VictorJuiz/thesis huggingface dataset:
Alkaline earth and rare earth complexes for the ring opening polymerisation of cyclic esters

This Thesis describes the use of alkaline earth and rare earth complexes bearing phenolate ligands as catalysts in the amine-initiated, immortal ring opening polymerisation (ROP) of cyclic esters. Mechanistic elucidation was performed and two propagation pathways are presented.
Chapter One introduces cyclic esters and catalytic routes to polyesters by ROP. Common techniques for polymer characterisation are described and an overview of relevant phenolate-supported ROP catalysts is given. Reversible chain transfer in ROP is also discussed.
Chapter Two describes the synthesis and characterisation of zwitterionic Group 3 complexes bearing bis(phenolate)-amino ligands and the development of the amine-initiated, immortal ROP methodology using this class of catalyst. Detailed studies into the ROP of rac-lactide using amines and a zwitterionic yttrium complex are presented and the mechanism of amine-initiated, immortal ROP was derived.
Chapter Three documents further amine-initiated, immortal ROP studies using a zwitterionic yttrium complex as the catalyst. The preparation of multiarm polymers is described and further investigations using the cyclic esters, ε-caprolactone and rac-β-butyrolactone are presented.
Chapter Four describes the use of Group 2 and lanthanide phenolate complexes in the amine-initiated ROP of rac-lactide. Bulk polymerisation studies revealed the generality of the amine-initiated, immortal ROP methodology and an alternative propagation pathway was derived from mechanistic studies.
Chapter Five details the synthesis and characterisation of Group 3 amide complexes supported by phenolate-amino ligands. Each complex was screened for ROP capability and amine co-initiators were employed.
Chapter Six contains experimental details and characterisation data for the new complexes and polymer products described in this Thesis.
CD Appendix contains crystallography .cif files, supporting information for each Chapter and spreadsheets containing polymerisation data.

Keywords: ring opening polymerisation
cyclic esters
immortal polymerisation
Advisor: Mountford, P
Synthesis of polyfunctionalised cyclopentanes

This thesis describes the syntheses of some polyfunctionalised cyclopentanes via intramolecular aldol condensations of sugar δ-lactone precursors.
The known azido carbpcycle (1S,2R,3S,4R,5R)-methyl [5-azido-1,2,3,4- tetrahydrpxy-2,3-O-isopropylidene-cyclopentane] carboxylate was prepared from 2- deoxy-2-iodo-3,4:6,7-di-O-isopropylidene-D-glycero-D-talo-heptono-1,5-lactone in five steps. The key reaction was a base-induced intramolecular aldol cyclisation of a 5- iodo-formyl-2,6-lactone. Borohydride reduction of the methyl ester gave an azido triol. Deprotection followed by reduction of the azide functionality produced an amino pentol. The analogous tetrahydroxy β-amino acid was synthesised from the azido carbocycle in three steps. The inhibitory activity of the amino pentol against human liver glycosidases is reported.
Two azido bicyclic lactones, (1R,4R,5R,6R,7R)-4-azido-5,6,7-trihydroxy-5,6-0- isopropylidene-2-oxa-bicyclo[2.2.1]heptan-3-one and (1S,4S,5R,6R,7R)-4-azido- 5,6,7-trmydroxy-5,6-O-isopropydilene-2-oxa-bicyclo[2.2.1]heptan-3-one, were prepared from 3,4:6,7-di-O<./em>-isopropylidene-D-glycero-D-talo-heptono-1,5-lactone in five steps. The (1R,4R,5R,6R,7)-compound was further elaborated to give an amino pentol via a series of borohydride reduction / deprotection / catalytic hydrogenation. A novel carbocyclic spirohydantoin was synthesised by two alternative routes. The second route also provided access to an N'-phenyl spirohydantoin. The inhibitory activities of the amino pentol and the spirohydantoin against human liver glycosidases are reported.
The azido bicyclic lactone triol (1R,4S,5R,6R,7R)-4-azido-5,6,7-trihydroxy-2-oxabicyclo[ 2.2.1]heptan-3-one underwent reduction of the azide functionality with concomitant epimerisation to give the (5S)-epimeric amine. The structure of this material was confirmed by X-ray diffraction analysis of a crystalline derivative. Treatment of the azido triol with base under non-aqueous conditions resulted in a retroaldol reaction to give the (5S)-epimeric azide, the relative configuration of which was determined by single crystal X-ray analysis. A third ketal protected azido bicyclic lactone was prepared via a base-induced retro-aldol epimerisation. Five tetrahydroxycyclopentane α-amino acids, including a pair of enantiomers, were synthesised from the azido bicyclic lactones. The structures of two of the α-amino acids were established by X-ray crystallographic analysis, whilst the enantiomeric compounds were identified using circular dichroism spectrometry.
The diketal protected (2R,3R,4R,5R)-tetrahydroxy-cyclopentane α-amino acid was incorporated into six oligopeptides. Peptide coupling at the C-terminus of the carbocyclic amino acid was carried out using two amino acid tert-butyl esters. Chain extension at the N-terminus was achieved by reaction with N-benzyloxycarbonyl protected amino acids in the presence of 1-(3-dimethylaminopropyl)-3-ethyl-carbodiimide hydrochloride as the carbodiimide reagent. Complete deprotection of a tetrapeptide is described.

