VictorJuiz/thesis huggingface dataset:
Olefin polymerisation using group 4 permethylindenyl complexes

This thesis discusses the development of permethylindenyl constrained geometry complexes (CGCs) as highly efficient slurry phase polymerisation catalysts capable of incorporating olefins at high and controllable levels and a niobium imido complex as an ethylene oligomerisation catalyst. Finally, a CGC and a niobium imido complex were combined on a single inorganic solid support with the aim of forming short chain branched linear low density polyethylene (LLDPE) from a single ethylene feedsource.
Ethylene (co)polymerisation, oligomerisation and tandem catalysis are introduced, with discussion of previously reported examples of catalysis of these processes. The synthesis, characterisation and immobilisation on inorganic solid supports of a range of permethylindenyl based CGCs (Me,R1SB(tBuN,3-RI*)MX2 where (Me,R1SB(tBuN,3-RI*) = {(3 R η5-C9Me5)(Me,R1)Si(tBuN)}2–), Me2SB(RN,I*)TiCl2 and Me2SB(tBuN,I*)Ti(Cl)CH2SiMe3) is discussed.
Slurry phase ethylene polymerisation studies were undertaken to investigate the effect of the amido fragment, initiator group, ansa bridge, metal centre and permethylindenyl moiety. Factors including temperature, time, scale, catalyst loading, scavenger, pressure and inorganic solid support were all investigated. High throughput polymerisations were also undertaken for the most active catalysts, and hydrogen response also studied.
Selected complexes were tested as ethylene/1 hexene, ethylene/1 octene and ethylene/styrene copolymerisation catalysts, with ethylene/1 hexene copolymerisations carried out under high throughput conditions and Me2SB(tBuN,I*)TiR2 (R = Cl and CH2Ph) tested on a large scale at SCG Chemicals Co., Ltd. (Rayong, Thailand). Solution copolymerisations were also carried out with Me2SB(tBuN,I*)TiCl2,Me2SB(tBuN,3-EtI*)TiCl2 and Me2SB(tBuN,Cp*)TiCl2.
Nb(NDipp)Cl3.THF.pyr was synthesised and used as a slurry and solution phase oligomerisation catalyst, with work undertaken to optimise conditions for ethylene trimerisation. Finally, both Nb(NDipp)Cl3.THF.pyr and Me2SB(tBuN,I*)TiCl2 were simultaneously supported on solid polymethylaluminoxane (sMAO) for use in the tandem catalysis of ethylene to form short chain branched LLDPE from a single ethylene feedsource.

Keywords: Tandem catalysis
Constrained geometry complexes
Oligomerisation
Olefin polymerisation
Copolymerisation
Advisor: O'Hare, D
Religious literacy for a secular age: approaches from secularism studies and affect theory

Religious literacy has become a widely invoked concept in scholarship, policy, popular discourse, and beyond. Since the 1990s, but more actively since 9/11, arguments in favor of training citizens to “get” religion and to understand why it matters “on the ground” have proliferated. A trans-Atlantic, Anglophone conversation has emerged as United States and United Kingdom educators and policymakers have called for increased engagement with, and public understanding of, religion. Often advancing one or more of the agendas of social cohesion, active citizenship, and democratic self-awareness, religious literacy emerges as a framework for addressing timely issues within pluralist settings. Frequently, advocates for religious literacy also call upon notions of secularity, explicitly citing the idea that the need for religious literacy results from our so-called secular society’s lost ability to interact with religious populations and identify religious tropes. Religious literacy, in this way, participates in the debate around religion’s place within the liberal-democratic public sphere and points to tensions underlying the category of the “secular.”
Despite the growing body of literature on such themes, there is a dearth of scholarly analysis connecting theories of secularism to current policy proposals. My thesis intervenes by linking critical secularism studies—an emerging field that rethinks the classic secularization narrative—to the dialogue on religious literacy. I argue that religious literacy, with its inherent emphasis on “literacy” has the capacity to set us on an all-too-narrow path from the start by advancing intellectualized and “linguisticized” conceptions of religions, which privilege the cognitive, textual, rational, and apparently democratically compatible aspects of religions. Challenging such presumptions, this project examines the discourse on religious literacy, using the tools of critical secularism studies and affect theory to expose some of the liberal assumptions underlying the conversation. The thesis, in response, proposes a fresh perspective on religious literacy that takes into account the affective and embodied dimensions of religions and the “secular.”

