Student surveys indicated an increase in the perception of skill in three main job categories with 90 percent of students indicating the academy met their training expectations and 86 percent indicating the academy prepared them for the job as a dispatcher. There was a weak correlation between student perception of training on the surveys and increase of score on the written exam indicating an increase in learning. [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.]

Within institutions of higher education, shared governance is an essential component to a healthy functionality. Among the many stakeholders at these institutions, students are the largest in number and hold primacy. Participation in student governance establishes a sense of shared ownership over their communities while also providing a unique avenue for students to gain wisdom and develop critical skill sets. Senior administrators at these institutions have many inherent challenges due to an organization that is largely decentralized and autonomous (Duderstadt, 2007). Regarding agenda setting, the Garbage Can Model (Cohen et al., 1972) was utilized as a theoretical framework. The purpose for conducting this study was to analyze Student Government Associations (SGA) at 8 select land-grant institutions of higher education in order to establish the answers to 4 research questions. (1) How do student leaders at select land-grant intuitions of higher education describe their policy priorities? (2) How do the presidents at the same institutions describe their priorities in select institutional or media documents? (3) To what extent are the agendas of SGAs and institutional presidents aligned? (4) How did student body presidents describe their working relationship with their respective institutional leader and does that impact agenda alignment? The answers to these questions were found utilizing a qualitative methodology. Specifically, official documents from the SGAs were reviewed and coded. Additionally, the student body presidents of 6 of the 8 universities in question were subjects in a semi-structured interview. Finally, official university documents, public remarks, and media coverage were analyzed and coded to establish the policy agendas for each institution's president. The study found that Student Government Associations conduct policy implementation in the form of organizational management as the most prominent agenda item. In addition to that, it was shown that SGAs prioritize campus infrastructure improvements, campus safety, and the overall wellness of the student body. Presidents at the same institutions discussed issues related to research and innovation most prominently. They also prominently discussed campus infrastructure. The semi-structured interviews and document analysis showed a minimal alignment between the agendas. However, student body presidents indicated that they did not necessarily anticipate alignment given the differences in their constituencies. They also mostly described having positive relationships built upon mutual trust despite the lacking alignment. Institutional presidents were also found to rarely prioritize issues related to campus safety and sexual assault in direct contrast with SGAs. These findings emphasize the importance of shared governance within these institutions. Positive relationships between SGAs and their presidents emphasize constructive communication and reciprocity between the subjects which leads to more buy-in by stakeholders and innovative ideas. [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.]

Predicated upon the contention that higher education (HE) lecturers perform in their classrooms in ways which have similarities with the performances that theatrical performers give for their audiences; this research set out to observe, listen to, understand, interpret and then represent in text the meaning an aesthetic conception of performance has for a small number of teacher-performers in a single UK HE institution. Whilst classroom performances differ in content, presentation and delivery there is a fundamental commonality of purpose; each performance is given with the intention of establishing change in the student audience - broadly defined as learning. Learning may not be the declared intention of performance outside of the classroom; however, theatrical performers use language, movement and other expressive devices to engage and influence their audiences. Their performances therefore also change the audience; whilst the audience may not feel they have learned anything through a traditional understanding of learning, they often leave performances, in some respect, different. The aim of this research has been to seek out and examine similarities between the HE lecture - one of the “forbidden pedagogies” according to Burgan (2006, p. 31) - and a notion of performance developed for this research, and to explore whether an understanding of any such similarities might enrich the repertoire of the HE lecturer. There are significant volumes of literature available which refer, separately, to teaching and learning in HE and theatrical performance. However, a dearth of literature exists where those domains interact. This work identifies that gap in the literature and plays a part in addressing it. This two-phase research has been undertaken in a single UK HE institution, using a descriptive case study approach in the second phase of the work (Yin, 2014). The first phase of data collection involved twelve overt and non-participatory classroom observations each with a different participant. Fifteen overt and non-participatory observations were conducted in the first element of the second phase – three with each of five cases who are subsequently referred to as the players. The second element of data collection in the case study phase involved a single semi-structured interview with each of the players. A further single, semi-structured interview – outside of the case study – was conducted with Serena. Serena is a senior member of academic staff who also performs at Bright Club venues – where academic research is ‘performed’ in a comedy club environment to audiences made up of academics, students and the general public looking for a ‘good night out’. Data analysis has been undertaken using Template Analysis (TA); utilising NVivo software for the classroom observations in the first phase and a hand-coded approach for the analysis of the observations and the semi-structured interview transcripts in the case study phase. The research offers three conclusions; founded upon notions of similarity, collaboration and liaison. The research has concluded that there is evidence to demonstrate a significant number of points of similarity between classroom and theatrical performance. The presence of such similarity should therefore encourage collaborations between teacher-performers and colleagues experienced in performance practice from both within and without the HE academy. Such collaborations, in contributing to both initial teacher preparation and continuing professional development activities, have significant potential to enrich the performance repertoire of the HE lecturer. The final conclusion is that improved liaison of, to use the performance vernacular, an ensemblic nature - between teacher-performers and those in the HE institution who play key roles in designing, developing, allocating and resourcing spaces used for classroom performance - offers potential to improve the spaces in which the HE lecture is delivered and, through that, to enhance the classroom experience of HE students.

Regulatory B cells (Bregs) play a critical role in the control of autoimmunity and inflammation. IL-10 production is the hallmark for the identification of Bregs. However, the molecular determinants that regulate the transcription of IL-10 and control the Breg developmental program remain unknown. The aryl hydrocarbon receptor (AHR) is an environmental sensor that binds to a variety of ligands, including physiological compounds derived from the digestion of dietary components by commensal microbiota. Here, we demonstrate that AHR regulates the differentiation and function of IL-10-producing CD19+CD21hiCD24hi Bregs and limits their differentiation into B cells that contribute to inflammation. Chromatin profiling and transcriptome analyses show that loss of AHR in B cells reduces expression of IL-10 by skewing the differentiation of CD19+CD21hiCD24hi B cells into a pro-inflammatory program, under Breg-inducing conditions. B cell AHR-deficient mice develop exacerbated arthritis, show significant reductions in IL-10-producing Bregs and regulatory T cells (Tregs), and show an increase in T helper (Th) 1 and Th17 cells compared with B cell AHR-sufficient mice. The most abundant source of AHR ligands are derived from the diet and the metabolism of dietary tryptophan. We have previously established a link between microbiota-driven signals in the gut and the differentiation of Bregs. Of the gut microbiota-derived metabolites, the short-chain fatty acids (SCFAs) are the most well characterised. More recently, the SCFA butyrate has been demonstrated to act as an AHR ligand in an intestinal epithelial cell line. Given the association of butyrate with AHR activation and the supporting findings showing that butyrate promotes Treg function, these data led us to hypothesise that butyrate acts via AHR to enhance Breg suppression. Here, we demonstrate that mice supplemented with butyrate reduces arthritis severity by inhibiting the differentiation of GC B cells and plasma cells, whilst maintaining Breg numbers and promoting the suppressive function of Bregs. We show that supplementation of mice with butyrate, changes the composition of the microbiota to favour species which metabolise tryptophan; a major source of AHR ligands. Therefore, we hypothesised that butyrate controls the balance between pro-arthritogenic and regulatory B cell differentiation, through the generation of microbiota derived AHR ligands. To date, the AHR ligands which direct Breg function are unknown. We rule out that butyrate acts as a direct ligand of AHR and establish that supplementation with butyrate increases the availability of 5-Hydroxyindole-3-acetic acid (5-HIAA), a downstream metabolite of serotonin, which we identify as a novel ligand of AHR in B cells. Mice supplemented with 5-HIAA promote Breg function and suppress arthritis severity, only in mice with AHR-sufficient B cells. Thus, we identify AHR as a relevant contributor to the transcriptional regulation of Breg differentiation and show that microbiota in the gut influence Breg differentiation by increasing the availability of AHR ligands.

