VictorJuiz/thesis huggingface dataset:
One-pot nitro-Mannich cascade reactions: new methodologies and synthetic applications

Pyrrolidine and pyrrolidinone rings are common motifs found in many biologically active natural products and drugs. Accordingly, our work focuses on the development of new methodologies for their one-pot synthesis.
An efficient diastereoselective nitro-Mannich / lactamisation reaction cascade of methyl 3-nitropropanoate with cyclic and acyclic imines for the direct preparation of trans-monocyclic and fused tricyclic pyrrolidinone derivatives was developed. The reaction is easy to perform, broad in scope and tolerates a wide variety of functional groups. For the monocyclic methodology, 28 examples with a very good average yield of 72% and excellent diastereocontrol (typical dr >98:2) were obtained using optimized conditions and varying the amine and the aldehyde reagents.
The methodology has been extended to the synthesis of 1,3,5-trisubstituted 4-nitropyrrolidinone derivatives using α-substituted 3-nitropropanoate. Using a one-pot protocol, 22 derivatives were synthesised in good yields (65% average) and diastereomeric ratios ranging from 3:1 to 30:1 in favor of the trans/trans diastereoisomer.
In addition, the nitro-Mannich / lactamisation cascade of methyl 3-nitropropanoate was developed further to allow the rapid synthesis of 5-isopropyl-4-nitropyrrolidin-2-one from reaction with ammonium acetate and 1-butyl-4-nitropyrrolidin-2-one from reaction with formaldehyde. Also, the synthetic utility of the nitro-pyrrolidinones formed was exemplified through various functional group modifications: the selective reduction of the lactam carbonyl, the reduction of the nitro group in the presence or absence of a carbonyl group and the reductive removal of the nitro group.
The development of an enantioselective version of the cascade under chiral Brönsted acid catalysis provided promising results (up to 90% ee). Moreover, various studies were undertaken to understand the mechanism of the reaction and the nitro-Mannich / latamisation cascade is now well understood. Furthermore, a formal synthesis of rac-Slaframine in 8 steps and 15% overall yield was achieved and it inspired additional work towards a nitro-Mannich / epoxide ring opening cascade.

Keywords: enantioselective
cascade
methodology
Slaframine
diastereoselective
multi-component reaction
nitro-Mannich
Advisor: Dixon, D
Investigating rare genetic variants in common migraine

Migraine is a highly prevalent headache disorder imposing a significant burden of disability on human health worldwide. The headache is believed to arise from activation of trigeminal pain pathways, with CNS regions also playing an integral role in attack initiation and progression. Recent genetic associations have been made, but there is a need to convert these into relevant experimental models to study underlying disease mechanisms. Herein, I detail functional analysis of two deleterious variants in the genes KCNK18 and SLC12A3, that segregate with migraine with aura in one large pedigree. Gene function has been studied in a range of cell models, from heterologous expression systems and primary neuronal cultures, to Induced Pluripotent Stem (iPS) cell-derived nociceptors. In this context, the protein products of KCNK18 and SLC12A3 have been shown to modulate parameters of neuronal excitability, including baseline membrane properties and firing patterns. Migraine attacks are not wholly attributable to perturbations in peripheral pathways. I have shown that these genes are also expressed within the CNS in a small number of discreet regions, suggesting a possible role in central processing. Utilizing recently defined genetic variants and physiological cell- based models, will provide a platform for mechanistic insights into migraine pathogenesis and allow for the development of drug screening assays for new migraine therapies.

