VictorJuiz/thesis huggingface dataset:
Synthesis of mono- and bicyclic azacycles via palladium- and ruthenium-catalysed enynamide cycloisomerisation

The initial aim of this project was to investigate ways of synthesising fused, spirocyclic and linked bicyclic amines. We built on methodology previously developed within our group, employing cyclic dienamides, prepared using the reductive cyclisation of bromoenynamides, as key structural building blocks for further annulation.
In the course of investigating the reactivity of these cyclic dienamides, we discovered a new efficient and general route to their synthesis, by employing palladium- or ruthenium-catalysed enynamide cycloisomerisation. A wide range of attractive dienamide scaffolds were synthesised from simple enynamide precursors in rapid, high yielding and operationally simple reactions, underlining their potential utility as an atom-economical source of azacycles.
Chiral enynamide substrates were used to generate 1,4-dienamides as a single diastereomer at the newly formed (quaternary) stereocentre. This relay of stereochemistry was exploited not only in the formation of monocyclic dienamides, but even in the formation of a spirocyclic product, and this bodes well for further stereocontrolled synthesis of polysubstituted azacycles.
Finally the palladium- and ruthenium-catalysed cycloisomerisation of enynamides was discussed and investigated mechanistically, utilising 1H NMR spectroscopy, timecourse and deuterium-labelling experiments.

Keywords: cycloisomerisation
ynamide
heterocycles
homogeneous catalysis
cyclisation
palladium
Advisor: Anderson, E
Networked cultural production: filmmaking in the Wreckamovie community

This thesis challenges core assumptions associated with the peer production of culture using the web-based collaborative film production platform Wreckamovie to understand how peer production works in practice. Active cultural participation is a growing political priority for many governments and cultural bodies, but these priorities are often implemented without a basis in empirical evidence, making it necessary for rigorous scholarship to tackle emerging networked cultural production. Existing work portrays peer production efforts as unrealistically distinct from proprietary, market-based production, incorrectly suggesting that peer production allows distributed, non-monetarily motivated, collaboration between self-selected individuals in hierarchy-free communities. In overcoming these assumptions, this thesis contributes to the development of a consolidated theoretical framework encompassing the complicated and multifaceted nature of networked cultural production. This theoretical framing extends Bourdieu’s theory of cultural production and reconciles it with Becker’s Art Worlds framework, and further embeds and draws on Benkler’s notion of commons-based peer production.
Concretely, this research tackles the emergence of new collaborative production models enabled by networked technologies, and theorizes the tensions and challenges characterizing such production forms. Secondly, this thesis redefines cultural participation and considers the divisions of labour in online filmmaking materializing from the interactions between professional and non-professional filmmakers. Finally, this study considers the social economies surrounding networked cultural production, including crowdfunding, and characterizes associated conversions of capital, such as the conversion of symbolic capital into financial capital.
Methodologically, this thesis employs an embedded case study strategy. It examines four feature film productions facilitated by the online platform Wreckamovie, as well as the online community within which these productions are embedded. The four production cases have completed all production stages, and have resulted in completed cultural goods during the course of data collection. This study’s findings were derived from two and half years of participant observations, interviews with 29 Wreckamovie community and production members, and the examination of archived production-related discourses (2006-2013).
Ultimately, this study makes concrete proposals towards a theory of networked cultural production with clear policy implications.

Keywords: peer production
digital labour
symbolic capital
conversion of capital
participant observation
online communities
Star Wreck 2pi
Sociology of cultural production
crowdsourcing
Benkler
Web 2.0
Iron Sky
Bourdieu
crowdfunding
ethnography
art worlds
cultural capital
cultural industries
embedded case study
networked cultural production
Cultural Sociology
social capital
collaborative online platform
Wreckamovie.com
Advisor: Meyer, E
Eynon, R
Gravity anomalies, flexure and the thermo-mechanical evolution of the West Iberia Margin and its conjugate of Newfoundland

