VictorJuiz/thesis huggingface dataset:
The tethered aminohydroxylation of allylic carbamates

The osmium-mediated aminohydroxylation reaction is a powerful oxidation that introduces a hydroxyl group and a protected amino group in a syn relationship across an olefinic double bond. This study concerns one approach to controlling the regioselectivity of this oxidation.
Introduction I
The mechanism, scope and limitations of the aminohydroxylation reaction are discussed, with particular attention to the asymmetric version, providing a background from which the newly developed methodology has emerged.
Results and Discussion I
Development of the reaction
This section concerns the original attempts to perform the tethered aminohydroxylation reaction, and early process optimisation to maximise the yield of aminohydroxylated product produced.
Scope of the reaction
This section details the results of the TA reaction as applied to further allylic carbamates demonstrating the applicability of the reaction to other olefinic geometries. The diastereoselectivity of the reaction in cyclic and acyclic systems is reported, and a model to explain the observed results discussed. Also covered within are the syntheses of the various substrates and proof of the stereochemistry of the products.
Mechanistic investigations
Work involving attempts to isolate a catalytic intermediate from the reaction is described. A crystal structure of this intermediate is discussed.
Introduction II
The isolation and physiological properties of the antibiotic compound hygromycin A are described. Prior synthetic routes towards this compound are discussed.
Results and Discussion II
Three approaches towards the aminocyclitol unit of hygromycin A, employing the tethered aminohydroxylation reaction, are outlined. Two of these allow for potential future development and completion of the synthesis.

Advisor: Donohoe, T
Fleets and Prouinciae in the Roman Republic: institutions, administration and the conceptualisation of empire between 260 and 49 B.C.

This research examines how, when and why the Romans assigned and defined the tasks of preparing and commanding fleets during the Republic. In doing so, it brings new evidence to bear on the wider debates about the nature of the prouincia and the institutional and administrative development of the Roman empire.
The communis opinio is that a prouincia originally represented a functional “sphere of operation” that was allotted or assigned to a magistrate and that it only later developed a geographical meaning with territorial connotations through the process of “provincialisation.” This research challenges that view through an analysis of the evidence for the definition, assignment and practical use of the prouincia classis and other prouinciae connected with the command of fleets. Drawing upon and analysing the lists of administrative arrangements to be found in the “annalistic” sections of the surviving books of Livy’s History, it argues that prouinciae were defined in specific geographical and functional terms long before the development of permanent territorial empire. This offers a new perspective which points to and elucidates the flexible use of the prouincia as a means of separating magistrates and promagistrates in space or by function in space. It argues that the rationale for this was to limit conflicts between commanders over command and triumphal rights.
By combining evidence from a wide range of sources after the loss of Livy’s History from 167, the research shows that the above rationale for demarcating prouinciae still applied in the first century B.C. However, it also demonstrates that there were significant changes with the assignment of vast Mediterranean-wide naval prouinciae in the first half of the first century B.C. It argues that the definition of these prouinciae was made possible by the development of a singular collective Mediterranean-wide ora maritima, which was brought about by the Romans’ increasing “acknowledgement of empire.” The negative political and institutional implications of these developments are also assessed.
Finally, in discussing the above, this research also provides new insights into the role and auctoritas of the Senate, the function and freedom of magistrates, and the Romans’ conceptualisation of their empire.

Keywords: Roman provinces
Roman magistrates
Antonius Creticus
ora maritima
Roman imperialism
Roman fleets
provincia
prouinciae
Roman triumph
Roman promagistrates
special commands
Lex Porcia
Roman History
terra marique
imperium
provinciae
ancient Mediterranean
Roman Republic
Pompeius
Roman navy
naval triumph
prouincia
extraordinary commands
Pompey
Roman Senate
Advisor: Prag, J
The names of wisdom