Keywords: Religious literacy
Public sphere
Secularism
Religious studies
Secular
Critical religion
Liberalism
Rationality
Nonreligion
Religious education
Tolerance
Affect theory
Civics
Advisor: Wood, WD
Schaefer, DO
Zachhuber, J
The molecular ecology of the Gentoo Penguin (Pygoscelis papua)

Gentoo Penguins (Pygoscelis papua) are marine mesopredators facing threats from anthropogenic environmental change, habitat loss, fisheries pressure, pollution, direct disturbance at colonies, and introduced pathogens. These philopatric seabirds breed across the largest geographic and latitudinal range of any penguin taxon. Given the large biophysical range of Gentoo Penguin habitats, evolutionary theory posits that localised biotic and abiotic interactions would place differential pressures on distinct populations of the species, affecting their genotypes and phenotypes. The host-pathogen interface is one such biotic interaction known to shape evolutionary trajectories. This thesis employs molecular techniques to examine the role of geographical variation on the genetic diversity of (I) the penguin as a host and (II) its enteric viruses, bacteria, and eukaryotic parasites. In this work, I uncovered strong host phylogeographic and population genetic structure according to neutral, mitochondrial, and immune gene (Toll-like receptor, TLR) markers. I also present experimentally-supported evidence of positive selection on TLR5, which points to localised pathogen-driven adaptation. Given the limited understanding of the pathogens circulating in modern Gentoo Penguin habitats, I also undertook parallel sequencing-based screening surveys to report novel viral, bacterial, protozoan and helminthic sequences associated with these seabirds and their sympatric species. Alongside undescribed diversity, I found evidence of greater-than-expected connectivity among the enteric microbes of spatially separate and genetically disparate Gentoo Penguins, as well as Pygoscelid-wide microbe commonalities. This research demonstrates the importance of studying species complexes and biotic interaction at the large scale, particularly in the face of emerging threats and the challenges inherent to wildlife disease monitoring in these remote habitats.

Keywords: pathogens
microbiome
wildlife disease
conservation genetics
population genetics
polar front
Antarctica
latitudinal gradient
toll-like receptors; TLRs
seabird
penguin
parasites
viruses
immunogenetics
Advisor: Smith, A
Hart, T
Rogers, A
Statistics in adjudicative fact-finding

Statistics and statistical evidence have been and are an important feature of litigation. Although common, how to appropriately manage and utilise statistical evidence in fact-finding has bedevilled courts across the common law world and led to rampant scholarly and judicial debates. If evidence ought to lead to a greater likelihood that the truth will be uncovered, it should be used in fact-finding. So far, what has been missing from the debates about statistical evidence is how the legal process should come to a view that statistical evidence is ‘good’ for fact-finding. The goal of this thesis is to articulate a framework by which decision-makers can use evidence law to admit, assess the usefulness of, and weigh statistical evidence. This thesis also seeks to address how the objections to statistical evidence may be categorised within the evidentiary processes of relevance, admissibility, weight and proof. First, the thesis describes objections to ‘General Factual Causation’, being the ability of the statistical evidence to be adduced to prove the existence of associations between variables in a state of nature. Second, it addresses the problem of how to infer the existence of a phenomenon in an individual from statistical evidence purporting to show an association between variables in a reference class. This question more than any other has dominated the discussion of statistical evidence, but it often misses how evidence law would and could respond to this issue. Third, this thesis canvasses difficulties arising from the proof of facts by statistical evidence and ‘objective probabilities’ derived from reference classes, including the problem of ‘naked statistical evidence’ and how or whether to use mathematical techniques to calculate the probabilities of individual events.