The West Iberia (WIM) and Newfoundland (NFM) continental margins formed over a succession of rift events related to the opening of the North Atlantic between the Late Triassic and the Early Cretaceous. They are characterized by a variable width Ocean- Continent Transition (Zone) where exhumed and serpentinized mantle has been cored.
Results from 1-D well backstripping along the Portuguese shelf suggest 40-45% greater extension factors (β) than previous estimates. In addition, the age and duration of both the Late Triassic-earliest Jurassic and the Late Jurassic rifting episodes have been better constrained. It appears, for example, that the Late Jurassic rift propagates northwards along the margin, as inferred for the continental break-up during the Early Cretaceous.
Combined backstripping and gravity modelling techniques (POGM), together with new bathymetry and sediment thickness grids, have been used to estimate the effective elastic thickness, Te, of the lithosphere. Results along closely space profiles in the WIM reveal that Te decreases from 15-40 km over unthinned Variscan basement to ≤ 15 km over stretched continental and transitional crust. Along strike, a good correlation is found between the modelled mechanical structure and the segmentation of the Variscan basement onshore. Discrepancies between observed and calculated anomalies are discussed in terms of other processes that affected the margin, such as serpentinization and inversion.
Thermo-mechanical rheological modelling techniques have also been tested. The compiled software inputs the β's constrained from POGM to determine the thermal structure of the margin, which, in turn, has been used to construct models of rheology and, hence, Te. The models predict an increase in the Te of thinned continental lithosphere with age since rifting, between < 20 and > 35 km, and suggest that processes such as ductile shearing and mantle serpentinization might have permanently weakened the lithosphere.
Results from POGM along conjugate profiles off WI and NF reveal a greater longterm strength of extended continental and transitional basement in the NFM (Te's of 10-40 km). This analysis further supports the hypothesis that the low Te's modelled in the WIM might be related to its complex structural framework. In order to explain the large asymmetries observed in the amount of basement subsidence (500-1300 in) between the WI and NF margins a lithospheric-scale "simple shear" rift model is proposed for the latest stages of rifting and continental break-up.

Advisor: Watts, A
E-cadherin loss of function in the murine intestine

E-cadherin (Cdh1), is a major component of epithelial adherens junctions, binds the Wnt pathway effector β-catenin and is lost at the invasive edge of colon cancers. Crypt stem cells give rise to 4 cell lineages that, with the exception of Paneth cells, travel along the crypt-villus axis over 3 days and are shed by anoikis. Gain of function of the Wnt pathway by a mutation in Adenomatous Polyposis Coli (Apc) disrupts enterocyte turnover to result in adenoma formation. Homozygote null Cdh1 is embryonic lethal, and heterozygote Cdh1 can promote Apc1638N induced adenoma formation, but we lack models that assess additional functions of Cdh1 in the adenoma to carcinoma transition. The aim of this thesis was to evaluate the effect of Cdh1 loss of function in the murine intestine, including in the setting of Wnt pathway activation. To do this, germline and intestinal specific conditional Cdh1 loss of function models were generated.
Conditional homozygous deletion of Cdh1 resulted in embryonic lethality using Villin-Cre. In adults, homozygous Cdh1 loss using the tamoxifen inducible Villin-CreERT2 led to intestinal inflammation, bacteraemia and disrupted crypt-villus architecture. Combined conditional homozygous deletion of Cdh1 and Apc resulted in Wnt pathway upregulation assessed by β-catenin immunolabelling. Strain dependent effects of Cdh1 heterozygosity were apparent on the Apc heterozygote background: ApcMin/&plus; Cdh1&plus;/- (C57BL/6J) had no effect on survival or adenoma phenotype compared to littermate ApcMin/&plus;; Cdh1+/fl increased adenoma burden in Apc&plus;/fl Vil-Cre animals (B6D2/C57BL/6J).
Low frequency recombination of Apcfl/fl using Lgr5-EGFP-IRES-CreERT2 bypasses the loss of heterozygosity event relied on in heterozygous Apc tumour models achieving a large adenoma burden within 4 weeks. Cdh1 loss did not alter survival or adenoma phenotype in this model, including the development of large caecal tumours. Immunolabelling of tumours from Apcfl/fl Cdh1fl/fl animals showed persistent E-cadherin protein expression, suggesting incomplete recombination or that double homozygote enterocytes failed to survive. In vitro adenoma culture was used to test whether E-cadherin loss was incompatible with enterocyte survival in the setting of Wnt activation. Apcfl/fl Cdh1&plus;/&plus; and Apcfl/fl Cdh1fl/fl adenoma were cultured in matrigel and treated with an adenovirus expressing Cre recombinase under a CMV promoter (Ad-Cre). Ad-Cre had no effect on Apcfl/fl Cdh1+/+ adenoma growth. Ad-Cre treated Apcfl/fl Cdh1fl/fl adenoma organoids showed cells where E‑cadherin loss resulted in Wnt pathway upregulation as assessed by nuclear β-catenin and Axin2 expression, and epithelial mesenchymal transition shown by upregulation of fibronectin, twist and vimentin. This work supports a role for E-cadherin in modulation of the Wnt pathway. Further investigation is required to define the cell adhesion versus Wnt regulatory functions of E-cadherin.