The Nāmamantrārthāvalokinī ('An Explanation of the Meaning of the Namemantras') is an early, and major, commentary on the Nāmasaṃgīti ('The Chanting of Names'). Written by the eighth century Indian ācārya Vilāsavajra, it survives in the original Sanskrit and in Tibetan translation.
The Nāmasamgīti enumerates the 'Names' of Mañjuśrī, the Mahayana figure embodying wisdom, and it exerted a strong influence on liturgy, ritual and meditation in the later phase of Buddhism in India (750-1200 CE). Vilāsavajra's commentary is written from a Yogācāra perspective and interprets the 'Names' within an elaborate ritual framework which consists in a maṇḍala that has Mañjuśrī as its central deity.
The central part of the thesis comprises a critical edition and annotated translation of the Sanskrit text of the first five chapters of Vilāsavajra's commentary, approximately a quarter of the whole. The critical edition is based on eight Nepalese manuscripts for which a stemma codicum is established. Two blockprint editions of the Tibetan translation are consulted at cruces in the Sanskrit. Their readings, treated as those of any other witness, are incorporated into the apparatus as appropriate. The edition is followed by textual notes.
Introductory material is divided into two parts. Matters relating to the Sanskrit and Tibetan materials are discussed in a section placed before the edition. These include a description of the manuscripts, discussion of the method of editing, establishment of the stemma codicum and an assessment of the Tibetan translation.
An introduction to the contents precedes the translation and is primarily concerned with an outline of the ritual structure of the commentary, giving particular attention to chapters 1-5. Evidence concerning the life and date of Vilāsavajra is considered, suggesting he should be placed in the latter part of the eighth century. Assessing the work's significance for the study of Buddhism, 1 suggest that it is of historical importance in that it throws light on the process by which Tantric methods were being related to soteriology in this period; and that it contains material, especially in the sādhana of chapter 4, that contributes to an understanding of the development of Tantric forms of Buddhist meditation. The work is also the only known instance of a commentary of a Yogatantra type that survives in Sanskrit.
West African labour and the development of mechanised mining in southwest Ghana, c.1870s to 1910

Wassa in southwest Ghana was the location of the largest mining sector in colonial British West Africa. The gold mines provide an excellent case study of how labour was mobilised for large-scale production immediately after the legal end of slavery, in the context of an expansive independent labour market. Divided into three sections, this thesis examines the practice of indirect labour recruitment for the mines during the formative years of colonial rule; the incorporation of ‘traditional’ credit relationships into ‘modern’ commerce. The starting point for this study is the analysis of precolonial strategies for mobilising labour. Part one examines the most pervasive and coercive employer-employee relationship in precolonial West Africa, namely the master-slave relationship. Even enslaved Africans could expect individual economic opportunity, and related to such, debt protection, and the power of labourers increased significantly after abolition. Starting in the 1870s, mine management found that the most effective way of recruiting long-term wage earners was through headmen; African authorities who established temporary patronage relationships with a group of labourers by offering them credit. Moreover, administrative and court records indicate that there were various forms of headship, some which the mines managed to impose greater regulation over than others. Therefore, part two demonstrates that issues of cost and control of recruitment differed depending on whether the labour recruiter had been furnished with the capital of a mining firm to conduct his business, whether he had done so with his own personal savings, or whether he was in the employment of the colonial government. Finally, part three takes a comparative look at headship and recruitment through rural chiefs, which began in 1906; two successive forms of non-free wage labour mobilisation. In 1909, mine management reverted to the headship system that many colonial commentators regarded as being more compatible with the colonial political order, albeit under considerably stricter regulations.

Keywords: Headmen
Recruitment
Wassa
Liberia
Ghana
colonial commerce
Mining
Advisor: Deutsch, J
Life in the rural Shanxi house: seasonal resonances and techniques of transformation in north-central China

This thesis gives an experiential account of notions of the home in contemporary rural China. Based on a year of fieldwork in a mountain village in rural Shanxi Province, the thesis explores everyday and ritual practices to investigate how people make themselves at home under conditions of political economic transformation. Villagers accommodate and resist conflicts of interest by negotiating boundaries of insiders and outsiders through the home. Differences of gender and generation come to the fore as people compromise between aspiration and pragmatism within the home under conditions of resurgent market competition. The theoretical concern of the thesis lies in connecting wider social processes to personal life projects through the intimate sphere of the home.
The rhythm of the seasons patterns the thesis into spring, summer, autumn and winter chapters, as the seasons were pivotal in ordering people’s everyday practices and ritual activities within a shared social and ecological environment. The opening chapter on the autumn harvest coincided with my arrival in the village. The chapter explores how labour, and particularly women’s labour, transforms the earth into affective belonging, and how women negotiate conflicts over food consumption between the agricultural and market economy. The winter chapter parallels tales of personal life history with wider kinship networks across various generations, while simultaneously tracing bodily pathways from the domain of the hot stove in the home to the cold grave in the fields. The next chapter begins with the celebratory periods of springtime during the New Year Festival, a time of ritual renewal in the home when women partook in a local domestic ritual of propitiating the little spirits of the house. At Qingming Festival villagers’ practices of worshipping the ancestors in the fields were juxtaposed with a tour company’s staging of an elaborate ritual revival of star worship in the village. Conflicting aspirations over the future of the past thereby tore fissures into the emerging ritual terrain between outside spectacle and inside convergence. The last ethnographic chapter looks at the summer as a time for regenerating life, particularly through marriage and children. Reciprocal caring cycles between different generations of women are central to balancing domestic and occupational aspirations in negotiation with the local implementation of the family planning policy. House-based rituals at children’s birthday parties and bridal farewell ceremonies formally celebrate the roles of matrilateral relatives.

