VictorJuiz/thesis huggingface dataset:
Aziridines and aziridinium intermediates in the asymmetric synthesis of beta-substituted-alpha-amino acids and 1,2,3,4-tetrahydroisoquinolines  

This thesis is concerned with the development of methodology for the regioselective ring-opening of aziridines and aziridinium intermediates and its subsequent application to the asymmetric synthesis of β-substituted-α-amino acids and 1,2,3,4-tetrahydroisoquinolines.
Chapter 1 introduces methods for the formation of aziridines and aziridinium ions and focusses on their utility as intermediates in synthesis.
Chapter 2 describes studies into the synthesis of aziridines from enantiopure α-hydroxy-β-amino esters and their subsequent conversion to the corresponding β-hydroxy-α-amino acids via either a regioselective ring-opening with Cl3CCO2H, or a rearrangement promoted by Cl3CCO2H. Application of this procedure to both syn- and anti-configured substrates enabled the syntheses of (S,S)-allo-threonine, (2R,3S)-threonine, (R,R)-3-hydroxyphenylalanine and (2S,3R)-3-hydroxyphenylalanine.
Chapter 3 details attempts to truncate the synthesis described in Chapter 2 by investigating the synthesis of enantiopure anti-β-hydroxy-α-amino acids via the intermediacy of aziridinium ions. These studies culminated in the development of a regioselective and stereospecific one-pot aziridinium formation and ring-opening protocol, leading to the synthesis of a range of C(3)-aryl and C(3)-alkyl substituted anti-β-hydroxy-α-amino acids.
Chapter 4 discusses the conversion of enantiopure anti-α-hydroxy-β-amino esters to anti-β-fluoro-α-amino esters via the regioselective and stereospecific ring-opening of an aziridinium intermediates in situ. The subsequent development of a one-pot deprotection strategy leads to a concise and expedient synthesis of anti-β-fluorophenylalanines. The extension of this methodology to access a representative anti-α,β-diamino acid is also demonstrated.
Chapter 5 describes the development of a one-pot diastereoselective rearrangement of enantiopure α-hydroxy-β-amino esters to 1,2,3,4-tetrahydroisoquinolines. The substrate scope of this reaction manifold is examined and application to the asymmetric synthesis of enantiopure 1,2,3,4-tetrahydroisoquinolines also discussed.
Chapter 6 contains full experimental procedures and characterisation data for all compounds synthesised in Chapters 2, 3, 4 and 5.

Keywords: Aziridiniums
Aziridines
Lithium Amide
Amino Acids
Tetrahydroisoquinolines
Advisor: Davies, S
Synthesis of complex γ-lactones mediated by manganese(III)

This thesis details the development of manganese(III) acetate-mediated oxidative radical cyclisation methodology. In particular, the use of radicals to form complex, highly sterically congested and strained carbo- and heterocycles in a stereocontrolled manner is described.
Chapter 1 gives a summary of the literature regarding three key areas relevant to this work. Radical reaction mechanisms are introduced, including the use of transition metals and lanthanides in C-centred radical cyclisations. The formation of highly sterically congested vicinal all-carbon quaternary stereocentres is also discussed. Finally, the use of radical cyclisation methodology for the synthesis of complex cyclic structures and applications in natural product total synthesis is examined.
Chapter 2 gives an account of the manganese(III) acetate-mediated cyclisation of 5-pentenyl malonates bearing a terminal aryl group. The effects of the aryl group are tested with a range of electronically varied substituents. The formation of bi- and tricyclic cyclopentane-lactones bearing adjacent quaternary-quaternary-tertiary stereocentres is demonstrated.
Chapter 3 demonstrates the synthesis of highly strained tricyclic bis-lactones. The metal complexes manganese(III) acetate and cerium(IV) ammonium nitrate are shown to give complementary stereoselectivity across a range of cyclisation substrates. Possible synthetic applications of tricyclic bis-lactones are also investigated.
Chapter 4 details an asymmetric formal synthesis of the proteasome inhibitor salinosporamide A. An oxidative radical cyclisation forms the key heterocycle in Danishefsky’s synthesis of this biologically important molecule, and showcases the use of the radical chemistry in natural product synthesis. Full experimental details, selected NMR spectra, and X-ray crystallographic data are also provided.

