VictorJuiz/thesis huggingface dataset:
Natural product inspired organic synthesis: enantiopure heterocycles modelled on pramanicin

This thesis is concerned with the synthesis of chiral pyrrolidinone scaffolds as mimics of the natural product pramanicin, and the evaluation of their antibacterial properties for use towards the development of potential novel antibacterial lead compounds.
Chapter 1 discusses the urgency of the antibiotic resistance problem as well as the current lack of new antibiotics in the drug pipeline. This dearth of new antibacterials is partly attributed to the combinatorial libraries used in the screening process which occupies a limited chemical space. By applying the natural product-inspired paradigm, it is hypothesised that a drug discovery process with a starting point based on a natural product, possessing intrinsic antibacterial properties, may provide insights to a novel class of antibacterials.
Chapter 2 describes the synthesis of three different scaffolds of oxygenated pyrrolidinones via a common bicyclic intermediate synthesised from L-pyroglutamic acid. The use of a mild and facile epoxidation condition utilising H2O2/tertiary amine afforded the epoxypyrrolidinones. α-Hydroxylation with “Davis oxaziridine” and a Ru-mediated dihydroxylation gave 2-hydroxypyrrolidinones and 2,3-dihydroxypyrrolidinones respectively. In all cases, a pendant Weinreb amide was used to introduce a variety of side-chains onto the parent pyrrolidinones. The enantioselective oxygenation of these scaffolds was accomplished as a result of the chiral [3.3.0] bicyclic intermediate.
Chapter 3 describes the attempted synthesis of oxygenated pyrrolidinones via tetramic acids. Although progress was thwarted by synthetic challenges discussed therein, a series of tetramic acids was synthesised. A synthetic sequence to install a 3-acyl moiety onto the parent tetramic acid core was accomplished via an O-acyl/C-acyl rearrangement using a series of carboxylic acids in the presence of excess DMAP. The use of a 3-acyltetramic acid with a pendant phosphorane permits a general synthetic route, compatible with a wide range of aldehydes, towards 3-enoyltetramic acids via Horner-Wadsworth-Emmons olefination. These tetramic acids are mimics of another class of bactericidal natural products which nonetheless allows the natural product-inspired paradigm to be investigated.
Finally, an analysis of the antibacterial properties of the synthesised compounds is discussed in Chapter 4. A cellular hole-plate bioassay with E. coli and S. aureus was chosen to provide a rapid assessment for active compounds. A correlation between the physicochemical properties and the observed activities of these active compounds suggested possible chemical modifications which could be undertaken in the future to improve their activities.

Keywords: antibacterial drugs
heterocycles
Natural products
Advisor: Moloney, M
Success nonetheless

A large part of the study of politics is dedicated to identifying the circumstances under which democracy will flourish. Putnam made a major contribution to this field through his concept of social capital as developed in Making Democracy Work. Putnam found that communities with a high number of civic associations –i.e. social capital- had a better chance of developing an effective style of democratic government.
This definition of social capital sparked much subsequent research and policy activity. It is argued here, however, that this work ignored the immediate needs of societies which do not have the required stock of social capital. There is still little guidance available on how effective government can be achieved even if the right societal circumstances are absent.
This thesis hopes to find inspiration from government agencies that were successful despite their challenging social capital conditions. It specifically looks at sixteen public utilities on the Caribbean islands of Aruba, Curacao and St. Kitts between 2005 and 2009. The thesis then systematically investigates the relationship between the performance of the agencies and the behaviour of their senior officials.
It emerges that in the absence of social capital, governance is in these cases mainly hampered by a deluge of irrelevant data. Successful utilities overcame this flood by constantly upgrading the quality of information, implementing a strict yet inclusive style of governance, and allowing strong leaders the space to translate words into actions. These outcomes suggest that social capital forms an important tool for ordering information, and that, in its absence, there are still alternative strategies available to secure success nonetheless.

Keywords: governance
public utilities
islands
social capital
Caribbean
small-scale democracies
small countries
Advisor: Hood, C
Discrimination and ethnic group identity as explanations of British ethnic minority political behaviour