Advisor: Fleet, G
Tectonic evolution of the Southern Ocean between Antarctica, South America and Africa over the past 84Ma

An improved method has been developed for carrying out 2-plate reconstructions, in which fracture zone locations are fitted to synthetic flowlines and magnetic anomaly picks are rotated and fitted to great circles representing other, not necessarily conjugate, anomaly isochrons. This enables the determination of finite rotation poles for regions with sparse data coverage, or where much of one or both plates has been subducted. Misfits and partial derivatives are calculated for each type of data, and combined in a single iterative inversion, allowing the direct calculation of confidence intervals. This method is then extended to a 3-plate reconstruction, taking closure into consideration.
The South American - African - Antarctic plate system is then studied. Fracture zone locations are identified from a gravity map constructed from GEOSAT altimeter data, and magnetic anomalies are identified from ship profiles. Two-plate reconstructions are carried out for each plate pair, giving good fits to the observed data, and then all three datasets are combined in a 3-plate reconstruction. Comparison of the results reveals a discontinuity in spreading in the Weddell Sea, believed to be related to pseudo-asymmetric spreading caused by ridge re-organisation in the Paleocene and early Eocene. A revised 3-plate inversion, taking this discontinuity into account, produces an internally consistent set of poles, indicating a closed 3-plate system since anomaly 34 (83Ma), with no evidence for a Malvinas Plate extending into the Weddell Sea in the Late Cretaceous. Disruption to the system from anomaly 32 (71Ma) until anomaly 24 (52Ma), appears to be related to the collision of Africa with Eurasia.
A study of the past motion, configuration and stability of the Bouvet Triple junction suggests that for the majority of the past 50Ma it has been in a RFF configuration, in theory considerably less stable than RRR, the other possible configuration.
Animal metaphor in the Egyptian determinative system: three case studies

Many languages, both ancient and modern, make use of devices similar to determinatives in Egyptian by which the meaning of a word can be made more specific. But determinatives are especially rich in their capacity for expression, particularly regarding words for abstract concepts through their extensive use of visually-based metaphor. Egyptological research is only now beginning to explore the many levels at which the system functioned. My thesis centres around the metaphorical usages of three signs - the Seth animal, the panther, and the crocodile.
The introduction lays out my aimes, methods, and textual sources. The first chapter sets my analysis against the backdrop of current research, beginning with a discussion of how determinatives have been treated in the past, comparing that with a survey of how modern linguistics has approached comparable systems in other languages, and finally laying out my own approach to the three signs under study. In the following three case study chapters, I first survey the evidence for how each animal was perceived in the 'real' world, before moving into a detailed analysis of their significance in the script, which is based on a contextually-grounded, diachronic study of the distribution patterns of each of the signs in five genres of text from the Old to the New Kingdom. In a final chapter, I compare my conclusions about the three determinatives, discussing their commonalities and singularities, and relaitng the results of the individual case studies to the workings of the system as a whole.
My aim is not only to achieve a better understanding of the particular shades of meaning these three animal signs impart to each of the words they determine, thereby leading to a better understanding of these words, but also to examine the wider conceptual metaphors the three determinatives represent.

Keywords: Seth animal
crocodile
panther
determinatives
Advisor: Baines, J
Solution reactivity studies of group 15 Zintl anions towards unsaturated substrates

This thesis describes selected reactivity studies of group 15 Zintl anion [E7]3– (E = P, As) derived cages towards a series of unsaturated organic molecules. The synthesis and characterization of forty-two compounds derived from [E7]3– cages are detailed herein.
A high yielding procedure for the synthesis of [HE7]2– (E = P, As) from the K3E7 Zintl phase has been developed. This solves prior issues with poor solubility and variable purity of the Zintl phases. The conditions required for the deprotonation of the phosphorus congener to [P7]3– are described.
The reactivity of both [P7]3– and [HP7]2– towards carbon dioxide and isolobal isocyanates and carbodiimides was explored. This yielded a series of monofunctionalized [E7R]2– cages, via a net hydropnictination of a C=N double bond of the organic substrate. The protonation chemistry of these anions was further investigated, resulting in the formation of the protic [HP7C(NHDipp)(NDipp)]– cluster. This anion is capable of further hydrophosphination chemistry to give a series of difunctionalized heptaphosphide cages.
The reaction of [E7]3– with alkynes results in the formation of the relatively unusual 1,2,3-tripnictolide anions. A series of such anions have been prepared, encompassing all of the previously reported anions and several novel species. Investigation of the coordination properties of these cyclopentadienyl analogues shows that they are superior π acceptor ligands.
A synthetic route to [P5]– as a compositionally pure solid, and some initial studies on its protonation chemistry are also additionally presented.

