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This thesis reports on the one-pot hydro/solvothermal synthesis of a range of mixed metal cerium oxides with potential catalysis applications. The produced materials were characterised using a wide range of techniques to understand the synthesis-dependent variations in crystallite size, morphology, surface absorbed species and redox properties. The hydrothermal synthesis of bismuth-substituted cerium dioxide is reported. The choice of starting reagents in the hydrothermal reaction was found to affect the crystallite sizes of the resulting Ce0.5Bi0.5O2-δ samples. The Ce0.5Bi0.5O2-δ samples with the lower crystallite size and hence larger surface areas were derived from the use of Ce(NH4)2(NO3)6 as the cerium source. In situ X-ray diffraction and X-ray absorption experiments indicate that the cubic structure of Ce0.5Bi0.5O2-δ is formed via formation of poorly ordered CeO2 followed by the reduction of bismuth and/or to the crystallisation of α-Bi2O3 from the bismuth starting reagents prior to its inclusion into CeO2. The solvothermal reaction of CeCl3 with LnCl3 (Ln = La, Pr, Gd and Tb) in polyethylene glycol at 240 °C yields a range of previously unreported Ce1-xLnx(OH)2Cl samples with a unusual morphology. Barring lanthanum, up to approximately 50% lanthanide-substitution was achieved. Contrarily, the series of Ce1-xLnx(OH)CO3 materials prepared via the use of nitrate precursors achieved only 20% lanthanide-substitution. The thermal decomposition of the lanthanide-substituted cerium precursors produces materials that adopt the fluorite type unit cell and retain their unique crystal morphology. X-ray absorption near-edge structure spectra recorded at the Pr and Tb K-edges indicates the existence of both in two oxidation states, Tb3+/Tb4+ and Pr3+/Pr4+. The results deduced from XANES spectra of the mixed oxides agree with the calculated lattice parameters refined from the X-ray diffraction patterns. The incorporation of lanthanide cations improves the reducibility of ceria as measured by H2-temperature programmed reduction. Three methods using alkoxide starting reagents have successfully been able to synthesise the ordered k-Ce2Zr2O8 phase. Powder X-ray diffraction shows that the cationic ordering can be achieved at temperatures as low as 1000 °C without the use of reducing gases. A study of both the local environment and structure of the zirconium substituted ceria samples reveals that the solvothermal method of synthesis produces materials that contain a larger quantity of Ce3+.

CLOCK/CYCLE (CLK/CYC) and PERIOD/TIMELESS (PER/TIM) are heterodimers which cyclically inhibit one another transcriptionally and post-translationally, required in adult Drosophila for the molecular oscillation controlling daily rhythms in activity. Prior work in the lab established that developmental reduction of PER and subsequent adult reintroduction does not affect adult rhythmic behaviour, whilst developmental PER overexpression or CYC reduction does. I sought to characterise the developmental role of CYC. Developmental CYC reduction specific to metamorphosis can impact adult behavioural rhythms, but CYC restriction throughout development does not appear to disrupt adult molecular rhythms. Developmental CYC restriction results aberrant neuroanatomy of small lateral ventral neurons (s-LNv), which control freerunning rhythmicity, with increased complexity and defects indicative of defective axonal function, which are present in late larval and early pupal stages. Spatial mapping reveals loss of CYC in neurons other than the s-LNvs contributes to this defect. However, the adult behavioural phenotype of a developmental CYC deficit is also associated with apparent defects in other clock neurons and expression markers for other clock-gene-expressing neurons indicate that developmental specification of these cells is altered in the absence of CYC. CYC mutants display a nocturnal profile in light-dark cycles, which cannot be rescued by adult-specific CYC. Nocturnality is a circuit property independent of s-LNvs, or the neuropeptide that bolsters s-LNv function, pigment-dispersing factor (PDF), which can be overriden by developmental CYC expression within s-LNvs. I characterised a network state, driven by continued photic stimulation via the visual pathway, histamine signalling and large lateral ventral neurons (l-LNvs) which, in the absence of activation of a blue-light photoreceptor, CRY, encoded by the cryptochrome gene, which allows autonomous light sensitivity in clock-gene-expressing cells, results in a hierarchical shift in which s-LNvs, and the neuropeptide through which they interact with other clock neurons, PDF, are dispensible for behavioural rhythms. Behaviour is not rescued in this network state following developmental CYC loss, echoing additional defects beyond the PDF cells, though developmental CYC rescue in PDF-negative clock cells can restore rhythmicity in this condition.