Keywords: lactone
quaternary
manganese
stereocentres
Advisor: Burton, J
Bayesian numerical analysis: global optimization and other applications

We present a unifying framework for the global optimization of functions which are expensive to evaluate. The framework is based on a Bayesian interpretation of radial basis function interpolation which incorporates existing methods such as Kriging, Gaussian process regression and neural networks. This viewpoint enables the application of Bayesian decision theory to derive a sequential global optimization algorithm which can be extended to include existing algorithms of this type in the literature. By posing the optimization problem as a sequence of sampling decisions, we optimize a general cost function at each stage of the algorithm. An extension to multi-stage decision processes is also discussed.
The key idea of the framework is to replace the underlying expensive function by a cheap surrogate approximation. This enables the use of existing branch and bound techniques to globally optimize the cost function. We present a rigorous analysis of the canonical branch and bound algorithm in this setting as well as newly developed algorithms for other domains including convex sets. In particular, by making use of Lipschitz continuity of the surrogate approximation, we develop an entirely new algorithm based on overlapping balls.
An application of the framework to the integration of expensive functions over rectangular domains and spherical surfaces in low dimensions is also considered. To assess performance of the framework, we apply it to canonical examples from the literature as well as an industrial model problem from oil reservoir simulation.

Keywords: gaussian processes
global optimization
radial basis functions
surrogate approximation
Advisor: Gould, N
Farmer, C
Electromagnetic forces in flexible systems

Some problems in electro dynamics have been studied in the light of electromagnetic field theory and computational techniques.
One is that of the retrograde motion of the electric arc – an old and intriguing problem of physics. A more complete model based on electrodynamics has been proposed for study of this problem. In this model, the plasma column is treated as a flexible conductor. The associated 3-dimensional boundary-value problem was solved by the boundary element method (BEM). It has been shown that the retrograde motion can indeed be understood in terms of electrodynamics and a number of the reported features of this phenomenon have been explained by the proposed model.
The others are concerned with a recent controversy in electrodynamics. It has been discussed in the thesis that Lorentz and Ampere force laws are equivalent in the sense of magnetostatics provided that the latter is appropriately used. The interactions of electromagnetic forces on the systems of the electromagnetic jet propulsion and the electromagnetic impulse pendulum have been examined. It turns out that the observations are consistent with the laws of electromagnetic energy and momentum. Two aspects of the water-arc explosion problem have been studied. One is the electromagnetic (EM) aspect which is calculated by the method of separation of the variables, the other is the magnetohydrodyuamic (MHD) aspect which is solved by the finite difference method (FDM). The numerical results of the two aspects show that neither the pure EM model nor the MHD model for the incompressible fluid could explain the explosive phenomenon; this strongly suggests that the shock wave produced by the under-water arc must account for the phenomenon. On the wire fragmentation, a preliminary study has shown that this phenomenon could be caused by the electromagnetically driven stress waves and a theoretical model has been proposed for further investigation. This is described in an Appendix to the thesis.

Advisor: Allen, J
High resolution secondary ion mass spectrometry analysis of trace elements in cereal grain and roots