Keywords: Stem cells
Migraine
Advisor: Cader, Z
The structures and properties of layered pnictides and oxychalcogenides

This work focuses principally on two compounds, CeCu1-xOS and LiFeAs, which have related layered structures but exhibit radically different physical properties. The nature of the air sensitivity of the ZrCuSiAs-type oxysulfide CeCu1-xOS has been investigated by neutron diffraction and magnetometry. It was found that this compound can be made fully stoichiometric, with structural and magnetic properties that are consistent with other LnCuOS compounds, indicating that this is a bona-fide Ce3+ compound. Upon air exposure, Cu ions are extruded from the sulfide layer to leave a Cu-deficient phase with contracted unit cell parameters and a diminished paramagnetic moment consistent with mixed-valence Ce3+/4+.The extruded Cu forms CuO and can be re-inserted into the sulfide layer by heating under a reducing atmosphere. This explains the anomalous behaviour of CeCuOS reported throughout the literature and has implications for the behaviour of other layered Cu-sulfides with oxidisable cations. At low temperatures Cu-deficient CeCu0.8OS was found to exhibit structural ordering of Cu+ ions and vacancies, resulting in a √—5a × √—5a basal expansion of the high-temperature unit cell.
The layered iron arsenide LiFeAs was synthesised and found to be superconducting below 17 K. Joint XRD/NPD measurements showed unambiguously that the compound adopts the anti-PbFCl structure with Li ions in a square-pyramidal LiAs5 environment. No evidence was found for an orthorhombic structural distortion at low temperatures. Further diffraction experiments showed that the compound can be made with non-stoichiometric compositions Li1-yFe1-y for small values of y (<0.05), as Fe can be accommodated on the Li site. This type of non-stoichiometry was found to strongly inhibit superconductivity (which was quenched entirely when y>0.02).
Three series of compounds of type LiFe1-xMxAs (M = Mn, Co, Ni) were synthesised and characterised struturally bu high-resolution XRD and/or NPD. Substitution by Co and Ni was found to cause a monotonic decrease in Tc, and Ni was found to be twice as effective at suppressing Tc as Co. MuSR measurements showed the penetration depth increasing with Co and Ni substitution, consisitent with the superconducting state becoming less robust. Substitution by Mn was found to strongly inhibit superconductivity, and this behaviour is reminiscent of the non-stoichiometric Li1-yFe1-yAs materials.
The structures and superconducting properties of LiFeAs and NaFeAs were studied under high pressures. Equations of state were obtained for each compound. Hydrostatic pressure was found to distort of the FeAs4 away from ideal tetrahedral geometry in both compounds. These changes caused a monotonic decrease in Tc in LiFeAs, but has a smaller and more complex effect on the Tc of NaFeAs. Furthermore, NaFeAs was found to undergo a structural transition above P = 22 GPa, but the high-pressure structure could not be solved and this will become a target for future work.

Keywords: Oxychalcogenide
Pnictide
Air sensitive solids
Solid state chemistry
Superconductivity
Advisor: Clarke, S
Retroviral writings: reassessing the postmodern in American AIDS literature

This thesis reassesses American AIDS literature of the 1980s and 1990s by focusing on four major writers: the poets Thom Gunn (1929-2004), James Merrill (1926-1995) and Mark Doty (1953-), and the novelist Michael Cunningham (1952-). It questions the dominant critical discourse on literature of the epidemic, contending that while competing versions of the postmodern provided useful models for reading AIDS in the 1980s and 1990s, it is now necessary to adjust the critical position in line with the intellectual turn away from the cultural theories of that time.
The introduction provides an overview of the most prevalent constructions of AIDS’ postmodernity through the period, arguing that critics were anxious to fit the epidemic to the theoretical models of the day, and going on to suggest that the writers under scrutiny actively question or even resist these models. Chapter One reads the later collections of Thom Gunn against his earlier work, arguing that he writes a "poetry of prophylaxis" which draws on his literary past in order to construct a defence against the uncertainties of the epidemic age. Chapter Two develops this question of self-reconstruction, examining the last two collections of James Merrill and his 1993 memoir in light of his own diagnosis with HIV. It proposes that in the renegotiation of his body, he might help the reader both remember and "re-member" him. Chapter Three turns to the work of Mark Doty, in particular the memoir Heaven’s Coast and the two collections, My Alexandria (1995) and Atlantis (1996), suggesting that Doty reclaims metaphor for palliative good at a time when AIDS theorists such as Paula Treichler registered scepticism during the "epidemic of signification". Chapter Four discusses the 1990s novels of Michael Cunningham, arguing that in order to “know” AIDS, outside of contemporaneous postmodern readings, it is necessary to "re-know" or "recognise" older literary models. The thesis ends with a brief account of post-1990s AIDS literature and theory, before concluding that each writer argues for models of literary continuity as a means of neutralising the possible creative rupture wrought by immunodeficiency.