Keywords: Main group chemistry
Inorganic chemistry
Advisor: Goicoechea, J
The impact of treatment and time on cardiovascular risk scores

Cardiovascular risk scores predict an individual’s risk of developing cardiovascular disease. Many were developed and validated in study cohorts on risk-factor lowering treatment – a cause of inaccuracy. In addition, risk scores are criticised as being biased towards the elderly due to the prominence of age as a risk predictor. Although present guidelines advocate the use of short-term (5-10 year) absolute risk scores, other approaches to redress this perceived imbalance such as lifetime risk scores are being considered.
The overall objective of this thesis is to identify the most appropriate cardiovascular risk score for use in general practice, taking account of the impact of treatment and time on assessed risk.
This objective was met by three different methods. First, a systematic review of cardiovascular risk scores was conducted. This explored the derivation of each score, including the extent of treatment. Next, doctors were interviewed in depth to understand their perception and use of risk scores. Finally, mathematical models were devised to determine whether a true difference in life expectancy exists at different ages but the same short-term cardiovascular risk. The models incorporated age-specific case fatality rates, competing risks and time preference to estimate the potential years of life lost due to a five-year treatment delay in different age groups with the same short-term coronary heart disease risk.
The findings demonstrate that cardiovascular risk scores do not take account of treatment effects. This significantly affects their application in clinical practice. In addition, there is little difference in potential life years lost between ages at the same risk level because of higher case-fatalities in older people. When time preference is considered, any residual case for treating the same level of short-term risk differently at different ages is abolished.
The overall conclusion is that the five to ten-year absolute cardiovascular risk score is the most appropriate approach to primary cardiovascular disease prevention. By overestimating risk in the young, other approaches benefit the few at the expense of the many.

Keywords: risk prediction
Cardiovascular risk
risk scores
Advisor: Mant, D
Glasziou, P
Millenarian religion and radical politics in Britain 1815-1835: a study of Southcottians after Southcott

The popular millenarian movement founded by Joanna Southcott (1750-1814) enjoyed a complex relationship with political radicalism in early nineteenth-century Britain. Southcott opposed radicalism during her lifetime, encouraging her followers to await a messianic agent of the millennium. Within two decades of the prophet’s death – as Southcott expected to give birth to this messiah – some surviving Southcottians became political radicals, most notably, John ‘Zion’ Ward (1781-1837) and James Elishama Smith (1801-57). Ward was a popular preacher during the agitations around the Reform Bill, Smith a radical lecturer, editor of Robert Owen’s journal Crisis, and ideologue within general trades unionism in 1833-34. The respective influence of each figure drew several hundred Southcottians into engagement with politics. This thesis presents a new interpretation of why such millenarians engaged with radicalism. Utilising a substantial range of Southcottian and radical sources, many previously unstudied, it challenges the existing explanations of Southcottian radicalism of E.P. Thompson, J.F.C. Harrison, Barbara Taylor and others. Through a close study of the religious experience, ideas and practices of Southcottians in 1815-35, it locates an altered disposition towards social activity through the evolving millennial theologies of Southcottian groups and the personal acquaintanceship of individual believers with radical freethinkers. Under the prophetic leadership of Zion Ward and John Wroe (1782-1863), earlier Southcottian notions of the respective roles of divine and human agency in the realising of the millennium were changed by 1830. This led Southcottians to a new sense of agency, where their own actions took on a millennial significance when directed towards the achievement of God’s perceived intentions for the world. For some, this presented engagement with political radicalism, even freethought radicalism, in a new light: as action apposite to their beliefs. This argument features an alternative theoretical framework for millenarian beliefs which takes account of the way conceptions of human agency can vary within religious movements centred on modern prophecy. In exposing the inadequacy of existing pre- and postmillennial categories to explain such beliefs, it demonstrates how visionary religion can inspire expectations of both disruptive and evolutionary change, and require both divine and human agency, in the realisation of the millennium. This is a study in religious history, orientated towards politics. It demonstrates that a sensitivity to how visionary religious ideas influenced individuals involved in political movements, aids an improved understanding of political motivations and ideals.