Composite materials are an attractive material for use in the aerospace and automotive sectors, due to their high specific strength and specific stiffness. However, most composites fail suddenly in a brittle manner, which may result in catastrophic failure. This inherent lack of tailorability in the mechanical response of composites has made their widespread application limited. Aligned discontinuous composites (ADCs) are a new type of material that offers increased mechanical tailorability, as subtle changes to the ADC microstructure can change its stress-strain response from high-strength linear elastic behaviour, to a non-linear response with high levels of pseudo-ductility. This work aims to understand mechanisms for mechanical tailorability in ADCs, and determine the suitability of ADCs for applications in real-world structures. A Virtual Testing Framework (VTF) is used and developed throughout this thesis, to give an in-depth understanding of the behaviour of ADCs. The VTF consists of a multiscale framework to simulate complete ADC specimens with hybrid or non-hybrid reinforcement; final failure of ADCs is simulated in the VTF by a non-linear fracture mechanics failure criterion. The VTF is successfully validated throughout this thesis against a variety of experimental data with good agreement. The first study explores the use of different hybrid fibre-type arrangements, to explore their influence on the pseudo-ductile behaviour of hybrid ADCs. The addition of a fibre-migration algorithm (used to capture the effects of fibre movement in ADCs during their manufacture), and developments to the fracture-based failure criterion, enable the VTF to successfully capture the effects of various levels of fibre-type grouping. Hybrid ADCs with larger groups of low-elongation fibres demonstrate a more brittle response, whereas intimate intermingling of the fibre-types increases pseudo-ductility. The ultimate strength and pseudo-ductility are then maximised by employing a fibre-type arrangement where the low-elongation fibres are completely isolated from one-another. Having shown variability in the fibre-type arrangement has a significant influence on tailorability, the concept of variability is explored further. Several new sources of variability and defects are added to the VTF, and the non-linear fracture-based failure criterion is further improved to accurately predict the failure of any type of ADC microstructure. The VTF indicates that the most critical source of variability (i.e. the source of variability that most readily promotes premature failure) depends on the microstructural design of the composite: hybrid-fibre ADCs are most sensitive to the fibre-type arrangement, while short-fibre non-hybrid ADCs are most sensitive to variability in the fibre overlap lengths, and long-fibre non-hybrid ADCs are more sensitive to weaker fibres. The VTF is then coupled with an intelligent optimisation routine to maximise the mechanical performance of ADCs that feature inherent variability. The use of a surrogate model helps minimise the number of design iterations before optimal design(s) are converged upon; surrogate modelling is also demonstrated to be invaluable when assessing the optimality of materials which feature high levels of inherent variability (such as ADCs). The true tailorability of ADCs is showcased, with an initial stiffness of 505 GPa, an ultimate strength of 1.92 GPa, or an ultimate strain of 3.92 % all achievable in ADCs via single-objective optimisation. While significant trade-offs between competing mechanical performance characteristics are found, useful combinations of mechanical properties remain, with an optimal ultimate strength & ultimate strain combination of 982 MPa and 3.27 %, or an optimal combination of 720 MPa yield strength & 1.91 % pseudo-ductile strain all possible. ADCs are shown throughout this thesis to fail by translaminar fracture, yet the resistance of ADCs to translaminar cracks has never been measured; the translaminar fracture toughness is therefore a key material property that must be characterised, to enable accurate failure predictions using the VTF, and to enable the use of ADCs as part of a damage tolerant structure. Specially-designed compact tension tests are performed to measure the translaminar fracture toughness of hybrid and non-hybrid ADCs for the first time in literature. Results show that the translaminar fracture toughness of non-hybrid ADCs is significantly higher than hybrid ADCs, and that analytical predictions of the translaminar fracture toughness are sufficiently accurate to ensure realistic failure predictions using the VTF. The new understanding and optimisation of aligned discontinuous composites demonstrates the feasibility of ADCs as an alternative material for the aerospace and automotive sectors. The models developed as part of this study can be used to support the design of new materials, perform parametric studies, and perform intelligent optimisation campaigns.

New challenges in structural biology are driving the development of new technology, such as photon counting pixel array detectors, and new modes of data collection, such as serial synchrotron crystallography (SSX), in macromolecular crystallography at synchrotrons. This in turn is creating the need for better algorithms and software to extract the maximum amount of information from the diffraction data. The aim of this project is to develop statistically robust methods for the integration and analysis of X-ray diffraction data to address these challenges. A method for estimating the background under each reflection during integration that is robust in the presence of pixel outliers is presented. This uses a generalised linear model (GLM) approach that is more appropriate for use with Poisson distributed data than traditional approaches to pixel outlier handling in integration programs. The algorithm is most applicable to data with a very low background level where assumptions of a normal distribution are no longer valid as an approximation to the Poisson distribution. A second algorithm for modelling the background for each Bragg reflection in a series of X-ray diffraction images containing Debye-Scherrer diffraction from ice in the sample is also presented. This method involves the use of a global background model which is generated from the complete X-ray diffraction dataset. Fitting of this model to the background pixels is then done for each reflection independently. Finally, a model for the observed reflection profiles is described for the purpose of improving the refinement of the crystal unit cell and orientation for still image diffraction data collected at synchrotrons. This model consists of two components: a Normal distribution is used to describe the distribution of wavelengths and a Multivariate Normal distribution (MVN) is used to describe the distribution of reciprocal lattice vectors for each reflection; this allows non-isotropic spot shapes to be easily described. The parameters of the model are estimated from the data via a simple maximum likelihood algorithm. The algorithms are incorporated into the DIALS integration package.

Feedback in higher education (HE) is an important determinant of student success despite its variable impacts. Assessment and feedback have also been highlighted as one of the least satisfactory aspects of the learning experience. However, more scholarship has focussed on what constitutes ‘good feedback’ than about the factors that influence how it is perceived, engaged with, and used by students. This study aims to redress this imbalance by investigating what measures can be taken by teachers to support feedback engagement processes. It explores how the existing literature on dialogism, technology, can be synthesised into a new model of feedback engagement. Principles from the resulting USM model were employed in the design of dialogic technology-mediated feedback practices used over a semester with 14 South Korean undergraduates on an academic writing course. Utilising a qualitative approach, data from reflections, questionnaires (N=14) and the main method, in-depth semi-structured interviews (N=13), were analysed to understand perceptions of the relationship between navigating the feedback activities and feedback engagement and use. The data was also used to consider how the model could be empirically enhanced. The findings were analysed inductively, and the practices reportedly contributed to feedback engagement in four ways. Dialogism supported understanding of peer/teacher feedback, facilitated group knowledge co-construction, and motivated feedback engagement. Open access to peers’ work helped participants to make comparisons and understand how their work could be improved. Screencast feedback was perceived to be more thorough, usable, and affectively supportive. After initial disappointment with feedback, participants reportedly engaged with the feedback by employing certain pre-introduced concepts related to learning from feedback. Overall, the practices were demonstrated to support the development of feedback receptivity. The data supported contributed to the refinement of the USM model; thus, contributions to both theory and practice were made.

This thesis presents a joint computational and experimental approach to developing a novel diamond surface termination with aluminium that has a negative electron affinity (NEA). There is a need for a thermally stable NEA for thermionic applications, since hydrogen termination desorbs from the diamond surface at thermionic temperatures. The choice of aluminium is based on it being a light, electropositive element that bonds strongly to different diamond surfaces. Using density functional theory, the adsorption of Al onto bare, oxygenated and nitrogenated diamond surfaces was studied. The two key parameters considered were the adsorption energy and the electron affinity values, for different coverages and configurations of Al. NEA values of up to -1.47 eV and 1.88 eV were observed for Al addition to the (100) and (111) bare surfaces, respectively, at 1 monolayer (ML) coverage, and up to -1.36 eV and -2.17 eV for Al addition to the (100) and (111) oxygen-terminated surfaces, respectively, at 0.25 ML coverage. Al adsorbed more strongly on the ketone O-terminated surface than the ether surface. Adsorption energies for the AlO-terminations were up to -6.36 eV/atom and -8.19 eV/atom for the (100) and (111) surfaces, respectively, at 0.25 ML Al coverage, considerably larger than that of H termination (~-4 eV/atom). Three different oxidation procedures were investigated experimentally. It was determined that oxidation of diamond by UV/ozone treatment results in a large ketone component on the surface, whilst also having ~1 ML coverage. The surface structure and electronic behaviour were determined for both hydrogen and oxygen terminations. AlO-terminations were fabricated experimentally by depositing Al onto O terminated diamond. Three different methods were explored: (i) thick-film deposition of Al followed by an acid etch to remove excess metal, (ii) thin-film deposition of Al by atomic layer deposition, and (iii) thin-film deposition of Al by electron-beam evaporation. Low work function and NEA were observed for each method, but these values were spatially and temperature dependant. Annealing caused a change in surface structure, identified as the incorporation of O atoms into the Al layer. Tests of thermionic emission showed a small emission current density, but at a higher temperature than attainable for H termination. Thus, AlO-terminated diamond shows promise but further optimisation is required for use in devices.