Keywords: gender
tourism
labor
ecology
season
kinship
development
women
life cycle
generation
China
reproduction
family
ritual
fertility
body
house
home
anthropology
Shanxi
Advisor: Hsu, E
Twistors in curved space time

This thesis is concerned with an investigation of twistorial structures present in curved Lorentzian space-times.
Chapter 1 introduces the basic definitions and some theorems that will be used later in the text.
Chapter 2 investigates generalised connections that arise in twister theory. First the Cartan con-formal connection is studied, and some of the geometry underlying it is shown to be that used by Fefferman and Graham C133. Also a condition that a space-time is conformal to vacuum is given. Secondly the theory of the Chern connection associated to a C.R. manifold is developed in such a way as to make the calculation of the connection associated to a twistor C.R. manifold straight forward. A new proof of the Chern theorem of existence and uniqueness is given. The Chern connection of a twistor C.R. manifold is then calculated, and discussed. In particular S-dimensionai C.R. manifolds arising as twistor C.R. manifolds are characterised. Canonical structures peculiar to the twister case are discussed. Applications of C.R. manifold theory to algebraically special space-times are suggested.
Chapter three analyses how various twistorial structures behave in linearised general relativity. First, deformations of the space of complex null geodesies corresponding to variations of the conformal structure of space-time are shown to be generated by hami1tonians. Those that correspond to variations in the metric satisfying the field equations are given, along with hamiltonians corresponding to different fields and field equations. Beneralisations to nonlinear equations are discussed.
These ideas are applied to hypersurface twisters in linearised theory, using fiat hypersurfaces and Cech cohoeology. Expressions are obtained for the deformation of the complex structure of the spaces and their evolution. The results are generalised to non flat hypersurfaces using Dolbeault cohomolcgy. It is shown that certain canonically defined forms on the spin bundle are preferred Dolbeault representatives for derivatives of the twister cohomology classes corresponding to the linearised field.
In chapter four I generalise the results of chapter three to curved space using the Chern connection. In particular twistorial formulations of the constraint equations are given, and a formula for the evolution that satisfies the the vacuum evolution equations is given in terms of an "infinity" twistor and a "time" twister. This is then discussed.
In chapter five I make some comments on the interpretation of a three form on the spin bundle discovered by B.A.J. Sparling as the gravitational hami1tonian. I then use this to show that one can give an interpretation of Penrose's quasi-local angular momentum twistor in terms of the canonical formalism.

Advisor: Woodhouse, N
Structural studies of malaria proteins

Malaria is a disease of global importance, causing hundreds of thousand of deaths a year. The majority or deaths are caused by Plasmodium falciparum, a parasite transmitted by the mosquito Anopheles. Its pathogenicity largely results from an ability to transform infected erythrocytes by creating knob-like structures that result in endothelial adhesion. Two major components of these knob structures have been identified as P. falciparum erythrocyte membrane protein 1 (PfEMP1) and knob-associated histidine rich protein (KAHRP). The extracellular fragment of PfEMP1 is responsible for antigenic variability and cytoadherence while its intracellular domain (ATS) connects to the cytoskeleton via interactions with other plasmodium-encoded proteins. In addition, perforin-like proteins (PLPs) with a MACPF domain have been identified in the genome of Plasmodium. PLPs are highly conserved and are expressed in various life-cycle stages of the parasite. They are believed to form pores in membranes of the host cell but their structure is yet unknown. The aim of the work in this thesis was to obtain new information about the structure and role of malaria proteins, thus giving a better understanding of the disease and its possible treatment. Studies of numerous designed constructs of the ATS family were carried out using biophysical methods including high resolution NMR and CD. These revealed that ATS domains are mainly unstructured with a relatively small folded core, consisting of a bundle of α-helices. Surprisingly, no evidence could be found for ATS binding to KAHRP in solution conditions although previous pull-down data had indicated an interaction. Bioinformatics analysis and yeast-two-hybrid data suggested, however, that there is a conserved protein interaction epitope on the central flexible part of ATS. It was shown, using fluorescence anisotropy measurements, that this part of ATS associates with a parasite protein containing a PHIST (Plasmodium helical interspersed sub-telomeric) domain. Expression constructs of the PLP protein family were designed and manufactured, with the aim of enabling structural studies of this putative pore protein.