This thesis looks at the role of discrimination and ethnic group identity as explanations of political behaviour of ethnic minorities in Britain. Chapter 2 examines vote choice and partisanship, arguing that a group utility heuristic explains the high level of support for the Labour party among ethnic minorities. I provide individual-level evidence of this heuristic by showing that ethnic minority voters support the Labour party to the extent that they are (i) conscious of the experiences of their ethnic group members with regards to discrimination, and (ii) believe that the Labour party is the best political party to represent their interests. These two attitudes mediate the effects of group-level inequalities. Chapter 3 asks whether Muslims are alienated from mainstream politics by Islamophobia and British military intervention in Muslim countries. I find that perceptions of Islamophobia are linked with greater political alienation, to a greater likelihood of non-electoral participation, but also to a lesser likelihood of voting. Likewise, disapproval of the war in Afghanistan is associated with greater political alienation and a greater likelihood of some types of non-electoral participation. I also provide strong evidence that Muslims in Britain experience more religious discrimination than adherents of other minority religions. Chapter 4 considers the interaction between the extreme right and ethnic minority political attitudes and behaviour. I find evidence that the extreme right British National Party (BNP) increases voting for the Labour party, at the expense of minor parties and abstention. Surprisingly, the BNP effect also benefits the other main parties. Although they do not benefit in increased vote share, Liberal Democrat and Conservative party and leader evaluations are more positive where the BNP stood and performed better in 2010, which I suggest is due to the electoral contrast provided by the BNP. Chapter 5 looks at the mobilisation effect of ethnic minority candidates on ethnic minority voters. I find a positive mobilisation effect of Pakistani and Muslim Labour candidates on Pakistani and Muslim voters, conditional on someone trying to convince the respondent how to vote. I also find a demobilisation effect of Labour Muslim candidates on Sikh voters.

Keywords: Islamophobia
extreme right
ethnicity
voting
Advisor: Fisher, S
The devil in the detail: demons and demonology on the early modern English stage

"The Devil in the Detail" explores the rationality of magical belief on the early modern English stage. I examine how demons and demonic magic were depicted in the theatre, arguing that playwrights ascribed a sense of realism to the devil’s methods. In explaining the devil's modus operandi and exposing the limitations of his magic, the stage validates supernatural belief and depicts the devil’s craft as plausible. More broadly, this thesis is situated within the ongoing debate over the relationship between magic and scientific thought in early modern Europe, confirming that demonology was not an irrational superstition but a valid pre-science. Set against a background of witch persecution and the widespread belief that demons were a material reality, the devil was both the subject of prevalent intellectual inquiry and a popular figure on the early modern English stage, featuring in at least fifty-two plays between 1509 and 1638. Underpinning this particular brand of entertainment is a cohesive and consistent ontological framework that dictated the extent to which the devil could - and could not - operate in the material world, entirely in keeping with the dominant demonological thought of the time. "The Devil in the Detail" focuses on seven devil plays: Marlowe's Doctor Faustus (c.1590), Greene's Friar Bacon and Friar Bungay (c.1590), John of Bordeaux (c.1590), Jonson's The Devil is an Ass (1616), Dekker, Ford and Rowley's The Witch of Edmonton (1621), Brome and Heywood's The Late Lancashire Witches (1634) and Shakespeare's The Tempest (1611). In each chapter, I demonstrate how these texts both adhere to orthodox demonology and emphasise the devil’s humanlike qualities. The final chapter presents the case for demonism in The Tempest.

Keywords: Devil
Theatre
Demonology
Early Modern
Magic
Advisor: Lewis, R
Processing of L2 words in bilingual children and adults: predictors, patterns, and tendencies

Within the context of foreign language learning, very little research has examined how learners process second language (L2) words in terms of which variables best predict their processing speed and which mechanisms best characterize bilingual lexical processing. The present study set out to address this gap by using a range of learner and lexical variables (such as vocabulary size, word length, and age of acquisition) as points of reference against which to identify the best predictors of children’s and adults' L2 lexical processing, and by comparing response latencies across stimulus conditions so as to identify the processing pattern specific to each age group. Thirty-nine primary-aged and 94 university-level Chinese learners of English performed a picture-naming task in English and then in Chinese, and then completed a Chinese-to-English task. The researcher analyzed and estimated how those learner and lexical variables predicted the recorded response latencies by means of multiple regression and structural equation modeling, and made cross-stimulus-condition comparisons with the use of analysis of variance. The results suggested that different aspects of vocabulary knowledge contributed significantly to predicting children's and adults' processing speed, and that shorter processing time was significantly and directly predicted by the younger age at which an L2 word was learned and its higher degree of word typicality. Both lexical association and conceptual mediation were present in L2 lexical processing irrespective of learners' age but in general the later an L2 word is learned, the greater the likelihood that the word is lexically accessed and processed. These results illustrate the crucial role that language experiences and conceptual structures play in influencing the ease or difficulty with which L2 lexical items are retrieved, and reflect the complexities and dynamics involved in processing bilingual lexicons. These findings will be discussed within the context of the role of research and theory in developing evidence-based pedagogical practice with a specific reference to vocabulary acquisition in children and adults learning foreign languages within input-limited contexts.