The thesis examines shifting representations of trade unions in the work of six contemporary poets. The thesis considers how it is that poets have come to contend with, and contribute to, narratives surrounding trade unions and industrial disputes, and puts these representations into conversation with one another. Through these conversations, the thesis attempts to question the ways in which our union narratives and our legacies are constructed, and to investigate the power dynamics that underpin the presentations of our histories (and the way they are presented to us), through a specific focus on what it means to tell the stories of our labour histories. Trade unions have long been at the forefront of the struggle for working conditions, pay and labour polics more broadly in the UK. Taking unions as the 'subject' and using poetry as the 'medium' enables the thesis to investigate the ways in which union narratives have come to occupy the relatively marginalised position they currently inhabit in the UK's polical and social landscape, while also putting forward an argument for these poems to be seen as a form of alternative 'storytelling', where questions of dominant narratives and official histories can be rightly contested. The fact that trade unions are as much about the individual as they are the collective ties into the poem's ability to affirm and extend 'community by being true to what is individual and particular'. My attention to trade unions allows an exploration of questions regarding shifting ideas of the collective, the individual and notions of (post-industrial) place. The thesis focusses on two distinct poetic eras: from 1972 to the late 1980s through the work of Barry MacSweeney, Tony Harrison and Sean O'Brien, and the 2010s, through the writings of Helen Mort, Steve Ely and Paul Bentley. The poems discussed bring influences from other poems, from movies and from 'official' narratives on to the page, sometimes brazenly, sometimes obscured, but always with a sense that they are writing out of and into a trade union history. The thesis explores these influences and that engagement with trade union history. The poets that my research examines see our union legacies as artful constructions, foregrounding an awareness of working-class stories and histories as products, products that have been manufactured and arranged, in the same way that the poems themselves are artfully rendered and established on the page. These poems (and my work) are a continuation of, and comment on, the 'legacy' of these trade union stories and histories.

The ritual and incantation series Šurpu 'Burning' is one of the most important sources for understanding religious and magical practice in the ancient Near East. The purpose of the ritual was to rid a sufferer of a divine curse which had been inflicted due to personal misconduct. The series is composed chiefly of the text of the incantations recited during the ceremony. These are supplemented by brief ritual instructions as well as a ritual tablet which details the ceremony in full. This thesis offers a comprehensive and radical reconstruction of the entire text, demonstrating the existence of a large, and previously unsuspected, lacuna in the published version. In addition, a single tablet, tablet IX, from the ten which comprise the series is fully edited, with partitur transliteration, eclectic and normalised text, translation, and a detailed line by line commentary.

Sporadic Creutzfeldt-Jakob Disease (sCJD) is the most common form of human prion disease. It is a rapidly progressive dementia with other associated neurological abnormalities which is invariably fatal, usually within 4-6 months of first symptoms, and affects around 80-100 patients in the UK each year. It is caused by propagation around the central nervous system of PrPSc, an abnormal conformational form of the host PrPC protein, which causes the transformation of PrPC to PrPSc, essentially self-replicating. This process causes neuronal loss and other pathological abnormalities, explaining the clinical presentation. sCJD is believed to occur as a de novo convolutional change which seems to occur as an unfortunate chance event. The existence of other forms of CJD, including variant CJD (vCJD) and iatrogenic CJD (iCJD) highlight the fact that the abnormally folded forms of the prion protein are infective agents, which can be transmitted by diet (from bovine spongiform encephalopathy - BSE - in cattle to humans in vCJD), or by medical intervention (predominantly from contaminated dura mater grafts, and cadaveric pituitary derived growth hormone in iCJD). These two routes of transmission can be associated with long intervals (up to around 40 years has been described) between exposure to the infective agent and subsequent symptom onset. It is possible that some cases classified as sCJD may in fact be acquired through other means of transmission. As part of the UK National CJD Surveillance process, the NCJDRSU collect data on potential routes of CJD transmission. In this thesis, I describe and analyse the data concerning three potential such routes for the definite or probable cases of sCJD reviewed by the NCJDRSU between 2010 and 2015 inclusive: 1) Packed red cell blood transfusion has been associated with iatrogenic transmission of variant CJD. We found no evidence of such transmission in sporadic CJD. I also describe the first two reported cases of sCJD occurring in patients with clotting disorders who had received numerous transfusions and other blood products; there have been no further published cases since this report, and these two cases are considered likely both to represent the chance development of sCJD. 2) Tissue and organ transplantation is another recognised route, with iatrogenic transmission of CJD described in corneal transplantation. A small number of sCJD patients have undergone surgery involving transplantation of tissues or organs. Although a few cases of interest were identified as recipients of potentially infective materials, including three patients who are suspected to have received dura mater grafts and one patient who underwent definite corneal transplantation, it was not possible to confirm the exact nature and source of these materials, meaning it is not certain that these cases definitely represent iatrogenic transmission. Therefore, I found no evidence that tissue or organ transplantation is responsible for the development of cases of iCJD among this patient cohort. 3) Other surgical procedures may convey the risk of transmission of PrPSc through incomplete sterilisation of instruments. I assessed the potential for UK sCJD patients to have come into contact with instruments used on another CJD patient, looking at associations between surgical procedures occurring within the same year, at the same hospital, and within the same surgical domain. While some such associations were identified, interpreting these associations is extremely difficult, in large part due to the absence of a suitable control group, as well as incomplete data availability. Overall, this work has identified no definite transmission of iCJD masquerading among the sCJD 2010-2015 patient cohort. There are significant limitations to each aspect of this work, in large part pertaining to incomplete medical records; these limitations are addressed in the relevant chapters. Some of these limitations may be difficult to overcome if future these studies are repeated in the future with a new cohort.

The prevalence of type 2 diabetes mellitus (T2DM) worldwide has increased dramatically in the last three decades. In 2014 there were 64.5 million individuals with diabetes in India alone. South Asians (SA) have a two to fourfold increased risk of T2DM at a significantly lower body mass index (BMI), occurring at a younger age and with a greater risk of diabetic related complications, when compared with white Europeans (EU). The rise in T2DM rates have coincided with increased levels of adiposity, 'westernised' diets and lower levels of physical activity, with more people living in urbanised environments. Even adjusting for these variables SA still have an increased risk of T2DM and the reason for this is unknown. Observational studies have demonstrated that SA phenotypically have higher levels of total fat (adipose tissue), less lean tissue (muscle), and lower cardiorespiratory fitness, as well as typically undertaking less physical activity compared with their EU counterparts. Whilst studies have indicated that these factors contribute to insulin resistance with varying degrees, the relationship between adipose tissue (AT) and insulin resistance has never been properly understood. Triacylglycerol is the main storage form of fat. Due to poor diet and lower levels of physical activity, excess calories are stored in adipocytes in several adipose tissue depots in the body. Location of depots appears important, and evidence indicates that visceral (VAT) and ectopic fat depots significantly correlate with insulin resistance. Subcutaneous adipose tissue (SAT), and specifically superficial subcutaneous adipose tissue (SSAT) depots, have been associated with lower levels of insulin resistance and metabolic inflammation. As well as fat depot location cellular response of adipocytes is relevant, adipocytes can either expand in size (hypertrophy), or increase in cell number (hyperplasia) to accommodate excess energy. Hyperplasia has been associated with lower levels of inflammation and insulin resistance whilst hypertrophy has been associated with increased risk of T2DM and pro-inflammatory metabolic state. Adipogenesis is the process by which new adipocytes are recruited and fully differentiate to mature adipocytes with the ability to safely store triacylglycerol. Impairment of this process and dysfunctional adipogenesis has been associated with insulin resistance, T2DM, increased number of hypertrophic adipocytes, small adipocytes and ratio of small to large adipocytes. South Asians have higher levels of total fat compared to EU, and it has been commonly presumed that more visceral and ectopic fat is present in SA causing insulin resistance. However, the limited number of studies analysing fat depots in SA have not all consistently demonstrated this. Cross-sectional studies of SA adipocyte morphology and function have found hypertrophic adipocytes associated with insulin resistance, but the causality and pathogenesis underlying these observations is not known. In 2007 the adipose tissue expandability hypothesis was proposed, implying that SA have limited ability to safely store fat in SSAT and therefore store excess fat in visceral and ectopic depots, causing insulin resistance and diabetes. To explore the relationship between adiposity and insulin resistance in South Asians the Glasgow Visceral and ectopic fat with weight gain in South Asians (Glasvegas) study was proposed in 2014. This thesis is based on initial findings as part of the Glasvegas study and includes meta-analysis conducted to investigate adiposity distribution in South Asians. Given limitations of cross-sectional research the best way to observe underlying mechanisms is via a prospective weight gain/overfeeding study. In this thesis a group of male SA and EU participants gained ~6.4% body weight via supplemental overfeeding diet. Measurements were taken at baseline and following weight gain. These included whole-body MRIs to analyse fat depots, metabolic rate assessments, fitness tests, mixed-meal tolerance tests, subcutaneous adipose tissue biopsies, physical activity and dietary measurements. The findings of this thesis demonstrated that whole-body insulin sensitivity decreased by 38% in young, lean South Asian men with ~6.4% weight gain, but not in white Europeans. Adiposity analysis indicated that South Asians at baseline had more total fat, subcutaneous, deep subcutaneous (DSAT) and liver fat, but not visceral fat. South Asians had twice as much DSAT compared to EU (0.17 litres vs. 0.08 litres, p=0.003) and more liver fat (4.11% vs. 2.05%, p=0.01). Meta-analysis of studies of SA adipose distribution supported the finding that male SA have more SAT but not necessarily VAT. The novel aspect of this study was prospective overfeeding. Unexpectedly the EU group gained more VAT than SA (0.56 litres vs. 0.23 litres, p=0.005) but there were no differences in liver or muscle fat gained between groups. White Europeans also gained significantly more lean tissue with overfeeding than SA (2.43 litres vs. 0.67 litres, p=0.02). There was no indication of a limited SSAT capacity in SA, which is contrary to expectations and the adipose tissue expandability hypothesis. Correlations were observed in SA with insulin resistance and the deep subcutaneous adipose tissue depot, which is larger in South Asians and metabolically akin to VAT. There were no contributions of fitness, physical activity or metabolic rate accounting for differences in insulin sensitivity. Adipocyte findings indicated that EU increased size of adipocytes by hypertrophy in response to weight gain, without any change in insulin sensitivity. South Asians conversely already had larger adipocytes but did not change mean size with weight gain. South Asians increased numbers of very small and large adipocytes, and this is associated with dysfunctional adipogenesis and T2DM. There was also a trend to adipocyte hyperplasia noted in SA. The combined findings of this thesis supported our hypothesis that SA would develop insulin resistance with weight gain, but adiposity findings were contrary to expectations. South Asians appear to have more subcutaneous and deep subcutaneous fat, but not visceral fat. This likely contributes to excess insulin resistance at lower BMI and there is evidence of dysfunctional adipogenesis with weight gain. Ongoing analysis of samples taken during this thesis, to investigate adipocyte gene expression and signalling pathways, is underway. Future studies are also required to help prevent adiposity in SA, reduce risk of dysfunctional adipogenesis and type 2 diabetes.