Keywords: Michael Cunningham
Postmodernism
Poetry
Thom Gunn
James Merrill
HIV
AIDS
Mark Doty
Literature
Advisor: Methven, J
Maintaining opportunism and mobility in drylands: the impact of veterinary cordon fences in Botswana

The recent revival of debates concerning livestock development in Africa follows the more widespread acceptance of paradigm shifts within rangeland science, and maintaining pastoral mobility is now recognised as fundamental for the future survival of pastoralism and sustainability of dryland environments. However, in southern Africa communal pastoral drylands continue to be enclosed and dissected by large-scale barrier fences designed to control livestock diseases, thus protecting lucrative livestock export agreements. This interdisciplinary research examines the extent to which these veterinary cordon fences have changed people’s access to, and effective management of, natural resources in northern Botswana and how fence-restricted resource use by livestock, wildlife and people has changed the natural environment.
Critical political ecology informed the approach, given its emphasis on socio-political and historical influences on resource access, mobility and user relationships. This enabled the biophysical effects of social changes to be investigated fully, thereby moving beyond a tradition of discipline-based studies often resulting in severely repressive rangeland policies. The research demonstrates how enclosure by veterinary cordon fences restricts patterns of resource access and mobility within pastoral drylands, with serious implications for both social and environmental sustainability. Enclosure increases the vulnerability of people to risks and natural hazards, while resource access constraints and pastoral adaptations to enclosure have favoured the increasing commercialisation of livestock production, thus obstructing pathways into pastoralism. While widespread environmental change in livestock areas cannot be attributed thus far to enclosure, the curtailment of wild migratory herbivores at the wildlife–livestock interface has caused some large-scale structural vegetation changes and there are indications that fence induced sedentarisation could be accentuating existing degradation trends. Given these changes, future rangeland policies in Africa should be aware of the social and environmental impacts associated with export-led disease management infrastructure and consider alternative, less intrusive, approaches to livestock development and disease control in extensive pastoral drylands.

Keywords: mobility
environmental change
pastoralism
drylands
veterinary cordon fence
Advisor: Thomas, D
Social knowledge and programme structure in representations of television characters

It was argued that the social psychology of person perception, mass communications and cultural studies can be related to viewers' representations of television characters. Mass communications needs to incorporate viewers' interpretations and programme structure. Social cognition could satisfy the former need and cultural studies the latter.
A literature review showed little research on viewers' interpretations of television programmes. There is a considerable body of research on person perception, gender stereotypes, the effects of viewing and programme structure.
A study of viewers' accounts of viewing soap opera showed that they become involved with the characters and find the programmes realistic. Soap opera plays an important role in their lives.
Viewers' representations of soap opera characters were examined using multidimensional scaling. This revealed stable, replicable character representations for Dallas, Coronation Street and EastEnders. The representations were compared with the oppositions which structure the programmes, Implicit Personality Theory and Gender Schema Theory.
Dallas characters were represented by themes of morality and power/activity. Power was correlated with gender, with some counter-stereotypic females.
Coronation Street characters were organised around morality/potency, gender (matriarchal) and approach to life. This related to person prototypes and contrasted with interaction patterns between characters.
EastEnders characters were represented by themes of morality/power, gender and approach to life/centrality. Free descriptions validated the attribute ratings and showed further features of the representation.
No socio-structural group differences in representation were found.
Viewers' character representations were a constructive integration of programme structure and social knowledge. The application of abstract knowledge to a structured domain was discussed.
Textual analysis of a narrative identified the 'role of the reader' and textual openness. This was related to stereotypes, narrative expectancies, myth and character representation.
Distinct types of divergence in viewers' interpretations of narrative were discovered. Further, a narrative containing two readings was interpreted in four distinct ways by viewers, depending on their perceived relationships with characters.
The conclusions and limitations of the research were discussed. Implications for person perception, stereotyping and textual analysis were examined. A taxonomy of factors relating to the interpretation and representation of television drama was presented.