Keywords: E-cadherin
genetics
intestine
murine
Advisor: Hassan, AB
Untir'd spirits and formal constancy

Critics who have noted the importance of Stoic constancy in Shakespeare 's Roman plays have failed to recognise the full complexity of the idea. It has two forms, both derived from the Stoic principle of homologia (consistency), and centred on the ideal of being always the same: Seneca's constantia sapientis, the rocklike or godlike virtue of the Stoic sage who is unmoved and unchanged by external circumstances; and Cicero's decorum (
De officiis I), virtue as the consistent playing of an appropriate part. Seneca is more concerned with heroic self-sufficiency, Cicero with social virtue, but both forms of the ideal contain a tension between concern for inner truth and external appearances.
In the late sixteenth century Stoic constancy becomes a subject of fierce debate as it is revived by the Neostoics, who stress the opposition of constancy and "opinion." Shakespeare's view of this debate may derive particularly from Montaigne, who moves from a Neostoic position to a sceptical critique of constancy as unattainable by inconstant man, and as less desirable than self-knowledge and flexibility.
Reading North's Plutarch with these themes in mind, Shakespeare sees in the lives of Brutus, Antony, and Coriolanus an Aristotelian pattern of ideal, defective, and excessive constancy - a pattern which he modifies, in the light of his understanding of Seneca, Cicero, and Montaigne, in the three Roman plays. He explores the tension which exists between the Senecan and Ciceronian forms of constancy, and indeed within each of them: a tension between heroic Stoic virtue ("untir'd spirits") and public role-playing ("forrral constancy"). Julius Caesar shows Roman constancy as essentially "formal," resting on pretence and self-deception; in Rome, ironically, constancy depends on "opinion." Coriolanus, by taking constancy to an extreme, demonstrates the self-destructive contradictions within it. Antony and Cleopatra, by contrast, embrace a Montaigne-like ideal of "infinite variety" and inconsistent decorum; Antony fails, but Cleopatra achieves in death a paradoxical fusion of constancy and mutability.
Quantum magnets with strong spin-orbit interaction probed via neutron and x-ray scattering