Schools once enjoyed the implicit trust of their community, and school leaders felt that they could take for granted the trust of both the internal and external constituencies. Trust in our society seems to be damaged and is in short supply (Tschannen-Moran, 2014). The Millennial generation (individuals born in the years 1981-1996) has become our largest workforce, and while their numbers are flooding the education ranks, there is a dearth of research on this talented generation of educators that needs to be uncovered. The purpose of this study was to assess the perceptions of Millennial teachers about developing trust with the building principal, their perceptions about establishing trust with colleagues, and their perceptions about forming trust with students and parents in a school setting. While there has been some research dedicated to the study of the Millennial generation in the workplace, there appears to be minimal research which contributes to an understanding of how school districts and building administrators can support Millennial teachers. This mixed-methods study provides quantitative and qualitative measures to school districts that pertain to Millennial teachers' perceptions of trust in a school setting. An analysis of the data indicated four emerging themes from this study of Millennial teachers' perceptions of trust namely, the influence of the principal as a coach; the impact of consistency in words and actions; the importance of a collaborative and supportive working environment; and the significance of honest and open communication. Through an understanding of the needs of the Millennial teachers, the findings of this research study provide school districts with evidence that could positively impact Millennial teachers' work environments and help to retain them in the profession. [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.]

This thesis explores the social construction and performance of Technological Human Enhancement Advocacy through multi-sited ethnographically inspired participant observation across a range of sites. It argues that advocacy efforts surrounding the ideal of technological human enhancement share the ideational feature of Techno-centrism - an object-level belief embedded in the material present while simultaneously future-oriented and thus principally immaterial. This purposive neo-dualism blurs 'real' and 'imagined' futures to satiate the materialist ontological grounding associated with the scientific worldview, while granting extended licence to more indulgent, compelling visions for technology as an enabler of affirmative, forward-facing action - including revivifying pursuit of humanist ideals associated with the modernisation project. The thesis makes contributions to three areas. Firstly, in substantive terms, it contributes towards sociological knowledge by detailing the intersubjective values, semiotic framing mechanisms and narrative tropes evoked to both justify and promote the notion of Technological Human Enhancement Advocacy (THEA), an area which remains under-researched. Secondly, the thesis makes a theoretical contribution through its modelling of a non- spatially determined constant which recurs across sites associated with THEA: The Techno-centred Imagination (TCI). Finally, the thesis offers a methodological contribution through its novel and creative application of multi-sited research strategy for the study of non-spatially determined cultures of extreme support for science and technology. A 24-month programme of fieldwork was undertaken, comprising multi-locational participant-observation, interviews and surveys. The thesis concludes that far from being new, the emerging social forms associated with THEA capture ambivalences which have long cast a shadow over late-modern society and culture. Although TCI appears most pronounced in the practice of transhumanism - where it is acted out in extreme, almost hyperbolic ways - the phenomena mirrors broader concerns around the future of science, technology and human self-identity in the new millennium. As such, it is deserving of further study.

The purpose of the thesis was to investigate if producing a slurry made from char particles could be used as a locally sourced alternative to diesel in developing countries for making electricity with engine generators. The lack of access to electricity in many areas of developing countries is seen as one of the biggest barriers to economic development. The research investigated all aspects of char slurry fuels including sourcing suitable feedstocks, conversion to char, micronisation and combustion in an engine. A slurry fuel testing facility was built for the purpose encompassing a small diesel engine generator, typical of what is available in developing countries for producing electricity. Analysis of a wide selection of chars made from several types of material showed that woody biomass was the most suitable for producing slurry fuels. The majority of chars made from agricultural residues were not suitable as the silicon content is likely to cause wear issues in engines. The grindability of chars made from biomass was good and the energy requirements to micronise to particle sizes suitable for an engine were small enough to make producing slurry fuels economically viable. It was recommended that low pyrolysis temperatures are used to make char for slurry fuels because they burn better in an engine whilst still having a high grindability. Two 10%wt. char-diesel slurry fuels were tested, one using a pyrolysis char, the other using a hydrothermal carbonisation (HTC) char. It was found that the HTC char burned better, producing less CO, THC and soot than the pyrolysis char based fuel because the carbon was less recalcitrant. Issues were found with the engine when using slurry fuels, particularly the injector needle which would sieze. Investigating better injector design and engine construction materials is a priority to make slurry fuels viable for developing countries.

Oligometastatic colorectal cancer represents an intermediate disease state potentially treatable with curative intent. Novel treatment strategies are expanding the opportunity to offer local treatment for limited metastatic disease. It is therefore increasingly important to define patients likely to benefit from these targeted treatments. Diagnostic imaging is central to patient management, to establish the burden and distribution of metastatic disease. This thesis explores the potential value of novel imaging biomarkers in patients with colorectal liver metastases (CRLM). In a prospective study, perfusion CT (pCT) and dynamic contrast-enhanced MRI (DCE-MRI) were performed prior to resection, and a retrospective series of patients with resected CRLM was collated. Resected metastases were analysed for relevant morphological features and IHC expression. Novel and conventional imaging variables were derived based on CT, MRI, pCT, DCE-MRI and 18F-fluorodeoxyglucose positron emission tomography (18F-FDG-PET), and their associations with histopathological features, immunohistochemical expression and patient outcomes analysed. A novel subregion analysis based on DCE-MRI data was developed to classify tumour subregions, using a histological reference standard. The results presented in this thesis confirm that the number and distribution of hepatic metastases are prognostic markers for patients with resected CRLM, and that higher SUVmean of liver metastases, and higher SUVmax of the background liver, are potential prognostic biomarkers. Histopathological assessment of resected CRLM highlighted that there is significant between and within patient variability of clinically relevant histopathological features and IHC expression, which would support the potential utility of imaging biomarkers to characterise multi- site disease. Analysis of functional imaging data demonstrated positive correlations between imaging variables and clinically relevant markers of tumour vascularity and metabolism, while subregion analysis of DCE-MRI data produced good spatial correlation with viable and non-viable tumour based on histopathology, with significant differences in derived phamacokinetic parameters between subregions.

Future pre-eclampsia research should ultimately improve patient care. For this to be possible, randomised trials must select, collect, and report outcomes that genuinely reflect the perspectives of key stakeholders, including healthcare professionals, researchers, and women with pre-eclampsia. The objective of this study was to develop a core outcome set for pre-eclampsia, along with standardised definitions, to ensure outcomes and outcome measures are consistently selected, collected, and reported across future primary research, secondary research, and clinical practice guidelines. A long list of 116 potential core outcomes was developed by undertaking a systematic review of 79 published pre-eclampsia trials and thematic analysis of 30 in-depth interviews of women with lived experience of pre-eclampsia. The long list of potential core outcomes was entered into a modified Delphi method. Four hundred and thirty-two participants, including 281 healthcare professionals, 41 researchers, and 110 patients, representing 31 high-income countries and 25 low- and middle-income countries participated in a three-round Delphi survey. One hundred and fifty-nine participants (37%) withdrew. Forty-seven consensus outcomes were identified and entered into a modified nominal group technique. Eleven healthcare professionals, two researchers, and three women with lived experience of pre-eclampsia prioritised 14 maternal, four fetal, and four neonatal core outcomes. A long list of 86 potential definitions were identified by reviewing four formal definition development initiatives, eight international and national guidelines, 11 Cochrane systematic reviews, and 79 pre-eclampsia trials. During a consensus development conference involving ten healthcare professionals and three researchers, consensus definitions were successfully developed for all core outcomes. Embedding the core outcome set within future pre-eclampsia research could make a profound contribution to advancing the usefulness of research to inform clinical practice, enhance patient care, and improve maternal and offspring outcomes.