Advisor: Argyle, M
Attitudes towards infertility in early modern England and colonial New England, c. 1620-1720

This thesis examines attitudes toward infertility in early modern England and colonial New England from c.1620 to 1720 through infertility’s representation in contemporary medical, religious, and literary sources. This study uses an expanded definition of infertility, namely a 'spectrum of infertility', to capture the tensions that arose during periods of infertility and experiences of reproductive failure such as miscarriages, stillbirths, monstrous births, and false conceptions. A spectrum, more than a modern definition, more accurately represents the range of bodily conditions experienced by early modern women and men that indicated reproductive disorder in the body; by extension, the language of infertility expressed fears about disorder in times of social, religious, and political crisis in early modern society. The two societies' relationship was often described through reproductive language and the language of infertility appears in both societies when order - within the body, within marriages, or within and between communities - was threatened. This thesis contributes to a growing body of scholarship on infertility in early modern society by analysing its presence in communications within and between early modern England and colonial New England. It argues that understanding the English origins of the colonists' attitudes toward infertility is fundamental both to understanding the close connection between the two societies and to providing context for the colonists' perceptions about their encounters with new lands, bodies, environments, and reasons for emigration. As a result, this thesis seeks to break new ground in providing an overview of social, medical, and cultural reactions in both England and New England, demonstrating that similar language and tropes were used in both regions to communicate concerns about infertility. Exploring the interplay between the many sources addressing this health issue more accurately represents the complexity of early modern attitudes toward infertility, and the intimacy of the relationship between the fledgling New England colonies and their metaphorical Mother England.

Keywords: social history of colonial New England
history of reproduction
social history of Early Modern England
history of infertility
Advisor: Pelling, M
Charters, E
Innovation in vocational education and training in England, Germany, and Austria : implications of practitioners’ perspectives for  policy development and college leadership

This research project conducted an in-depth, qualitative assessment of vocational education and training (VET) teachers’ perceptions of pedagogic innovation, with an emphasis on obstacles and supporting factors. The main research question was: “How do teachers’ roles and perspectives shape innovation processes in VET and what does this imply for the development of teaching and learning practices?” Three clusters of subsidiary questions were derived around thematic foci: ‘perceptions and concepts’, ‘documentation of practice’, and ‘dynamics, limitations, and lessons for innovation’.
Based on analytical strategies derived from grounded theory, two phases of interviews – the first with ten experts and the second with 62 VET practitioners at 20 colleges – were conducted in England, Germany, and Austria, with a focus on full-time VET (Further Education Colleges, Berufskollegs, and Berufsbildende Mittlere und Höhere Schulen) in the 16-19 age range. Classroom observation preceded semi-structured, 30 to 60 minute interviews with teachers.
The study builds on previous research and existing frameworks such as Lipsky’s concept of ‘street-level bureaucracy’ and Flyvbjerg’s ‘critical cases’. However, it fills a gap in the literature by focusing on practitioner perceptions, motivations, professionalism, autonomy, work contexts, and own learning in relation to pedagogic innovation, whilst tracing relevant connections to educational policy, college management, and societal influences.
Teachers are shown in multiple roles as inventors, designers, and implementers of innovation, facing nine categories of obstacles. Those include limited time and budgets, bureaucracy and lack of autonomy, problems with project planning and execution, and issues related to lack of support. In addition, this study provides a comparative investigation of practitioners’ interpretations of key terms (‘pedagogy’, ‘didactics’, ‘innovation’), revealing differences between England on the one hand, and Germany and Austria on the other, based on different degrees of autonomy and innovative focus. Based on such findings, the study details recommendations for college leaders and policy makers for facilitating pedagogic innovation, placing each in their respective national contexts.