This thesis is about computational theory in the setting of the mathematics of information. The first goal is to demonstrate that many commonly considered problems in optimisation theory cannot be solved with an algorithm if the input data is only known up to an arbitrarily small error (modelling the fact that most real numbers are not expressible to infinite precision with a floating point based computational device). This includes computing the minimisers to basis pursuit, linear programming, lasso and image deblurring as well as finding an optimal neural network given training data. These results are somewhat paradoxical given the success that existing algorithms exhibit when tackling these problems with real world datasets and a substantial portion of this thesis is dedicated to explaining the apparent disparity, particularly in the context of compressed sensing. To do so requires the introduction of a variety of new concepts, including that of a breakdown epsilon, which may have broader applicability to computational problems outside of the ones central to this thesis. We conclude with a discussion on future research directions opened up by this work.

The structural style of salt-rich extensional basins may significantly differ from those in salt-free settings. One key observation is growth folds, developed above the upper tips of propagating normal faults, may persist throughout extension in salt-rich settings, whereas they are largely transient features in salt-free settings, which are often breached during early extension. A second difference is salt-rich basins containing salt diapirs may structurally overprint regional extension and impart further strain on the surrounding country rock, typically as drape folding or radial faulting. Growth folds, drape folds and radial faults are ubiquitous in these salt-rich settings, however, uncertainties remain with respect to: (i) how extensional strain is accommodated above and below salt; (ii) how growth folds evolve and the underlying controls on geometry; (iii) how strain is accommodated around rising salt diapirs; and (iv) the implications for these structures for hydrocarbon exploration. To address these issues, three-dimensional seismic reflection data from the Halten Terrace (offshore Norway) and the Santos Basin (offshore Brazil), a compiled database of growth fold geometry and occurrence in models and in nature, and a series of kinematic trishear models are used. The results demonstrate that: (i) growth folds may accommodate significant amounts of extensional strain in salt-rich settings, affecting our ability to determine kinematic coherence and deformation related to thick-skinned, whole-plate stretching and independent, gravity-driven deformation; (ii) growth folds establish their near-final width early during folding, whereas fold amplitude increases with fault throw, and thus, the shape and size dramatically changes throughout folding; (iii) the causal mechanism for radial faulting will likely change as roof thickness varies during diapirism reflecting the interplay of the sedimentation rate and salt volumetric flux; and (iv) growth folds and radial faults adjacent to diapirs provide a rare opportunity to target vertically-stacked hydrocarbon reservoirs.

One of the larger questions within the study of X-ray Binaries currently concerns the geometry of the accretion disc during the so called ’hard state’. A model involving a truncated disc is often used to explain the properties of the hard state, but there is still disagreement on the extent to which it is necessary. Presented in this thesis are three studies related to this issue. The first looks into the changes in the accretion geometry using an argument based around radiative efficiency. Periods of exponential decay before and after the soft- to hard-state transition are found. The e-folding times of these decays are measured and it is found that this value changes from ~12 days in the soft state to ~7 days in the hard state. This factor ~2 change would be expected if there is a change from a radiatively efficient regime to a radiatively inefficient regimee. The second concerns the treatment of absorption from the Interstellar Medium in studies of X-ray Binaries. Column densities for the most abundant elements are found and compared with previous results for a number of sources. Simulated data is also used to test the impact of using incorrect column densities and older X-ray absorption models on spectral analysis. It is found that the use of incorrect absorption parameters can have a large effect on the results of spectral fitting. The third directly tests for the presence of a truncated disc by fitting a model to energy spectra from the XMM-Newton/EPIC-pn instrument. The model assumes the accretion disc extends down to rISCO at all times, and is fit to a large range of observations in both the hard and soft states. In the majority of cases there is no explicit need for a truncated disc in either the soft or hard state.