This thesis is a study of aboutness. It defends the claim that we have singular thoughts about ordinary objects and argues that an essential part of how we do so is by maintaining singular representations. This proposal allows us to avoid traditional, unsatisfying conceptions of the scope of singular thought while restoring the sense in which such thought is a distinctively epistemic achievement. Reconnecting the study of aboutness with epistemology promises to alleviate the sense of directionlessness in the contemporary literature, offering a firmer grip on the phenomenon along with new, systematic resources for its investigation. Chapters 1-2 explore the effects of contextualist machinery on orthodox views about singular thought. It is widely thought that if there is to be a plausible connection between the truth of a de re attitude report about a subject and that subject's possession of a singular thought, then there can be no acquaintance requirement(s) on singular thought. Chapter 1 shows that this view rests on a faulty picture of how we talk about attitudes. Indeed, the truth of a de re attitude report cannot be taken to track the singular/non-singular distinction without collapsing it. A new, contextualist picture is needed. That there must be a distinction between singular and non-singular intentionality is emphasized in Chapter 2, where a key explanatory role for singular thought - brought out by a thought experiment due to Strawson - is examined. I show that the role does not call for any distinctive kind of mental content. Once we abandon the two widespread views questioned in Chapters 1-2, our grip on the phenomenon of singular aboutness is loosened: it is not constitutively tied to the kinds of attitude-reporting data or mental content by which it is often assumed to be revealed. Where are we to look for insight? What makes something the object of a singular thought? According to Russell, it is a datum of intuition that singular thought involves a kind of knowledge; a theory of aboutness will precisify the intuitive notion of 'knowing which thing one is thinking about' in order to capture this demand in a philosophically revealing way. If Russell is right, teasing out this connection to knowledge will allow us to see what it takes for a particular thing to be the immediate subject matter of thought. Chapter 3 discusses Evans's theory of this kind. Chapter 4 examines recent work by Dickie. While serious concerns emerge in each case, insights recovered are used to precisify Russell's requirement, leading to a novel picture of singular representation and the epistemic character of this achievement. While the chapters follow a narrative, providing an extended rationale for the proposal in Chapter 4, each may be read in isolation by those familiar with the philosophical issues. For those who are not, the Introduction provides sufficient background.

Vehicle electrification is a technology pathway being adopted by original equipment manufacturers (OEMs) to either reduce or eliminate tailpipe emissions. However, electric vehicles (EV’s) that employ a rechargeable energy storage system (RESS) still face significant barriers within the marketplace when compared to incumbent internal combustion engine (ICE) vehicle technology. One of these barriers is ensuring that the RESS lasts the life of the product or maintains customer satisfactory performance over a warranted life (such as 10 years or 100,000 miles of customer usage). There has been comparably little published research critically examining the effect of vibration on high voltage (HV) batteries within battery electric vehicles (BEV) and hybrid electric vehicles (HEV). Subsequently the effects of vibration on RESS components and subsystems are potentially a major cause of in market durability failures. The following thesis presents the findings from an International Engineering Doctorate (EngD (int.)) investigating factors influencing the vibration durability of HV batteries and components. This research programme has the objective of providing the underpinning knowledge that allows manufacturers to improve the mechanical durability and performance of EV battery assemblies with respect to vibration. This objective has been achieved through several novel studies within three primary areas of investigation. Firstly, the research focused on defining the “in-service” vibration environment of BEV components and assemblies through the analysis of vibration measurements from contemporary BEVs. This study was the first to synthesise a vibration profile that is representative of a durability life of 100,000 miles of UK customer usage from multiple real world BEV measurements. The presented profile can be employed by academics and engineers to underpin future vibration durability assessments of BEV battery components. The second avenue of investigation was to characterise the natural vibration and modal response of EV components and assemblies. This was to determine their susceptibility to vibration excitation, as identified from measurements of the in-service environment. It was also the first of its kind to fully characterise the natural vibration characteristics and mode shapes of lithium-ion pouch cells via modal analysis techniques. The final objective was to determine the durability behaviour of EV components and assemblies, by subjecting them to vibration, via state of the art single and multi-axis test techniques, which were the equivalent of a typical vehicle life (10 years) or customer mileage (100,000 miles). As well as defining the degradation characteristics of a contemporary BEV module and multiple EV cells, the impact of packaging variation and state of charge (SOC) on cell ageing was also determined. In conclusion, this research thesis defines innovative testing techniques and characterisation data, which can be employed by engineers to predict the warranty performance, with respect to the effects of in-service vibration, of future EV battery assemblies.

This thesis explores how the changing masculinities of the 21st century have affected how young men connect to musical theatre as a genre that has been stereotypically seen as gay. The investigation is first located in the theoretical framework of masculinities, utilising the concepts of the male sex role, hegemonic masculinities and inclusive masculinity to chart how the performance of the male gender has changed over the past century. The project then adopts an empirical approach to a group of 161 men and 25 women, establishing a methodological framework for correlating sexual orientation with attitudes towards musical theatre. There is a further honing of this methodology through the adoption of Jenifer Toksvig's 'The Fairytale Moment' exercise, which identifies how each participant connects to narrative through a core emotional drive. Finally, this data is tested through three case studies of how individual participants connect to 'Les Misérables', 'Wicked' and 'Soho Cinders', concluding that the emotional content of musical theatre is now as desirable to straight men as it is to women and LGBT men.

In twistor theory the nonlinear graviton construction realises four-dimensional antiself- dual Einstein manifolds as Kodaira moduli spaces of rational curves in threedimensional complex manifolds. We establish a Newtonian analogue of this procedure, in which four-dimensional Newton-Cartan manifolds arise as Kodaira moduli spaces of rational curves with normal bundle O + O(2) in three-dimensional complex manifolds. The isomorphism class of the normal bundle is unstable with respect to general deformations of the complex structure, exhibiting a jump to the Gibbons- Hawking class of twistor spaces. We show how Newton-Cartan connections can be constructed on the moduli space by means of a splitting procedure augmented by an additional vector bundle on the twistor space which emerges when considering the Newtonian limit of Gibbons-Hawking manifolds. The Newtonian limit is thus established as a jumping phenomenon. Newtonian twistor theory is extended to dimensions three and five, where novel features emerge. In both cases we are able to construct Kodaira deformations of the flat models whose moduli spaces possess Galilean structures with torsion. In five dimensions we find that the canonical affine connection induced on the moduli space can possess anti-self-dual generalised Coriolis forces. We give examples of anti-self-dual Ricci-flat manifolds whose twistor spaces contain rational curves whose normal bundles suffer jumps to O(2 - k) + O(k) for arbitrarily large integers k, and we construct maps which portray these big-jumping twistor spaces as the resolutions of singular twistor spaces in canonical Gibbons-Hawking form. For k > 3 the moduli space itself is singular, arising as a variety in an ambient complex space. We explicitly construct Newtonian twistor spaces suffering similar jumps. Finally we prove several theorems relating the first-order and higher-order symmetry operators of the Schrödinger equation to tensors on Newton-Cartan backgrounds, defining a Schrödinger-Killing tensor for this purpose. We also explore the role of conformal symmetries in Newtonian twistor theory in three, four, and five dimensions.

Liquid Lewis acids based on boron(lll), Aluminium(lll), Gallium(lll), and antimony (III) chlorides were all synthesised and characterised by spectroscopic and physical measurements. These liquid Lewis acids fall into 2 categories, Al and Ga based liquid coordination complexes (LCCs) and B and Sb based ionic liquids. The ionic liquids were synthesised to have a Lewis acidic cation, as halometallate ionic liquids typically have Lewis acidic anions. Boron based borenium ionic liquids, and liquid coordination complexes were both shown to be highly acidic, meaning potentially be utilised much like chloroaluminate ionic liquids, which have received much attention for their acidic catalytic abilities. The strategy used to synthesise borenium ionic liquids was successfully applied to SbCI3 as well. The successful synthesis of commercial quality lubricants by 1-decene oligomerisation was achieved using both LCC catalysts and with borenium ionic liquids. These catalysts represent safer, “greener” alternatives to the current industrial catalyst, BF3.