This thesis presents information on the subcellular localisation of two important trace elements, selenium and arsenic, in wheat, rice and rice roots for what is believed to be the first time. The general aim of this work was to illustrate the potential of using physical science techniques to solve biological problems. High resolution secondary ion mass spectrometry was undertaken using the CAMECA NanoSIMS50 with a sensitivity down to ppm concentrations and a lateral resolution of less than 100 nm. Selenium in wheat grain was found to be distributed across both the bran layer and the endosperm region with Se-rich hotspots found in the aleurone cells and a higher intensity of Se in the subaleurone region. Arsenic in rice grain was found in two key regions. In grains with high As and high dimethylarsinic acid (DMA) content, As was predominantly localised to the subaleurone region yet in lower concentration, hydroponically grown As(III)-treated grains the As was only localised to the aleurone layer near the ovular vascular trace (OVT). A combined NanoSIMS and S-XRF experiment revealed As hotspots near the OVT. A combination of high pressure freezing, high resolution secondary ion mass spectrometry and TEM was used to localise As in the roots of rice plants revealing a contrasting subcellular distribution of As and Si in the roots even though arsenite and silicic acid are transported across the plasma membranes by the same transporters. Fe plaque forms only on the root epidermis and was shown to be a strong sink for As. Colocalisation of S with As in the vacuoles of the endodermis, pericycle and xylem parenchyma supports the notion that As is stored as arsenite-phytochelatin complexes in the roots while Si is localised in the endodermis cell walls and is not strongly affected by the Lsi2 mutation.

Keywords: high resolution SIMS
plant science
iron
materials science
microscopy
selenium
nutrition
trace elements
arsenic
Advisor: Grovenor, C
Building workers’ power against globally mobile capital: case studies from the transnational garment sector

Garment sector trade unions have proved largely powerless to combat hypermobile transnational capital’s systematic extraction of surplus value from the newly industrialized Global South. Optimized conditions for accumulation coupled with the 2005 phase-out of the Multi-Fibre Agreement (MFA) have meant a radical geographic reconfiguration of the globalised garment industry heavily in favour of capital over labour.
The thesis approaches the global garment sector from multiple vantage points across the world with the goal of uncovering the obstacles to workers' organisation, examine workers' strategies of resistance, and analyse the changing composition of labour and capital within the clothing commodity chain. The thesis highlights five distinct but interconnected case studies including a transnational workers campaign from a garment factory in Honduras; a history and present-day feasibility of establishing a transnational collective bargaining from El Salvador to Turkey to Cambodia; the prospects for a countermovement in the organizing strategies at the bottom of the clothing commodity and supply chain in Bangalore; the growth of a 'full package' denim manufacturer in changing the relationship between 'buyers' and 'suppliers' on the outskirts of Bangalore; and finally a continuation of this analysis the case of a strike at a monopoly footwear supplier in China.
The central research question is: How do workers build power and establish workers' rights in the globally hypermobile garment sector? Ultimately, what is demonstrated within this thesis is that the actions of garment workers shaped and circumscribed the actions of capital in the sector, and as capital transformed new landscapes for accumulation new vistas for opposition begin to emerge.

Keywords: workers' rights
global value chains
labour movements
garment sector
globalization
Advisor: McDowell, L
Determination of the CKM phase γ at LHCb using the decay mode B± to DK± and a study of the decays D0 to KS0K±π∓ using data from the CLEO experiment

This thesis documents studies of CP violation in B± to [KS0h⁺h⁻]DK±, (h = π/K) decays using data taken by the LHCb experiment during 2011, and the first measurement of γ to be made at the Large Hadron Collider (LHC), γ = (45+43-38) degrees.
Also included is a study of D0 to KS0K∓π± decays using CLEO III and CLEO-c data, resulting in the first amplitude models to be published for these decays and a measurement of the ratio of their branching fractions.