Keywords: statistical inference
fact-finding
statistical evidence
causation
evidence law
Advisor: Bagshaw, R
Parthian Nineveh 

The archaeology and history of the Parthian period (c. 150 B.C. – A.D. 250) in Iraq has received little serious attention from scholars in recent years. This thesis used objects in British museum collections from Nineveh as a focus for the study of this period in Northern Mesopotamia, combining traditional archaeology and numismatic analysis with scientific studies.

Chapter I presents a critical analysis of the excavated evidence for the occupation of Nineveh in the Parthian period with special attention to distinctive artefacts such as figurines, lamps, and molded bowls. Chapter II uses petrographic and chemical analysis of selected ceramics to elucidate the materials and methods of manufacture, with particular attention to identifying local and foreign wares. Special attention is paid to glazed wares. Chapter III is a numismatic study based on the major hoard of Parthian bronze coins of Nineveh. A complete re-classification of the hoard not only identifies a number of new coin types, but also provides a revised list of rulers who issued coins at Nineveh. Chapter IV investigates all aspects of Roman involvement with Nineveh and its place in the stormy relationship between Rome and Parthia. Evidence is advanced for there having been contingents of Roman troops stationed at Nineveh and the site placed within its context in the state of Adiabene.

Keywords: Parthian numismatics
ancient Iraq
Nineveh
ancient Near East
ceramic petrography
Roman Empire
Parthian
Mesopotamia
Advisor: Tite, M
Transition metal fluorides as lithium ion cathodes

More energy dense lithium ion batteries are essential for the production of long-range electric vehicles and all-electric aircraft. These next generation batteries will require high capacity cath- ode materials that move beyond the lithium intercalation chemistry of current electrodes. On paper, transition metal fluorides are among the most promising cathode materials, combining high electrode potentials (2.6 V to 3.5 V vs. Li+/Li) with three to six times the theoretical capacity of conventional cathode materials. However, their commercial application has been hindered by their inability to cycle in a truly energy dense format (i.e. at high active material concentra- tion) and ultimately the inadequate understanding of their electrochemical capabilities and limitations. Both of these issues have been largely resolved as a result of this DPhil project. First I design a materials system that is practically ideal for reversible high-capacity cycling as well as detailed mechanistic study. This is achieved through the development of a new colloidal synthesis method for single-crystalline, monodisperse transition metal fluoride (FeF2, CoF2) nanorods. Size and shape control are demonstrated, and a chemical reaction pathway and nu- cleation and growth mechanism are proposed. Next I present an ionic liquid electrolyte (1 molal lithium bis(fluorosulfonyl)imide in N-methyl-N-propylpyrrolidinium bis(fluorosulfonyl)imide) that forms a stable solid electrolyte interphase, prevents the fusing of particles, and consequently precludes the major failure mechanisms associated with transition metal fluoride cathodes. The use of this electrolyte with the iron(II) fluoride (FeF2) nanorod system results in near theoretical capacity (570 mA h g−1) on discharge and charge, with extraordinarily stable cycling (>90% ca- pacity retention after 100 cycles). This stability is maintained for over 200 cycles at relatively high cycling rates (C/2) and temperatures (50 ◦C). By combining the unique vantage point afforded by this novel materials system with the morphology preserving qualities of our new electrolyte, I am further able to characterize the discharge/charge mechanism with an unprecedented level of detail. High-resolution analytical transmission electron microscopy reveals intricate morphological features, lattice orientation relationships, and oxidation state changes that that provide a new and comprehensive understanding of the discharge/charge (conversion) reaction mechanism. This new mechanistic understanding defines the structural and chemical origins of reversible cycling and cell failure in transition metal fluorides and unearths new concepts such as an inherently high discharge rate capability in FeF2.