Polymer nanocomposites represent a growing and important field from academic, environmental, and commercial viewpoints. Filled rubber composites of car tyres are a prime example, as improvement of the material properties and reduction in the carbon footprint are both of interest. However, even with continued research into this subject, questions remain concerning the causes of the observed properties of these composites, namely the non-linear reinforcement and the presence of significant strain softening. This report documents the examination of polybutadiene rubber composites with multiple techniques to characterise and determine the cause of the non-linear phenomena. The macroscopic material properties were characterised with rheological measurements, while the nanoscale composite structure and polymer dynamics were examined with small angle neutron scattering and quasi-elastic neutron scattering, respectively. Different filler compounds, carbon black, precipitated silica, and Stöber silica, were utilized to provide additional data to build an improved picture of the composite systems. A hydroxyl end functionalised polybutadiene chain known to segregate to silica substrates was used for examination of polymer interfacial dynamics and changes to composite material properties when used as an additive. Reinforcement of the rubber with the addition of all the fillers was noted and analysed to determine the causes. A significant observation was the change in the mechanical properties of the silica filler composite with the presence of the end functionalised polybutadiene; decreased reinforcement and changes to behaviour under significant strains were noted. Changes to the nanoscale correlations of the silica filler with the presence of the end functionalised polybutadiene was observed with small angle neutron scattering, and determined to be from steric stabilisation of the silica particles. Hindered polymer dynamics near the silica filler surface were noted with quasi elastic neutron scattering. Neither the particle correlations nor the polymer dynamics were found to shift with the application of strain to the composite samples, in contrast to the alterations noted in the mechanical properties. From the information gathered on the composite microscopic and macroscopic properties a model for the composite behaviour was devised. The reinforcement of the rubber with the addition of filler material was determined to be a result of the networking of the filler particles. The strain softening was found to be caused by the breakages of filler bridging contacts and thus involved only a small fraction of the total material.

Although it has long been portrayed as the nation’s ‘moat defensive’, recent examinations of Anglo-French rivalry during the long eighteenth century have revealed that the English Channel was, in reality, a highly permeable and vulnerable maritime border territory. Within this context, the Channel Islands assumed a strategic and tactical significance which was vastly disproportionate to their physical size, population or resources; emerging as what Morieux terms ‘a lynchpin of control' over local shipping and trade. Although a great deal of research has been already undertaken – particularly in relation to the Channel Islands’ role as a base for commerce-raiding and intelligence gathering – much of this has covered the entire long eighteenth century. However, it was only during the Great French War that the British government embraced the military potential of the Channel Islands to the fullest; not only exploiting the inhabitants’ knowledge of the seas and intimacy with her ‘enemies’, but also transforming the archipelago into a chain of offshore fortresses. In addition, prior scholarship has often focused on individual aspects of the Channel Islands’ involvement in the Great French War; while local historians have tended to embrace the ‘Great Man’ approach, examining the period through the lens of the careers of local commanders. Consequently, this thesis seeks to provide a more complete picture of the Channel Islands’ role within Britain’s military and naval strategy; integrating an examination of local defence and security with several of already well-covered topics. Moreover, in light of the fact that existent scholarship has often centred upon ‘Great Men’, it is hoped that the thesis shall serve to better demonstrate the extent to which the celebrated achievements of Don, Doyle and D’Auvergne rested upon the efforts of a number of ‘unsung heroes’.

The events surrounding the collapse of the second Labour government in the summer of 1931 represented a watershed in twentieth century British politics. They brought to a close the ‘uneasy equilibrium’ which had characterised the country’s political life since 1918, ensconcing a Conservative-dominated National government in power for the remainder of a decade marked by continuing economic uncertainty and the mounting threat of war. They also precipitated a crisis of political identity within the Labour party. Deprived of the founding generation of its leadership and with its parliamentary strength decimated, the ‘gradualist’ approach which had long characterised its politics was seemingly left in tatters. Yet Labour returned to office in 1940 as a key partner in the wartime coalition; in 1945, it secured a sweeping electoral landslide of its own, allowing it to implement much of its traditional programme. It is the contention of this thesis that the party’s recovery during the 1930s was made possible by the crucial contribution of the trade unions. With Labour’s political leadership substantially weakened after 1931, the unions assumed a pivotal role in shaping the party’s direction, to the extent that by 1940, its political culture, organisation and policy had been decisively remade. The identity which developed in these years continued to characterise Labour’s politics for a generation, through the ‘high tide’ of the 1945 Attlee government, into the 1950s and beyond. This was a hugely significant and underappreciated achievement in the context of the destruction of labour movements that attended the retreat of political democracy across much of Europe during the 1930s. This thesis seeks to investigate and understand the crucial contribution of the trade unions to this redevelopment of Labour’s political culture through an exploration of key aspects of the party’s organisation in the period 1931-1940.

This Thesis describes the development of novel catalytic dearomatisation methodologies of indolyl and pyridyl systems for the synthesis of spirocyclic and annulated products. Chapter 1 provides an introduction to this area of research and reviews related reactions, as well as setting out the research objectives. Chapter 2 describes the cyclisation of indole-alkyne systems I, using Ag(I) or Au(I) catalysis, to selectively form either spirocyclic indolenines III or carbazoles IV in high yield through a common vinyl metal intermediate II. An efficient and reusable heterogeneous catalyst system was also found for the synthesis of indolenines III. A high-yielding asymmetric spirocyclisation methodology was later developed by using the silver salt of a BINOL-derived chiral phosphoric acid V to furnish spirocycles in up to 89:11 er. Finally, these methodologies were applied in brief studies towards the natural product spirobacillene B VI and in an accidental synthesis of actinopolymorphol B VII. Chapter 3 details the cyclisation of indole α-diazocarbonyls VIII, using Rh(II)-, Pd(II)-, Cu(II)- and SiO2-based catalysts to selectively form 6 different products, namely spirocyclic indolenines IX, oxindoles X and XI, as well as annulated indole isomers XII, XIII and XIV. This work is, to the best of our knowledge, a record number products prepared through catalyst-selective synthesis. A number of diverse mechanistic pathways were proposed in this work, including a surprising reaction involving atmospheric oxygen. Finally, Chapter 4 describes the cyclisation of pyridine-, pyrazine- and isoquinoline-ynones XV to generate annulated products XVII, which are presumed to form via a vinyl silver species such as XVI. This work ultimately led to a high-yielding 5 step dearomative synthesis of the alkaloid (±)-lasubine II XVIII.

This thesis is the first major study of modern archaeological attempts to infer ethnic identity from the material record, in research on the Anglo-Saxon migrations to Britain after the end of Roman rule. It places these studies in their intellectual context, critically assesses their explicit methodologies and unstated analytical assumptions, and compares them with recent work in ethnic sociology. It asserts that Anglo-Saxon archaeology would benefit from drawing upon the most recent insights of this particular field, because, the thesis demonstrates, current scholarship relies upon epistemologically questionable categories, such as coherent 'Germanic' groups. The thesis uses post-structuralist philosophy to show that this reification results from belief that empirical methods can answer questions about ethnic identity unanswerable through purely archaeological means. In particular, it uses the philosophy of Jacques Derrida to show that even the subtler of such attempts rely on material interpretations based not on empirical observation, but pre-rational acts of interpretative choice originating from culture historical intellectual contexts. The thesis then proposes possible alternatives, in conversation with recent historiography that treats the 'end' of the Roman world as a transformation of civic and military hierarchies of power in the wake of Roman state collapse. This produced complex renegotiations of gender identity and methods for the expression of status. The thesis uses the philosophy of Gilles Deleuze and Félix Guattari to reinterpret two important early Anglo-Saxon cemeteries as well as the most important literary sources for Britain in the fifth century. This reinterpretation reveals that prioritising questions of ethnicity has precluded appreciation of the participation of the inhabitants of lowland Britain in such processes of renegotiation. The alternative interpretation offered instead does not deny the occurrence of migration to Britain in the fifth century, but posits that abandoning questions about the presence or absence of non-demonstrable ethnic identities can give those who experienced and witnessed such migration their part in the story of the transformation of the Roman world.

This thesis argues that Roger Fry should, in part at least, be placed within a tradition of British, Protestant, art criticism. To this end I compare his work with that of the leading nineteenth-century British art critic John Ruskin. I discuss the problems both men had in engaging with a predominately Catholic art form, and place their work within a wider British tradition. I consider their personal histories and how they gave a similar interpretation of art history. I explore the work of both men on Venetian art and artists with particular references to Ruskin’s The Stones of Venice and Fry’s writings on Bellini and Giotto. I examine how Fry sought to distance artworks from the culture that produced them and how this affected his view on art history. I compare Fry’s aesthetic ideas with the Theocentric theory of art advanced by Ruskin in the second volume of Modern Painters. Here I compare their respective formalist ideas. I discuss how Fry’s formalism led him to reject Impressionism and champion the Post-Impressionists. I examine the controversy surrounding the 1910 and 1912 Post-Impressionist exhibitions and how they raised the question of the moral value and use of art. I end with a discussion of Ruskin’s concept of the Theoretic faculty and contend that Fry held a similar concept. Overall I argue for the presence of continuity between Fry’s early and later ideas on art criticism and history that can partly be explained by his religious background.