This study investigates sign language interpreted television drama through the development of a multimodal annotation tool, enabling the empirical analysis and assessment of the in-vision sign language interpreter in television drama. The provision of in-vision sign language interpreters in television drama is part of a growing area of demand for interpreters working in the field of audio-visual translation. By their very presence within the television frame, it is clear that the interpreter becomes part of the semiotic web; it appears, however, that they are failing to demonstrate an awareness of the multimodal nature of the audiovisual text, or a true understanding of the genre in which they are working. I have integrated perspectives from a number of disciplines which include audiovisual translation, film studies, and multimodality, to develop the annotation scheme, labelling specific features of the drama and rendition, to be used in ELAN, a platform that supports the development of a multimodal analysis tool. I have used the tool to analyse a corpus of interpreted dramas, thus testing the robustness of my approach and providing insights into current interpreting practice. The analysis shows that the delivery of the interpretations raises a number of issues that appear to contradict the conventions and norms found in television drama, audiovisual translation, and British Sign Language. These issues are discussed, and their impact on construction of the target language is demonstrated, and how this, in turn, alters the viewer's relationship with the drama. As the first in-depth empirical investigation of sign language interpreted drama, this thesis has a considerable impact in understanding not only current approaches, but also those required. The analysis of the case studies highlights how the underpinning theories have implications both in the teaching of and for the profession of sign language interpreted television drama, and in the wider profession in general.

Clutter is an everyday form of material culture in the home. It is increasingly prominent in popular culture and yet is under-researched by social scientists. This thesis fills this gap, working to understand clutter as a discourse, as part of everyday practices, and as something which co-constructs identities. It contributes to literatures on material culture, home life and temporal experience, drawing on research conducted with people who hoard and people who do not hoard, and a discourse analysis of decluttering texts. This is reported over three chapters of analysis. The first defines clutter. I argue all clutter is defined extrinsically, subjectively and as a problem. Clutter can also be internally differentiated into two forms: rooted clutter and flowing clutter. Rooted clutter is 'stuck', framed by memory and the past. Flowing clutter is mobile, orientated towards the present and the future. The second chapter explores clutter's relationship to time using ideas of rhythm, life transitions and memory. Rooted clutter and flowing clutter and made and managed through different rhythms. The meaning of clutter changes through the process of life transitions, and is engaged with to materially enact them. Rooted clutter as a memory object communicates gaps, absences and forgettings. The third and final analysis chapter considers clutter and home. Clutter norms and practices vary by room; this develops into a conceptual argument that home is a multiple assemblage of dwelling. Clutter's agency, in discourse and practice, is explored. Material agencies of home are shown to structure and mediate clutter practices. Finally, clutter is explored as an identity object; keeping as a material practice is discussed. Keeping clutter embodies selfhood and is an act of dwelling(-as-cultivation). Overall, this thesis shows clutter to be an important part of everyday life at home, making and mediating domestic experiences with objects and through time.

This thesis is the culmination of nearly four years' worth of ethnographic research on a south London housing estate which discusses a complex battle for control on many fronts. The estate has always had a chequered reputation. Squatting, petty crime and anti social behaviour meant that during the 80 and early 90s it was on the council's hard to let list. Accounts from the estate suggest that historically a network of committed residents had led action to keep the deviant side of the estate under control. However, over time, local commitment waned, resident friendship networks shrank and the criminal behaviour started to become more serious. Some more recent high profile violent incidents involving young people meant the council looked to provide added support in the form of commissioning professional services to address the perceived increase in serious youth crime. Unfortunately, these interventions largely disempowered residents, who saw the embers of their relational ways of working criticised and ignored. Previous resident run youth projects attempted to develop relationships with the young people and their families, aiming to develop social controls based on intergenerational obligations. However, very few residents were committed enough to spend their own personal time to support young people, and those who were still engaged saw their influence decreasing. By contrast, the commissioned services ran for only a couple of hours a day and attracted young people from further afield than just the estate. However, despite its popularity with young people, the professional youth delivery failed to improve the situation and was accused of making matters worse. The introduction of professionals made the residents take a step back, ending a long established norm of residents working together to tackle youth deviance through informal friendship building activities. This, coupled with the increase in young people on the estate, meant that it has become almost impossible for informal networks to develop social control mechanisms. The generational disconnect, amplified by the arrival of professional help, contributed to the development of a street based culture among the young people. This is as much an account of the battles between the residents and professionals, to prove the legitimacy of their differing approaches, as it is a battle against the increasingly deviant behaviour of particular groups of young people.