Keywords: transition metal fluoride
nanoparticle
transmission electron microscopy
reaction mechanism
lithium ion battery
conversion cathode
ionic liquid electrolyte
Advisor: Pasta, M
Towards the total synthesis of pectenotoxin-4

Chapter 1: Introduction This chapter provides the background of the pectenotoxins (PTX), which includes details of their isolation, structure, and biological activity. Subsequently, the total syntheses of PTX-4 by Evans and of PTX-2 by Fujiwara are discussed. Finally, past efforts of the Donohoe group towards the synthesis of PTX-4 are summarised.

Chapter 2: Synthesis of the ABC fragment This chapter details the retrosynthesis and forward synthesis of the C1–C16 ABC fragment of PTX-4. Moreover, the chapter features extensive discussions on the optimisation efforts for key steps, including the osmium-catalysed double oxidative cyclisation step and the 1,2-hydride shift spiroketalisation cascade. Other major challenges, such as the unexpectedly difficult removal of an Evans oxazolidinone auxiliary, are also discussed.

Chapter 3: Synthesis of the E fragment This chapter describes the retrosynthesis and forward synthesis of the C19–C30 E fragment of PTX-4. Experiments to troubleshoot and develop workarounds for an irreproducible regioselective hydroiodination step to give a vinyl iodide product early in the synthesis are documented. Finally, the synthesis of the C31–C40 F fragment of PTX-4 is briefly covered.

Chapter 4: Uniting the ABC and E fragments This chapter discusses the elaboration of the ABC fragment into its vinyl boronic ester analogue for the planned rhodium-catalysed Hayashi–Miyaura 1,4-addition with the E fragment to unite the two major PTX-4 fragments. Optimisation studies for key reactions arealso discussed and include an allylation reaction, the 1,4-addition, and a dihydroxylation–ketalisation cascade to form the D ring.

Chapter 5: Experimental This chapter lists all experimental procedures for the reactions described in this thesis, as well as the characterisation data for the compounds synthesised.

Keywords: osmium
oxidative cyclisation
natural product synthesis
total synthesis
Advisor: Donohoe, T
Obligation and modality

This thesis investigates the structure of legal obligation. Each essay in it defends, more or less directly, the claim that legal obligation has a normal modal logic: this logic is classical and guarantees that whatever follows from what is legally obligatory is itself legally obligatory. Knowing what follows from our legal obligations, and so knowing their logic, matters whether we care about obeying the law or avoiding the coercive power of the state. Essay 1 defends the inference scheme of deontic explosion, which says that conflicting obligations entail any obligation at all. The logic of legal obligation is normal only if it validates this scheme, which is standardly assumed to be absurd. But deontic explosion for legal obligation is not absurd. The scheme shows that the law effectively gives up on guiding our action as soon as any of our legal obligations conflict. Essay 2 defends the classicality of the logic of legal obligation. Some dialetheists claim that legal obligations can be inconsistent: the same action can be both legally obligatory and not legally obligatory. These dialetheists assume that the semantic or asserted content of a legislature’s enactment is the law. But the law controls the interpretation of its own instruments: the legal content of an enactment is the law. Inconsistencies in legislation give no reason to doubt classicality since such inconsistencies are resolved by standard legal principles. Moreover, the law assumes the impossibility of inconsistent legal obligations when determining rights and duties. Essay 3 evaluates perspectivalism, which holds that legal obligations amount to claims by the law about moral obligations. This popular view is committed to a theoretically unnecessary distinction between strong and weak legal-deontic modalities. It also entails that the law implausibly claims that it doesn’t claim what it doesn’t claim. Atomism, which denies that legal obligation can be resolved into more fundamental modalities, suffers from neither of these difficulties.