Keywords: HTL
Berufskollegs
pedagogy
Vocational Education and Training
FE Colleges
Germany
street-level bureaucracy
innovation
England
critical case
Austria
berufsbildende Schulen
grounded theory
HAK
BHS
interviews
VET
qualitative
full-time vocational education
Advisor: Ertl, H
The effect of magnetic fields in chemistry and biology

This thesis is concerned with the effect of static and oscillatory magnetic fields on the yield of radical recombination reactions and the proposal that such effects may constitute a possible mechanism for the interaction of environmental electromagnetic fields with biological systems.
A brief overview of research pertaining to the biological effects of environmental electromagnetic fields is presented. Next, the concept of the radical pair is introduced and the theory of its behaviour in solution is examined in order to illustrate the mechanism by which magnetic fields can affect its probability of separation.
Three different experimental systems involving the attack of free-radicals on DNA are presented. The extent of DNA damage is assayed in the presence and absence of a static magnetic field. These systems involve the killing of yeast cells as observed by the growth of subsequent colonies, direct observation of strand breaks to DNA, in vitro, by gel electrophoresis and the direct observation of intra- nuclear DNA damage by microgel analysis. In all systems, magnetic field effects are observed but are difficult to reproduce consistently.
The design of novel apparatus for the observation of resonant radiofrequency effects is described. The application of a 30-40 MHz oscillating magnetic field is found to alter the yield of exciplex fluorescence in the photoreaction of anthracene-d10 and 1,3-dicyanobenzene. The effect is interpreted in terms of a change in the efficiency of singlet andleftrightarrow; triplet interconversion in the {anthracene cation - DCB anion} radical pair when the oscillating field is in resonance with hyperfine splittings in the DCB anion radical.
Back to nature: geologically informed consolidants for stone museum artefacts

The Back to Nature project was developed as a collaborative doctoral award between the British Museum and the School of Geography and the Environment, University of Oxford. The British Museum has a large collection of limestone artefacts, some of which have deteriorated to an extent that a consolidation treatment, to improve internal cohesion, has been deemed necessary to ensure the value of the artefacts is maintained. Previous consolidation practices within the museum had centred on the use of organic consolidants. In the past, inorganic consolidants had been considered ineffective chiefly due to poor penetration depth and inconsistent deposition within the stone. Recent scientific developments within conservation, particularly the development of nano-limes, coupled with a trend towards treatments offering physical and chemical compatibility, led to the British Museum reconsidering the use of inorganic consolidants.
Three inorganic consolidants: ammonium oxalate treatment, Calcite In-situ Precipitation System (CIPS), and CaLoSil have been investigated by the Back to Nature project to assess their potential for use on the British Museum’s deteriorated limestone artefacts. The investigation involved a developmental sequence of four experimental phases to assess the effectiveness of each consolidant upon freshly cut, artificially pre-weathered, and naturally weathered stone samples. In all experiments an organic silane Wacker SILRES BS OH 100 was used as a comparison. A variety of analytical methods were used including: Equotip, GrindoSonic, Scanning Electron Microscopy, Karsten Tubes, Drilling Resistance Measurement System, spectrophotometry, X-ray Diffraction and Ion Chromatography.
Experiments show that the CIPS treatment could hold promise for use as a consolidant. Ammonium oxalate only appears to provide consolidation at the surface level, and CaLoSil would need modifying and more investigation before using in the museum environment. The differences noted between experiments on artificially weathered and naturally weathered stone indicate that a two-step process, involving testing on both types of samples, would give the best indication of consolidant effectiveness. High variability between samples shows a large number are needed to give an accurate interpretation of change due to consolidation.

Keywords: consolidation
stone conservation
limestone
inorganic
Advisor: Viles, H
Fletcher, P