Land use change is a major driver of species loss worldwide, the extent and intensity of agricultural land use poses particular pressures for biodiversity and the ecosystem services it provides. In recent years, agroecosystems have seen the introduction of 2nd generation bioenergy crops in order to tackle anthropogenic climate change, providing a renewable alternative to fossil fuels. In this thesis I study the impact of cultivating two commercial perennial energy crops (PECs), Miscanthus x giganteus and willow short-rotation coppice, when compared to the cereal crops they replace. I investigate processes relevant to the provisioning of pollination and decomposition services and explore patterns of soil element bioaccessibility alongside analyses of the similarity and diversity of soil bacterial communities. When compared to cereals, I find a consistent increase in pollinator (hoverfly, bumblebee and butterfly/moth) wildflower visitation in the margins of willow but not Miscanthus. In Miscanthus, opposing trends arose for different pollinator taxa: butterflies/moths were more frequent flower visitors in Miscanthus margins than cereal margins, while hoverfly flower visits were most frequent in cereal margins. Furthermore, the availability of margin wildflowers was enhanced in willow but not Miscanthus and the seed set of margin phytometers was similar between Miscanthus and cereals. Cultivation of willow, in particular, may therefore yield local conservation benefits for both wildflowers and pollinators. However, there was no evidence for enhancement of pollinator activity in cereals adjacent to either PEC, indicating that the strategic cultivation of these crops is unlikely to enhance pollinator service provision in the wider agri-environment. For investigated soil elements, bioaccessibility in PECs did not differ significantly to cereal controls, and denaturing gradient gel electrophoresis (DGGE) revealed no difference in the diversity of bacterial communities. Similarly, DGGE fingerprint patterns did not indicate the development of crop specific assemblages, demonstrating that the mobility of soil elements and structure of bacterial communities were principally determined by factors other than the identity of the crop cultivated. Investigation of meso-microfaunal decomposition rates in Miscanthus using litter bags demonstrated an impact on decomposition processes, with a significant increase in winter decomposition rates in the PEC when compared to cereals.

Breakdown: Mechanical Dysfunction and Anthropomorphism is a practice-led research project examining the role of mechanical breakdown in the anthropomorphic process. Current theoretical approaches to mechanical breakdown identify it as a homogenous, revelatory event "a sort of breach opened up by objects." (Baudrillard, 2004: 62). Breakdown challenges this stereotyping and seeks to examine the range of gesture and affect that differing forms of mechanical breakdown exhibit. In doing so it also develops Sherry Turkle's notion of anthropomorphism as a connective rather than ascriptive process (2005: 351) in the light of Karen Barad's "performative account of material bodies" (2007: 139). Leading this research is Breakdown, the making, remaking, exhibition and reexhibition of 36 breaking-machines. These breaking-machines; simple mechanical devices made from reconfigured found materials; approach breakdown and fail during their exhibition. They are then repaired or reconfigured by the artist 'live' while still on show. Throughout the research this role of the artist as repairman became a key method. The continual recombination of human and machine responding to the call of breakdown allowed for a more detailed understanding of the gestures of mechanical breakdown. This performative relationship considers the posthuman decentring of the Vitruvian man in the writing of Rosi Braidotti (2013: 2) and Karen Barad's agential realism (Barad, 2007: 44) both of which insist that the human, rather than bounded and individual, be considered as part of a dispersed network of interacting parts. The thesis begins by investigating the performative relationship of Breakdown in detail. It describes a machine-human body that is materialised fleetingly by mechanical dysfunction. Through an intimate relationship with one machine, it then goes on to identify a typology of breakdown: seize, play, burnout and cutting loose, concluding that each emits differing expanding and contracting forces around which bodies disperse and coalesce. Finally, employing the flicker of a thaumatrope and the making of the science fiction film robot, the thesis posits that anthropomorphism is an integral element in the dissipation and reformation of human-machine bodies.