Keywords: CLEO
LHC
LHCb
CP violation
Dalitz Analysis
CERN
Advisor: Wilkinson, G
Malde, S
Proton radiotherapy uncertainties arising from computed tomography

Proton radiotherapy is a cancer treatment which has the potential to offer greater cure rates and/or fewer serious side effects than conventional radiotherapy. Its availability in the UK is currently limited to a single low-energy fixed beamline for the treatment of ocular tumours, but a number of facilities designed to treat deep-seated tumours are in development. This thesis focusses on the quantitative use of x-ray computed tomography (CT) images in planning proton radiotherapy treatments. It arrives at several recommendations that can be used to inform clinical protocols for the acquisition of planning scans, and their subsequent use in treatment planning systems.
The primary tool developed is a software CT scanner, which simulates images of an anthropomorphic virtual phantom, informed by measurements taken on a clinical scanner. The software is used to investigate the accuracy of the stoichiometric method for calibrating CT image pixel values to proton stopping power, with particular attention paid to the impact of beam hardening and photon starvation artefacts.
The strength of the method adopted is in allowing comparison between CT-estimated and exactly-calculated proton stopping powers derived from the same physical data (specified in the phantom), leading to results that are difficult to obtain otherwise. A number of variations of the stoichiometric method are examined, identifying the best-performing calibration phantom and CT tube voltage (kVp). Improvements in accuracy are observed when using a second-pass beam hardening correction algorithm.
Also presented is a method for identifying the proton paths where stopping power uncertainties are likely to be greatest. Estimates of the proton range uncertainties caused by CT artefacts and calibration errors are obtained for a range of realistic clinical scenarios. The current practice of including planning margins equivalent to 3.5% of the range is found to ensure coverage in all but the very worst of cases. Results herein suggest margins could be reduced to <2% if the best-performing protocol is followed; however, an analysis specific to the CT scanner and treatment site in question should be carried out before such a change is made in the clinic.

Keywords: medical physics
proton beam therapy
computed tomography image artefacts
radiotherapy treatment planning
charged particle therapy
proton therapy
Advisor: Peach, K
Hill, M
The legitimacy of international legal institutions

This thesis is about the legitimacy of political authority in general and international legal institutions (ILIs) in particular. It is divided into two parts with three chapters corresponding to each part. The first part presents an account of legitimate political authority that is based on Joseph Raz's service conception of authority but also makes some important modifications to it. The central claim of the first part is that the legitimacy of political authorities in general, as measured by the standard of Raz's Normal Justification Thesis, depends in a crucial way on the ability of the subjects to get involved –more so than Raz is prepared to admit– in the activities that are relevant in the political domain.
The thesis offers a general account of legitimate political authority, i.e. one that is valid for any type of political authority. The second part, however, examines the implications of this account for the legitimacy of ILIs. These are non-state authorities, such as the World Trade Organisation or the International Criminal Court, that deal with problems of global political relevance. Because of this global approach, the subjects of ILIs (i.e. those whose reasons are to be served by the ILI) are not confined to the boundaries of regions or states, but distributed across the world. ILIs operate by creating, interpreting, and applying public international law.
Despite some striking differences between ILIs and other types of political authority (particularly states), I argue that they all ought to be measured by the same standard of legitimacy, namely the Normal Justification Thesis. But I also argue that the requirements for meeting this standard of legitimacy may vary according to the type of political authority (especially with regard to the requirement of democracy).

Keywords: democracy
legitimacy
international organisations
authority
Joseph Raz
transparency
participation
moral reasons
Advisor: Tasioulas, J
McDermott, D
Analysis of DMD translocations