Keywords: ATS
KAHRP
Plasmodium
Malaria cytoadherence
PHIST Domain
PfEMP1
Advisor: Campbell, I
Gilbert, R
Sampling the sensitivity of climate models

The sensitivity of climate models in particular, and nonlinear models in general, is a topic of great interest. Quantifying this sensitivity by brute force numerical exploration is often computationally untractable due to the large number of parameters involved, and it is widely hoped that a small number of effectiveparameters′(l∈earcomb∈ationsofthephysicalparameters)maydominatethemodelresponseandhenceeasethetaskofsensitivityanalysis.A≠wmethodforidentify∈gthiseffective dimension' of the model response is introduced and applied to two simple models. General issues of identifying the response are discussed. No low dimensional response is found in the more complex model considered.
Charge state manipulation of silicon-based donor spin qubits

Spin properties of donor impurities in silicon have been investigated by electron spin resonance (ESR) techniques for more than sixty years. These studies gave us a contribution towards understanding some of the physics of doped semiconductor materials in general, which is the platform for much of our current technology. Despite the fact that donor electron and nuclear spins have been researched for so long, ESR studies of their properties are still giving us interesting insights. With the introduction of the concept of quantum information in the 1980s, some properties of donor spins in silicon, that were known from the fifties (such as long relaxations), have been reinterpreted for their potential application in this field. Since then, incredible experimental results have been achieved with magnetic resonance control, including manipulation and read-out of individual spins. However, some open questions are still to be answered before the realisation of a spin-based silicon quantum architecture will be achieved. Currently, ESR studies still contribute to help answering some of those questions. In this thesis, we demonstrate electrical and optical methods for donor charge state manipulation measured by ESR. Recent experiments have demonstrated that coherence time of nuclear spins may be enhanced by manipulating the state of donors from neutral to singly charged.
We investigate electric field ionisation/neutralisation of arsenic donors in a silicon SOI device measured by ESR. Below ionisation threshold, we also measure the hyperfine Stark shift of arsenic donors spins in silicon. These results have, for instance, implications on how fast individual addressability of donor spins may be achieved in certain quantum computer architectures. Here, we also study optical-driven charge state manipulation of selenium impurities in silicon. Selenium has two additional electrons when it replaces an atom in the silicon crystal (i.e. double donor). The electronic properties of singly-ionised selenium make it potentially advantageous as spin qubit, compared to the more commonly studied group-V donors. For instance, we find here that the electron spin relaxation and coherence times of selenium are up to two orders of magnitude longer than phosphorus at the same temperature. Finally, we demonstrate that it is possible to bring selenium impurity in singly-charged state and subsequently re-neutralise them leaving a potential long-lived 77Se nuclear spin.

Keywords: Selenium
Solid State Physics
Qubit
EPR
Spin
Quantum Information
Silicon
Advisor: Morton, J
Benjamin, S
Synthesis of the pyrrolidinone core of oxazolomycin A

This thesis describes the development of synthetic strategies towards the densely functionalised pyrrolidinone core of the polyene β-lactone-γ-lactam antibiotic oxazolomycin A.
Chapter 1 The oxazolomycins
The oxazolomycins, a unique class of biologically active molecules containing a spiro-fused β-lactone-γ-lactam ring system are introduced. The isolation, structural elucidation and biological properties of the oxazolomycins as well as those of the structurally related inthomycins are reviewed.
Chapter 2 Previous syntheses
The two total syntheses of neooxazolomycin and the synthetic approaches to the pyrrolidinone core of oxazolomycin A and KSM-2690 B are evaluated.
Chapter 3 Project aims
An outline of the synthetic strategy employed in this project and details of the novel retrosynthesis of the pyrrolidinone core of oxazolomycin A are discussed.
Chapter 4 Synthetic studies towards the pyrrolidinone core of oxazolomycin A
The synthetic studies carried out towards the pyrrolidinone core of oxazolomycin A are described in detail. The preparation of an advanced intermediate containing the five chiral centres, four of which are contiguous, was achieved in twenty steps as a single diastereomer and as a single enantiomer.
Chapter 5 Synthetic studies towards the middle fragment of oxazolomycin A
A novel synthetic approach to the diene fragment contained in oxazolomycin A is reported. The formal synthesis of a dienyl iodide, in four fewer steps than previously reported was accomplished.
Chapter 6 Conclusions and future work
A summary of the synthetic work reported in this thesis and proposals for future study are presented.
Chapter 7 Experimental
Full experimental procedures and characterisation of compounds are reported.
Chapter 8 References
A complete list of citations employed in the previous seven chapters is provided.

Keywords: Antibiotics
Total synthesis
Natural products
Advisor: Donohoe, T