Advisor: Williamson, T
Endicott, T
Job search and migration

Standard models of within-country mobility assume that all migration is speculative: workers move to search for jobs in other labour markets. I establish a new stylised fact showing that the majority of cross-regional migration in the US is in fact with a job in hand, as a result of a job offer from another region. The fact that a significant fraction of migration is a result of cross-regional hiring, and that this hiring is subject to search and matching frictions, has important implications for the level of regional mobility and hence regional differences within a country. In the first two chapters, I show empirically that the availability of cross-regional employment opportunities does matter for workers’ migration behaviour. Using US panel data, I demonstrate that the observed gap in migration propensity between the more and less educated workers can be partly explained by differences in labour market frictions. The less educated workers find job search in more distant regions much more difficult, which limits their options to move for a specific job and reduces their overall mobility. This result opens a new policy channel in addressing regional differences and those left behind: the importance of the ability to find a job before moving suggests a large social return to improving regional search and matching for less educated groups. In the third chapter, I explore the theoretical implications of an imperfect search and matching process on the existence and persistence of regional disparities. First, I show that if the efficiency of the search and matching process increases in the size of the labour market, migration will serve to exacerbate, not equilibrate, the differences in regional economies. A bigger labour market will experience higher wages and lower unemployment rates, attracting migrants from other regions and thus accelerating the process of regional divergence. At the same time, larger labour market frictions in the smaller regions reduce firms’ incentives to hire there, curtailing cross-regional hiring and hence the opportunity to move for a specific job. The interaction of these two forces give rise to multiple equilibria and explain how, in the presence of labour market frictions, regional disparities can be large and persistent at the same time.

Keywords: job search
regional economic differences
internal migration
Advisor: Stevens, M
Adams, A
Mathematical problems in algorithmic trading and financial regulation

We study algorithmic trading strategies in order driven markets. We make three contributions to the literature. One, we show how a market maker employs information about the momentum in the price of the asset to design liquidity provision strategies. The momentum in the midprice of the asset depends on the arrival of liquidity taking orders and the arrival of news. Buy market orders (MOs) exert a short-lived upward pressure on the midprice and sell MOs exert a downward pressure of the price. We employ high-frequency data to estimate model parameters and show the performance of the market making strategy. Two, we model the trading strategy of an investor who spoofs the limit order book (LOB) to increase the revenue she obtains from selling a position in an asset. The strategy employs, in addition to sell limit orders (LOs) and sell market orders (MOs), a large number of spoof buy LOs to manipulate the volume imbalance of the LOB. Our results show that spoofing considerably increases the revenues from liquidating a position. The spoof strategy employs, on average, fewer sell MOs (than a strategy without spoof LOs) and from executing roundtrip trades that are initiated by buy spoof LOs that are inadvertently filled and subsequently unwound with sell LOs. Spoofing is illegal and difficult to detect. We show that as the financial penalty for spoofing increases, the spoof strategy relies less on spoof LOs. There is a critical point where the gains from spoofing are outweighed by the financial penalty, so it is optimal no not to spoof the LOB. Three, we show how the supply of liquidity in order driven markets is affected if LOs are forced to rest in the LOB for a minimum resting time (MRT) before they can be cancelled. The bid-ask spread increases as the MRT increases because market makers (MMs) increase the depth of their LOs to protect them from being picked off by other traders. The expected profits of the MMs increase when the MRT increases. The intuition is as follows. As the MRT increases, there are two opposing forces at work. (i) The longer the MRT, the more likely the LOs are to be filled and, on average, shares are sold at a loss. (ii) because the depth of the posted LOs increases, the probability that the LO is picked off by other traders before the end of the MRT decreases. The net effect is that a longer MRT leads to a higher expected profit. We also show that the depth of LOs increases when the volatility of the price of the asset increases. Also, the depth of LOs increases when the arrival rate of market orders increases because it is less likely that LOs will be picked off by the end of the MRT. Finally, our model also makes predictions about the overall liquidity of the market. We show that MMs choose to supply the minimum amount of shares per LO allowed by the exchange because expected profits are maximised when liquidity provided is lowest.

Advisor: Cartea, A