This thesis presents details of x-ray and neutron scattering experiments used to probe quantum magnets with strong spin-orbit interaction. The first of these systems are the three-dimensional iridate compounds, in which the three-fold co-ordination of IrO6 octahedra has been theoretically hypothesized to stabilize anisotropic exchange between Ir4+ ions. This novel interaction between these spin-orbital entangled, Jeff=1/2 moments is described by a Hamiltonian first proposed by Kitaev, and would be the first physical realization of this Hamiltonian in a condensed matter system. This thesis details the determination of the structure of a new polytype within these compounds, the 'stripyhoneycomb' γ-Li2IrO3. Furthermore, through resonant magnetic x-ray diffraction experiments on single crystals of β-Li2IrO3 and γ-Li2IrO3, an incommensurate, non-coplanar structure with counter-rotating moments is found.
The counter-rotating moment structure is a rather counter-intuitive result, as it is not stabilizied by Heisenberg exchange between magnetic sites, however, the Kitaev exchange naturally accounts for this feature. As such, these experiments reveal, for the first time, systems which exhibit dominant Kitaev interactions. The ordering wavevector of both β- and γ-Li2IrO3 polytypes are found to be identical, suggesting that the same magnetic interactions are responsible for stabilizing magnetic order in both materials, despite their different lattice topologies. Following this, the spinel FeSc2S4 is considered. Here, despite the presence of strong exchange between Fe2+,/sup>, and the fact that these ions sit in a Jahn-Teller active environment, the system does not order in the spin or orbital degrees of freedom. A 'spin-orbital singlet' has been theoretically proposed to describe the groundstate of this system, and here inelastic neutron scattering (INS) is used to probe the resulting triplon excitations. This allows determination of microscopic parameters in the single ion and exchange Hamiltonians, and moreover experiments in external magnetic field reveal the true spin-and-orbital nature of these triplon excitations. Finally, Ba3CoSb2O9, a physical realization of the canonical triangular antiferromagnet model is explored with INS and the high energy excitations from the 120 degree magnetic structure are found to display significant differences from those calculated by linear spin wave theory, suggesting the presence of quantum dynamics not captured in the 1/S linear spin wave expansion.

Keywords: Neutron Scattering
Resonant Magnetic X-ray Diffraction
Frustration
Spin-Orbital Singlet
Spin Orbit Coupling
Condensed Matter Physics
Kitaev Hamiltonian
2D TAF
Advisor: Coldea, R
Risk factors for violence in psychosis: meta-analysis and Cox regression analyses investigating the association of established and novel risk factors for violence

Current treatment practice guidelines in a number of countries mandate the assessment of violence risk in all patients diagnosed with schizophrenia. Although more than 100 different instruments have been developed to facilitate the assessment of violence risk, few have been specifically validated for use in those with schizophrenia. Recent work instead suggests that these instruments are typically associated with lower predictive validity in samples with schizophrenia when compared to that achieved in diagnostically heterogeneous samples, leading to concerns that these instruments omit risk factors that may be specific to the prediction of violence risk in this population. The present thesis therefore aimed to investigate the predictive validity of a number of risk factors for violence in those with schizophrenia. Firstly, to identify key risk factors for violence, a meta-analysis was undertaken, finding that although a number of criminal history risk factors are strongly associated with violence risk, nonetheless a number of risk factors rarely assessed by existing violence risk assessment instruments were significantly associated with violence in those with schizophrenia; most notably a history of attempted suicide. Results of this review also suggested that although the criminal history domain is most strongly associated with violence risk, nonetheless, there is considerable variability in the magnitude of association for the individual risk factors. Study two therefore aimed to investigate this variability and found that a history of violence was most strongly associated with subsequent violence. Study three aimed to identify whether suicidal behaviour, which has rarely been considered risk factors for violence in previous work, incrementally contributes to the prediction of violence. A simple risk model composed of young age, comorbid substance use disorder, previous violence, and a history of suicidal threats, explained as much predictive validity, as measured by the area under the receiver operating characteristic curve, as established risk assessment instruments such as the HCR–20, LSI–R, PCL–R, and VRAG. Current risk assessment approaches may therefore need revision in light of these findings.