Keywords: James Elishama Smith
Zion Ward
Joanna Southcott
John Wroe
Radical Politics
Millenarianism
Advisor: Shaw, J
Expansion methods for high-dimensional PDEs in finance

We develop expansion methods as a new computational approach towards high-dimensional partial differential equations (PDEs), particularly of such type as arising in the valuation of financial derivatives. The proposed methods are extended from [41] and use principal component analysis (PCA) of the underlying process in combination with a Taylor expansion of the value function into solutions to low-dimensional PDEs. They enable calculation of highly accurate approximate solutions with computational complexity polynomial in the number of dimensions for PDEs with a low number of dominant principal components.
For the case of PDEs with constant coefficients, we show existence of expansion solutions and prove theoretical error bounds. We give a precise characterisation of when our methods can be applied and construct specific examples of a first and second order version. We provide numerical results showing that the empirically observed convergence speeds are in agreement with the theoretical predictions. For the case of PDEs with varying coefficients, we give a heuristic motivation using the Parametrix approach and empirically test the methods' accuracy for a range of variable parameter stock models.
We demonstrate the applicability of our expansion methods to real-world securities pricing problems by considering path-dependent and early-exercise options in the LIBOR market model. Using the example of Bermudan swaptions and Ratchet floors, which are considered difficult benchmark problems, we give a careful analysis of the numerical accuracy and computational complexity. We are able to demonstrate that for problems with medium to high dimensionality, around 60-100, and moderate time horizons, the presented PDE methods deliver results comparable in accuracy to benchmark state-of-the-art Monte Carlo methods in similar or (significantly) faster run time.

Keywords: Mathematical finance
High-dimensional PDEs
Financial derivative pricing
Asymptotic expansions
Advisor: Christoph, R
The use of electrokinetics to enhance the degradation of organic contaminants in soils

The application of an electric field to contaminated soil specimens and the resulting electrokinetic phenomena have been combined with the degradative actions of bacteria to create a novel method for the remediation of contaminated land. Currently, the vast majority of remediation projects involve disposing of contaminated soil in landfill. With the introduction of, and increases in, landfill tax in the UK, this option is becoming less desirable, and so robust, more sustainable techniques are required, such as bioremediation. A major problem with the implementation of bioremediation is the bioavailability of contaminating chemicals. Reduced accessibility of bacteria to the chemical(s) they are attempting to degrade can lead to significant increases in required remediation times, as well as the possibility of significant residual contamination, the levels of which cannot be easily further reduced. This thesis addresses the problem of bioavailability of contaminants in soils, and has investigated the use of electrokinetic phenomena as tools to bring about an increase in this factor, leading to improved biodegradation. Soil contaminated with pentachlorophenol (sodium salt) was subjected to an electric field in a number of experiments, with significant transport of the initially ionic chemical noted. The transport and fate of this chemical were tracked throughout each experiment, along with properties of the soil pore fluid. Significant changes in soil chemistry were noted (particularly pH or moisture content, depending on the experiment). The effect of pH change was found to be particularly important in this respect, with acidic conditions hindering both movement and bioavailability. A method of applying an electric field to contaminated soil containing degrading bacteria was developed which minimised the changes to these parameters within the soil. A significant increase in the effectiveness of the remediation was noted with this technique, with substantially faster degradation found to occur.

Keywords: electrokinetics
clay
Advisor: Sills, G
Thompson, I
Small places, large issues: identity, morality and the underworld at the Spanish-Moroccan frontier of Melilla

Situated on the north-eastern coast of Morocco, the Spanish enclave of Melilla is a paradigmatic case of an unusual yet increasingly common kind of community. These are small, rather isolated communities with no industry or natural resources of their own, which rely heavily on capital and labour drawn from outside. Together with Ceuta, Melilla is one of the two only land borders between Europe and Africa. The enclave’s economic and political set up reflects its geopolitical importance. Across the border from Melilla lies the Moroccan province of Nador, home to one of the largest communities of Moroccan emigrants in Europe and a steady source of unskilled labour on which the Spanish enclave relies. Connections across the border are strong, including kinship links, employment networks and a wide range of both legal and illegal commercial transactions.
Based on twelve months of fieldwork conducted on both sides of the border, this thesis departs from prevailing images of the borderland as either an abstract space of ‘creolisation’ and ‘hybridity’ or a locus of resistance to state power, and suggests, instead, that we carefully consider the large-scale political and economic processes through which places like Melilla and Nador are produced, and analyse the ways in which such global structures shape local reality. A fundamental aim of the thesis, therefore, is to elucidate the nature of the relations between space, place and capital at the Spanish-Moroccan frontier, and understand how such relations affect the lives of those who inhabit the region. This involves thinking about the language of a ‘community’ and the discourses and practices of morality that sustain it; analysing discourses of ‘us’ vs. ‘them’ in contexts of institutionalised economic inequality; and understanding local conceptions of identity, morality and legitimacy, and how the three interact.

Keywords: Nador
smuggling
identity
borderland
Melilla
informal economy
Rif
morality
Advisor: Dresch, P
Parkin, R