Keywords: Vocabulary learning and teaching
Bilingual learners
Lexical characteristics
Spoken production
Lexical processing
Advisor: Murphy, V
The public debate about the formulation of the Basic Law of the Federal Republic of Germany, 1948-1949

Four years after the end of the National Socialist dictatorship and a disastrous major war, basic rights and democratic government were enshrined in the Basic Law for the Federal Republic of Germany in May 1949. Thus parliamentary democracy was formally and institutionally reintroduced to Western Germany at the Bund level. Successful implantation of democracy, however, requires not only constitutional arrangements but also, and perhaps more importantly, participation on the part of the people in the democratic process. Through analysis of the public involvement in the Basic Law's formulation and the impact of the public debate on the deliberations of the Parliamentary Council between September 1948 and May 1949, the degree of participation of Germans in the three Western zones of occupation, upon which the new West German state could subsequently build, is explored. Initial answers are suggested in chapter II and then developed in subsequent chapters as various contentious topics debated by the Parliamentary Council are examined. Anti-parliamentarianism, the search for a new symbol, newspaper perceptions as a reflection of the reality of interaction between occupier and occupied in the constitution's formulation, and the public debate about the nature and status of the second chamber, about the relationship between God and the Basic Law, and about full equality for women are analysed.
The nature and extent of the public debate 1948-1949 make clear that the German population of the Western zones had already begun to think and function in a democratic fashion on the Bund level. This thesis suggests that the creation of an institutional framework, such as the Basic Law, should not be overemphasized at the expense of the developing democratic culture in post-war Western Germany. Without the gradual democratization of the population already well underway when the provisional constitution came into force on 23 May 1949, it is unlikely that the Federal Republic of Germany could have established itself so successfully so quickly.

Advisor: von Strandmann, H
Positional cloning of the gene responsible for dent's disease

The hypervariable locus DXS255 in human Xp11.22 has a heterozygosity exceeding 90% and has therefore facilitated the localization of several disease genes which map to the proximal short arm of the X chromosome, including the immune deficiency Wiskott-Aldrich syndrome and the eye disorders retinitis pigmentosa, congenital stationary night blindness and Aland Island eye disease. In addition, a microdeletion involving DXS255 has been identified in patients suffering from Dent's disease, a familial X-linked renal tubular disorder which is characterized by low molecular weight proteinuria, hypercalciuria, nephrocalcinosis, nephrolithiasis (kidney stones) and eventual renal failure. Two YAC contigs were constructed in Xp11.23-p11.22 in order to aid transcript mapping; the first centred on the DXS255 locus, the second mapping distal to the first and linking the genes GATA, TFE3 and SYP to the OATL1 cluster. Eleven novel markers were generated, one of which contains an exon from a novel calcium channel gene. Four putative CpG islands were detected in the region. Analysis of the microdeletion associated with Dent's disease using markers from the DXS255 contig demonstrated that it is confined to a 370kb interval. A YAC overlapping this deletion was hybridized to a kidney-specific cDNA library to isolate coding sequences that might be implicated in the disease aetiology. The clones thus identified detect a 9.5kb transcript which is expressed predominantly in kidney, and originate from a novel gene (CLCN5) falling within the deleted region. Sequence analysis indicates that the 746 residue protein encoded by this gene is a new member of the C1C family of voltage-gated chloride channels. The coding region of CLCN5 is organized into twelve exons, spanning 25-30kb of genomic DNA. Using the information presented in this thesis, other studies have identified deletions and point mutations which disrupt CLCN5 activity in further patients affected with X-linked hypercalciuric nephrolithiasis, confirming the role of this locus in renal tubular dysfunction.

Advisor: Graig, I
The C-Band All Sky Survey

The C-Band All-Sky Survey (C-BASS) is a 1 GHz bandwidth survey of the radio sky in both intensity and polarization at a frequency of 5 GHz and with a resolution of 0.8. Northern and Southern sky coverage is provided by antennas located at the Owen’s Valley Radio Observatory (OVRO) in California, and the MeerKAT support base in South Africa, respectively.
The primary science goal of C-BASS is to provide a highly sensitive C-Band all sky intensity and polarization map to augment the WMAP/Planck surveys. Removal of foregound contamination will place a limit on the success of Cosmic Microwave Background (CMB) experiments that attempt to detect the B-Mode polarization of the CMB. We will provide a HEALPix map (Nside=128) with an r.m.s. noise of 0.13 mK/pixel in Stokes Q and Stokes U, and a confusion limited r.m.s. noise of 0.8 mK/pixel in Stokes I. Removal of foregrounds at the higher frequency CMB surveys will be significantly improved by this lower frequency constraint.
This thesis describes the development of the C-BASS gain-stabilized receiver capable of making sensitive measurements of both galactic total intensity and polarization. The receiver features a novel digital backend to provide spectral detail across the frequency band of interest. The analog signal conditioning uses a double sideband mixer to mix the RF frequencies to a DC–1000 MHz baseband for digitization. By changing the mixer frequency and/ or duplicating the signal conditioning and digital hardware, the RF frequency coverage can be modified for other projects.
I also describe the process of converting a 7.6 m telecommunications dish to a high performance radio astronomy platform. The discussion includes dish surface measurements, optical design, and the development of an inexpensive telescope servo controller. The antenna conversion process and receiver design can be used to significantly reduce capital costs of future experiments, which is especially useful for short timescale experiments. The African VLBI (Nordling, 2012) is currently following a similar route to repurpose antennas across the African continent.