Spacecraft sent to Mars have revealed that some ancient martian environments were habitable for life. Attempting to detect the organic matter that this potential life may have left behind has been a priority for several missions. However, the search for both biotic and abiotic organic compounds on Mars has yielded only organochlorines, which have an ambiguous origin. Recently it has been recognised that perchlorate (ClO4-) salts found on the surface of Mars are interfering with the heating experiments used by rovers and landers to search for organic matter. The potential for other oxygen-containing salts to disrupt thermal experiments has received comparatively little attention. In this thesis it is shown that the iron sulfate mineral jarosite thermally decomposes and releases oxygen at temperatures that would interfere with the detection of macromolecular organic matter. Experiments using synthetic jarosite samples revealed that during thermal decomposition sulfur dioxide and oxygen are released concurrently at a ratio of 2:1. In the presence of organic matter only the sulfur dioxide is detected, along with the carbon dioxide resulting from the combustion of carbon compounds. Prolonged exposure to water eventually causes jarosite to decompose into goethite. It was found that goethite can retain organic matter that was originally preserved in jarosite. The results demonstrate that though jarosite should be considered a problematic mineral for thermal experiments on Mars, goethite deposits in close proximity to jarosite may be good targets for organic matter detection. Jarosite and goethite have been observed on Mars by both rovers and orbiters. The transition from a habitable world to the present environment was marked by volcanism that created jarosite-forming, acidic, sulfur-rich conditions. The improved knowledge of the thermal extraction of jarosite and goethite containing samples will therefore be relevant in the analysis of a significant part of Mars’ geological history.

The Isle of Wight is a small island off the south coast of England. As with much of the developed world the island's water supply is effectively universal, and is secure against all but the worst droughts. However, the frequency and magnitude of future droughts are anticipated to be worse than those on historic record due to the influence of climate change. While preparations against future water shortage are important, such measures must be efficient in terms of cost and abstractions due to pressure to keep costs to consumers low and minimize the impact on the environment. The development of a representation of future climate change which balances precision with the need to fully represent uncertainty is fundamental to water planning where such efficiency is required. In this, the Isle of Wight can also represent a useful case study for climate change forecasting methodology applicable to the wider UK and beyond. A second challenge is presented by the geological and hydrological complexity of the island. Erosional and tectonic forces have altered the island's geology and, as an island, a dense network of small catchments determines drainage to sea. This Thesis presents a complete modelling process for the assessment of changing water resource availability in such a case of high heterogeneity in which few assumptions can be made regarding hydrological processes. Empirical techniques are employed to determine functional groundwater units and detect correlations between river flows and groundwater elevations. Projections of climate change are reconciled against the distribution of historic observations. Finally, a modified drought index is introduced, allowing the impact of changed drought distributions on multiple water sources to be compared with historic events.

The following study explores the, as-yet largely unexplored question within film studies of a ‘folk cinema’ through research and two practical film projects: the finished dramatic feature Blackbird (2013), and the 4th draft of a script for a dramatic feature in development, False Faces (2016). Drawing from aspects of Scottish folk culture, both films explore different forms of what a rooted, Scotland-based ‘folk cinema’ could be. In addition, the creation of an annual film festival – the Folk Film Gathering – has created a forum in which some of the issues of an emergent folk cinema could be explored with audiences in Scotland. The question of a folk cinema grows increasingly pertinent both globally and locally, particularly within an European cultural landscape where the traditional arts are increasingly resurgent, and upon a global stage where the indigenous peoples movement has led to reevaluations of concepts of tradition, indigeneity and autochthony. My PhD by practice attempts to explore, both theoretically and practically, some of the possible implications of a folk cinema, interlinking local and global contexts. In doing so I have made particular use of aspects of cultural studies and anthropological theory, such as the writing of James Clifford, Faye Ginsburg and Jay Ruby, which I believe to be a relatively untapped critical resource for wider film studies. Whilst opening discussion attempts to consider the question of folk cinema globally, as an issue that may be pertinent for diverse filmmaking traditions in world cinema, my practical filmmaking work is firmly rooted within a contigent and highly-localised attempt to explore such questions within Scotland. In particular, I explore the practical implications of a cinematic pursuit of ‘ethnographic verisimilitude’, and the translation of oral forms into a filmic narrative, whilst questioning the validity of ‘folk cinema’ that arises from ‘etic’ viewpoints, outside a depicted community. Ultimately, consideration of my practical work explores how the theoretical ideals of an emergent folk cinema are negotiated in the more unruly, worldy domain of filmmaking practice and whether, ultimately, an autochthonous Scottish ‘folk cinema’ is possible.

This thesis presents two bodies of work, both related to automated optical fibre positioning in highly-multiplexed astronomical instrumentation. Part one concerns the development and prototyping of a pick-and-place fibre positioner for WEAVE, a new 1000-fibre spectrograph for the 4.2 m William Herschel Telescope. This research has helped shape the positioner's final design and has included development of three novel techniques to enhance predicted performance: i) a scheme for automatically calibrating the fibre measurement system; ii) an algorithm for finding the centre of an imaged fibre with superior accuracy and speed; and iii) a robot motion control scheme to greatly reduce field reconfiguration time. Following these developments, and with rigorous testing of the proposed industrial robotic components, it is found that the performance of the positioner is likely to meet WEAVE's scientific requirements. Part two of this thesis presents a new design of piezoelectric motor for 'tilting spine' fibre positioners. Tilting spine technology already allows simultaneous positioning of fibres in high-density fields, but has two significant drawbacks: i) fibres are tilted, resulting in optical losses; and ii) actuators require signal amplitudes of > 100 V, placing performance-degrading limitations on the control system. The new motor has a more efficient mechanism and a drive voltage of just ± 9 V, allowing new control approaches that vastly improve the technology's capabilities. Prototyping has shown a closed-loop positioning accuracy of < 2.8 μm, lower than any other published technique. A 50% reduction in optical loss is shown to be feasible by trading some accuracy for a spine length increase. It follows that any survey using this motor would have a higher signal-to-noise ratio and/or would complete faster than with the existing technology.

This thesis examines the formation of the anarchist movement in Spain, from the collapse of the movement in the early 1890s to the consolidation of the Confederación Nacional de Trabajo (CNT) in 1915. The grassroots anarchist print culture established over these years was central to the movement’s survival and expansion. Periodicals were the site in which anarchist ideology and practice came together, where abstract ideas were given meaning in relation to contexts and developments over time. The anarchist press, and the groups which produced it, also gave the movement an informal structure which it otherwise lacked. Together, the ideas and networks established by print formed the cultural foundations of the movement, prior to its mass expansion during the First World War. The first section of this thesis examines the movement’s relationship with violence in 1890-1898. In these years, popular violence, terrorism and state repression had a profound impact on the ways in which anarchist practice was conceived. The anarchist press provided a forum for debates between anarchist factions over the legitimacy of violence, while at the same time it attempted to stabilise the movement in the face of the broad, heavy-handed repression of the Spanish state. It failed in this last regard, and by 1896 the movement and its press had collapsed. The second section focuses on the recovery of the movement from 1899 to 1906. In this period, the movement made its first consolidated effort to establish education as a revolutionary strategy, which became seen as the prime means to cement anarchist culture and practice in local contexts. Print was central to these developments, carrying the anarchist educational message into new areas and assisting in the establishment of centres and schools. The third, and final, section discusses the attempts to unite the movement around the organisational theory of syndicalism, from the first articulations of these ideas in Barcelona in 1907-1910 to the consolidation of the CNT in 1915. The spread of – and in some cases, resistance to – syndicalist ideas outside Cataluña relied on the networks of anarchist publishing which had been established over the turn of the century. Yet, by helping to create an alternative, more formal, structure within the movement, the anarchist press sowed the seeds of a decline in its own heterogeneity and significance. This was symbolised by the establishment of the syndicalist daily Solidaridad Obrera in Barcelona in 1916, and the subsequent contraction of anarchist publishing elsewhere in Spain.

Inherited metabolic diseases (IMD’s) are a large class of heterogeneous genetic disorders caused by dysfunction within a single pathway of intermediary metabolism. In many of these diseases, the dysfunction of metabolic enzymes leads to the accumulation of toxic metabolites which disrupts the normal development of the central nervous system. With the advent of treatments that positively influence neuropsychological outcomes, there is a need for sensitive and objective neuropsychological measures that allow patients to be systematically tracked in order to understand the efficacy of existing treatments. In this thesis, a neuropsychological test battery consisting of attention, language and oculomotor measures was developed to accurately describe individual and developmental differences between IMD patients and healthy developing controls. The functioning of five diseases was examined: Morquio syndrome (\(N\) = 12), Hurler syndrome (\(N\) = 3), Maroteux-Lamy syndrome (\(N\) = 2), Tyrosinemia type I (\(N\) = 13) and Tyrosinemia type III (\(N\) = 5). Findings indicated that disease effects were not homogeneous across tasks, and that performance on the same tasks was not uniform across diseases. The obtained data offers a promising basis for understanding how biological factors influence the severity and timecourse of developmental effects in future research.