Keywords: violence
risk factors
Advisor: Fazel, S
Simultaneous identification and control of discrete time single input single output systems

This thesis is concerned with suboptimal adaptive control of discrete linear stochastic processes whose parameters are unknown. The suboptimal adaptive controllers considered are (i) Open Loop Feedback Optimal (OLFO) controller, (ii) self-tuning controller, and (iii) optimal k step ahead controller. Two more controllers, certainty about parameter (CAP) controller and no learning (NOL) controller, that provide bounds on the performance of these adaptive controllers are also considered. Performance of these controllers have been evaluated for a first order process through monte-carlo simulations.
Simulation of OLFO controller together with the bounding controllers for the first order process when there is only one unknown parameter revealed that OLFO controller is unsuitable to control unstable processes and would be an unwise choice even for controlling stable processes. Selftuning and OK controllers have been simulated for the first order process with all the parameters unknown. Three cases for the unknown parameters have been considered. They are: (i) constant unknown parameters (ii) slowly time-varying unknown parameters and (iii) rapidly time-varying unknown parameters. Simulation results showed that in certain regions of the unknown parameter space the cost produced by self tuning controller and OK controller are very similar, in certain regions the OK controller produces lesser cost than the self-tuning controller and in certain other regions both controllers perform very badly. But self-tuning controller always took only half as much computing time as OK controller.
A necessary condition for convergence of OK controller to a linear constant parameter controller having the same functional form as CAP controller is found out using the ideas of uniform complete observability. For a first order process under OK controller the only occasion the condition would be violated is when there is 'turn-off'.
Finally, it is shown that using the combined state/parameter estimator in the place of extended Kalman filter the computational requirement of OK controller can be reduced. For the first order process, OK controller with the combined estimator took only sixty percent as much computing time as the OK controller with extended Kalman filter without any appreciable deterioration in the performance.

Advisor: Jacobs, O
Effects of environmental change on plant performance and plant-herbivore interactions

Global environmental change fundamentally affects plants and their interactions with other species, and this has profound impacts on communities and ultimately ecosystems. In order to understand the mechanisms involved, we need to elaborate on the combined effects of different global change drivers on multiple levels of plant organization, including the biochemical level (production of defence compounds), the whole organism, the population, and the plant-herbivore interaction level. This thesis investigates (1) the combined effects of factors related to climate change and habitat fragmentation on Brassica nigra and (2) the effects of Zn soil pollution on the heavy metal hyperaccumulator Noccaea caerulescens at these different levels. Common garden and greenhouse experiments with B. nigra applied drought stress and elevated CO2 to examine climate change impacts, while crossing treatments (inbreeding and between-population outbreeding) were used to investigate habitat fragmentation effects. Heterosis was lost under drought stress, and there were several interactive effects of the experimental treatments that varied within and among populations. In a greenhouse experiment with N. caerulescens, plants were grown on soil with different amounts of zinc. Plants had greater herbivore resistance when grown on Zn-amended soil, and invested more in herbivore tolerance when grown on soil without added Zn. In general, the results indicate that factors related to global environmental change have complex and interactive effects on different levels of plant organization. The findings are discussed in terms of their implications for ecology, evolution and conservation.

Keywords: climate change
secondary metabolites
soil pollution
plant defence
habitat fragmentation
environment dependence
metal hyperaccumulation
conservation
Advisor: Leimu-Brown, R
Bullock, J
Illegitimacy in a handloom weaving community

This is a study of illegitimacy in a rural industrial district in which the phenomenon became extremely common during the early nineteenth century, subsequently declining sharply in frequency from around the 1840s to levels reminiscent of the preceding century.
In the normal course of events a thesis within the field of socio-economic history will often evolve from the author having first selected a subject, then an approach to its study, and finally a location for implementing or testing his model. However in the present case the subject matter was virtually thrust at the author by his chance acquaintanceship with Culcheth's poor law papers the bulk of which, having been discovered in an attic, passed into his custody in 1965 to be dried out and sorted. The surprising volume of bastardy papers and account books led to a perusal of the parish registers and to the discovery of an illegitimacy ratio sometimes exceeding 30% of registered births.
This was sufficiently odd to warrant further investigation, although four years elapsed before the author was in a position to embark on the task ... [see pdf file for full abstract].