Duchenne and Becker muscular dystrophies (DMD, BMD) are allelic X-linked diseases which affect approximately one in 3500 male newborns. They are caused by mutations in a gene positioned on the short arm of the X chromosome at Xp21. The first indication of the location of this gene was the description of rare females expressing DMD and who were found to have constitutional X;autosome translocations with an X chromosome breakpoint at this site. There are now 24 such females known worldwide. They express DMD as a consequence of preferential inactivation of the normal X chromosome. In order to contribute to the understanding of the aetiology of mutations causing DMD and the aetiology of constitutional translocations, two types of study have been performed here. Firstly, the detailed mapping of the X chromosome breakpoints of DMD-associated X;autosome translocations has been investigated. The results of this study have been compared with data on the physical distribution of mutations causing DMD in male patients. Secondly, one translocation, an X;l translocation with an autosomal breakpoint at Ip34, has been selected for more detailed investigation and the DNA sequence has been determined at the site of the rearrangement.
Translocation breakpoint mapping studies were performed by somatic cell hybrid analysis. Hybrids were karyotyped and this information was used to construct a hybrid panel for the purpose of determining the autosomal localisations of anonymous DNA probes. The mapping of seven probes using this panel is described.
The work described in this thesis revealed that the distribution of translocation breakpoints within the DMD gene appears to be random and may differ from the distribution of mutations in male patients. The X;l translocation whose breakpoints are cloned and sequenced was found to involve two expressed loci, one coding for dystrophin on the X chromosome and one for the leukocyte antigen related protein on chromosome 1. Sequence data revealed that a deletion of four to seven nucleotides from the X chromosome and a duplication of two to five nucleotides are associated with the translocation. The possible involvement of trinucleotides adjacent to the breakpoints, and of a LINE, a SINE and a stretch of potential Z-DNA within 1 kb of the X chromosome or the chromosome 1 breakpoint, is discussed.

Advisor: Craig, I
Boyd, Y
Empowerment through Hindu nationalism?

This dissertation explores whether women and men can be empowered through cultural nationalism based on religious/ethnic identities. Religious fundamentalism is typically not associated with women's empowerment. As a patriarchal, Hindu nationalist party that advocates violence, the Shiv Sena is also an unlikely agent of women's empowerment. Yet, the Sena has been attracting numerous women who claim to have gained confidence through the party. Using the Shiv Sena as my case study, I interviewed four male and seven female Shiv Sena members using the biographic narrative method. By examining their biographic narratives and interviews of their families and colleagues, I was able to delineate the different empowerment cycles for men and women in Shiv Sena and determine each participant's level of empowerment.
The empowerment framework defined by Jo Rowlands (1997), which distinguishes between personal, collective, and relational empowerment, serves as the basis of my assessment of women's and men's empowerment. As violence is generally disregarded as a means of empowerment, I discuss it in relation to the construction of empowering cultural identities. While establishing theoretical frameworks regarding empowerment, cultural identity and gender, I also examine the disempowerment of Maharashtrians (whom Shiv Sena originally represented) by the socio-economic and historical conditions of Bombay, India. I then demonstrate how Shiv Sena, led by its Chief, Bal Thackeray, has constructed a new hegemonic masculine identity for Maharasthrian men as a means of empowerment. In the final chapters, I examine Shiv Sena's impact on the lives of individual women and men. This analysis revealed that despite the patriarchal constraints imposed by the Sena, women were becoming personally empowered in both the private and public spheres. In contrast, while Shiv Sena men were achieving collective empowerment in the public sphere, they had more difficulty becoming personally empowered in both the home and workplace.

Advisor: Peach, C
Prompt neutrino production in the 1982 beam dump experiment at CERN

Principles of beam dump experiments are reviewed and the 1982 beam dump at CERN using the Big European Bubble Chamber is described in detail. Neutrino events have been detected using both the bubble chamber and its associated electronic detectors. Prompt event rates are established for Vμ , Ṽμ , Ve and Ṽe . The prompt rates are consistent with lepton universality. The charm production cross-section required to explain the prompt electron-(anti)neutrino signal is approximately 16-105/μb per nucleon, assuming linear dependence of this cross-section on nucleon number. This range of values reflects the fact that we have not been able to find a model which is consistent with all aspects of the data.
The neutral to charged current ratio for electron-neutrinos is found to be 0.23 ±0.16. The expected number of tau-neutrino events is estimated and kinematic and visual searches for tau-neutrino interactions are described. One visually detected candidate is described in detail. No positive evidence for a tau-neutrino interaction has been found. From the ratio of neutral to charged current events in the data we infer that no more than 4% of the prompt charged current events and 40% of the total prompt signal may be attributed to tau-neutrinos at 90% CL.

Advisor: Myatt, G