In this thesis, we study the existence, uniqueness, and regularity of systems of degenerate linear stochastic integro-differential equations (SIDEs) of parabolic type with adapted coefficients in the whole space. We also investigate explicit and implicit finite difference schemes for SIDEs with non-degenerate diffusion. The class of equations we consider arise in non-linear filtering of semimartingales with jumps. In Chapter 2, we derive moment estimates and a strong limit theorem for space inverses of stochastic flows generated by Lévy driven stochastic differential equations (SDEs) with adapted coefficients in weighted Hölder norms using the Sobolev embedding theorem and the change of variable formula. As an application of some basic properties of flows of Weiner driven SDEs, we prove the existence and uniqueness of classical solutions of linear parabolic second order stochastic partial differential equations (SPDEs) by partitioning the time interval and passing to the limit. The methods we use allow us to improve on previously known results in the continuous case and to derive new ones in the jump case. Chapter 3 is dedicated to the proof of existence and uniqueness of classical solutions of degenerate SIDEs using the method of stochastic characteristics. More precisely, we use Feynman-Kac transformations, conditioning, and the interlacing of space inverses of stochastic flows generated by SDEs with jumps to construct solutions. In Chapter 4, we prove the existence and uniqueness of solutions of degenerate linear stochastic evolution equations driven by jump processes in a Hilbert scale using the variational framework of stochastic evolution equations and the method of vanishing viscosity. As an application, we establish the existence and uniqueness of solutions of degenerate linear stochastic integro-differential equations in the L2-Sobolev scale. Finite difference schemes for non-degenerate SIDEs are considered in Chapter 5. Specifically, we study the rate of convergence of an explicit and an implicit-explicit finite difference scheme for linear SIDEs and show that the rate is of order one in space and order one-half in time.

Rockfall threaten infrastructure and people throughout the world. Estimating the runout dynamics of rockfall is commonly performed using models, providing fundamental data for hazard management and mitigation design. Modelling rockfall is made challenging by the complexity of rock-ground impacts. Much research has focused on empirical impact laws that bundle the rock-ground impact into a single parameter, but this approach fails to capture characteristics associated with the impact configuration and, in particular, the effects of rock-shape. While it is apparent that particular geological settings produce characteristic rock-shapes, and that different rock-shapes may produce characteristic runout dynamics, these aspects of rockfall are poorly understood. This study has focused on investigating the mechanics behind the notion that different rock-shapes produce characteristic runout dynamics and trajectories. The study combines field data on rockfall runout, trajectory and dynamics, laboratory analogue testing in controlled conditions, and numerical modelling of the influence of rock-shape. Initially rock-shape, deposition patterns and rockfall dynamics were documented at rockfall sites in Switzerland and New Zealand. This informed a detailed study of individual rock-ground impacts on planar slopes in which laboratory-scale and numerical rockfall experiments were combined to isolate the role of rock-shape on runout. Innovatively, the physical experiments captured the dynamics of impacts and runout paths using high speed video tracking and a sensor bundle with accelerometers and gyroscopes. Numerical experiments were performed using a 3-D rigid-body rockfall model that considers rock-shape, and has allowed the variability of rockfall behaviour to be explored beyond the limitations of physical experimentation. The main findings of the study were on understanding rockfall-ground impacts, the influence of rock-shape on rockfall dynamics, and influence of rock sphericity. By measuring velocity, rotational speed, impact and runout character, it has been possible to quantify the variability of individual rock-ground impacts as a function of rock-shape. Investigation of single rebounds reveals that if classical restitution coefficients are applied, $R_n$ values greater than unity are common and rebounds are highly variable regardless of constant contact parameters. It is shown that this variability is rooted in the inherent differences in the magnitudes of the principal moment of inertia of a rock body brought about by rock-shape. Any departure from a perfect sphere induces increased range and variability in rock-ground rebound characteristics. In addition to the popular description of a rock bouncing down slope, rebounds involve the pinning of an exterior edge point on the rock, creating a moment arm which effectively levers the rock into ballistic trajectory as it rotates. Observations reveal that the angle of the impact configuration plays a key role in the resulting rebound, whereby low angles produce highly arched rebounds, while large impact angles produce low flat rebounds. The type of rebound produced has a strong bearing on the mobility of the rocks and their ability to maintain motion over a long runout. The mobility of rocks is also shown to be related to rotation, which is governed by the differences in the principal inertial axes as a function of rock-shape. Angular velocity measurements about each principal inertial axis indicate that rocks have a tendency to seek rotation about the axis of largest inertia, as the most stable state. Rotations about intermediate and small axes of inertia and transitions between rotational axes are shown to be unstable and responsible for the dispersive nature of runout trajectories, which are inherent characteristics of different rock-shapes. The findings of this research demonstrate the importance of rock-shape in rockfall runout dynamics and illustrate how it is essential that the rock-shape is included in rockfall modelling approaches if the variability of rockfall behaviour is to be simulated.

This dissertation studies the intersection between the sharing of individual specific risks and business cycle risks. Individual specific or idiosyncratic risk sharing is typically hampered by moral hazard, and in Chapter 2 we propose a new theory of debt finance as an effective mechanism for sharing idiosyncratic risks. But business cycle or systemic risk sharing is also affected by the means of idiosyncratic risk sharing. Departures from full systemic risk sharing can dampen the incentive compatibility constraint allowing a greater degree of idiosyncratic risk sharing (Chapter 1). Entrepreneurs’ productive risk can quickly transform into low employment, as wages fall below marginal revenue products of labour (Chapter 3). Market prices for systemic risk insurance do not necessarily internalise balance sheet externalities, resulting in excessive swings in leverage and factor market wedges of inefficiency (Chap- ter 4). Sometimes, agents have private information about the risks faced by their projects, and how they correlate with the broader economy. When this is the case, optimal systemic risk sharing arrangements must allocate business systemic risk in a way that deters entrepreneurs from herding among their peers (Chapter 5).

The geography of Scotland, with a highly undulating hinterland, long and indented coastline, together with a large number of islands, means that much social and economic activity is largely located at the coast. The importance of the coast is further highlighted by the large number of ecosystem services derived from the coast. The threat posed by climate change, particularly current and future sea level rise, is of considerable concern and the associated coastal erosion and coastal flooding has the potential to have a substantial effect on the socioeconomic activity of the whole country. Currently, the knowledge base of coastal erosion is poor, which serves to hinder the current and future management of the coast. This research reported here aimed to establish four key aspects of coastal erosion within Scotland: the physical susceptibility of the coast to erosion; the assets exposed to coastal erosion; the vulnerability of communities to coastal erosion; and the coastal erosion risk to those communities. Coastal erosion susceptibility was modelled here within a GIS, using data for ground elevation, rockhead elevation, wave exposure and proximity to the open coast. Combining these data produced the Underlying Physical Susceptibility Model (UPSM), in the form of a 50 m2 raster of national coverage. The Coastal Erosion Susceptibility Model (CESM) was produced with the addition of sediment supply and coastal defence data, which then moderates the outputs of the UPSM. Asset data for dwellings, key assets, transport infrastructure, historic assets, and natural assets were used along with the UPSM and CESM to assess their degree of exposure to coastal erosion. A Coastal Erosion Vulnerability Model (CEVM) was produced using Experian Mosaic Scotland (a geodemographic classification which identifies 44 different social groups within Scotland) to classify populations based upon 11 vulnerability variables. Dwellings were assigned a CESM and CEVM score in order to establish their coastal erosion risk. This research demonstrated that the issue of coastal erosion will impact on a relatively low number of properties compared to those impacted by flooding (both coastal and fluvial) as many dwellings are already protected by coastal defences. There is therefore, a considerable future liability, and great pressure for coastal defences to be maintained and upgraded in their current form. The use of the CEVM is a novel inclusion within a coastal erosion assessment for Scotland. Use of the CEVM established that coastal erosion risk is not distributed equally amongst the Scottish coastal population and highlighted that risk can be reduced by either reducing exposure or reducing vulnerability. Thus far in Scotland, reducing exposure has been the primary management approach, which has a number of implications with regards social justice. This research identified the existing data gaps that should be addressed by future research in order to further improve coastal management in Scotland. Future research should focus on assessing historical coastal change rates on a national scale, improve modelling of national scale wave exposure, enhance the information held about current coastal defences and, determine the direct and indirect economic cost associated with the loss of different asset types. It is also necessary to clarify the social justice implications of using adaptation approaches to manage coastal erosion as well as establishing a method to communicate the susceptibility, exposure, vulnerability and risk aspects whilst minimising the potential negative impacts (e.g. property blight) of releasing such information.