Keywords: digital
CMB
cosmic microwave background
b-mode
radio
FPGA
foregrounds
polarization
radiometry
Advisor: Jones, M
Spectral interferometry for the complete characterisation of near infrared femtosecond and extreme ultraviolet attosecond pulses

This thesis describes methods for using spectral interferometry for the complete space-time characterisation of few-cycle near-infrared femtosecond pulses and extreme ultraviolet (XUV) attosecond pulses produced via high harmonic generation (HHG). Few-cycle pulses tend to exhibit one or more of the following: (1) an octave-spanning bandwidth, (2) a highly modulated spectrum and (3) space-time coupling. These characteristics, coupled with the desire to measure them in a single-shot (to characterise shot-to-shot fluctuations) and in real-time (for online optimisation and control) causes problems for conventional characterisation techniques. The first half of this thesis describes a method, based on a spatially encoded arrangement for spectral phase interferometry for direct electric-field reconstruction (SEA-SPIDER). SEA-SPIDER is demonstrated for sub-10fs pulses with a central wavelength near 800nm, a bandwidth over 350nm, and a pulse energy of several nano-Joules. In addition, the pulses exhibit a modulated spectrum and space-time coupling. The spatially-dependent temporal intensity of the pulse is reconstructed and compared to other techniques: interferometric frequency-resolved optical gating (IFROG) and spectral phase interferometry for direct electric field reconstruction (SPIDER). SEA-SPIDER will prove useful in both femtoscience, which requires accurate knowledge of the space-time character of few-cycle pulses, and in HHG, which requires the precise knowledge of the driving pulse for seeding into simulations and controlling the generation process itself. Pulses arising from HHG are known to exhibit significant space-time coupling. The second half of this thesis describes how spectral interferometry may be performed to obtain the complete space-time nature of these fields via the use of lateral shearing interferometry. Finally, it is shown, via numerical simulations, how to extend the SPIDER technique for temporal characterisation of XUV pulses from HHG by driving the process with two spectrally-sheared driving pulses. Different experimental configurations and their applicability to different laser systems are discussed. This method recovers the space-time nature of the harmonics in a single shot, thus reducing the stability constraint currently required for photoelectron based techniques and may serve as a complimentary method for studying interactions of XUV attosecond pulses with matter.

Keywords: spatially encoded arrangement
attosecond
high harmonic generation
spectral phase interferometry for direct electric-field reconstruction
SPIDER
spectral interferometry
space-time coupling
femtosecond
Advisor: Walmsley, I
The phylogeography and systematics of Cardamine hirsuta

Cardamine hirsuta L. is an emerging model system in developmental genetics, where natural genetic variation within C. hirsuta provides the means to investigate the genetic basis of morphological traits. This thesis investigates the geographical structure and genealogical history of genetic variation within C. hirsuta and identifies its closest relatives. This will enable the accurate selection of species for comparison with C. hirsuta when making interpretations of evolutionary processes, and provide a better understanding of morphological character evolution in C. hirsuta.
The phylogeographic history of C. hirsuta was reconstructed using multiple chloroplast and nuclear markers and widespread accession sampling from across its native range. A distinct group was identified within C. hirsuta, restricted to the high mountains of East Africa. Climate suitability modelling showed that Pleistocene glacial dynamics have had a strong effect on the distribution of genetic variation within C. hirsuta.
The phylogeographical data generated here was used to investigate the origin of C. hirsuta in the Azores, an oceanic archipelago. The Azores are dominated by an endemic chloroplast haplotype which is associated with an endemic phenotype. Thus, C. hirsuta appears to have diversified in situ in the Azores.
Phylogenetic analyses of Cardamine, restricted to diploid species to remove the confounding effects of polyploids, found that C. hirsuta is most closely related to C. oligosperma, a western North American species. Multiple loci and extensive intraspecific sampling were brought to bear to demonstrate that C. hirsuta and C. oligosperma are reciprocally monophyletic. Cardamine pattersonii, a restricted endemic from north-west Oregon is likely to be an allopolyploid, with C. oligosperma as the maternal parent and possibly C. nuttallii as the paternal parent.

Keywords: Azores
Last Glacial Maximum
phylogenetics
Atlantic fringe
palaeodistribution modelling
Cardamine hirsuta
phylogeography
Cardamine
Advisor: Scotland, R
Carine, M
Tsiantis, M