VictorJuiz/thesis huggingface dataset:
An investigation of virial coefficients of gases

The most widely used experimental method for studying the forces between pairs of molecules is the determination of the second compressibility virial coefficient, B, defined by: z = Pvm/RT = 1 + B/Vm + C/V2 + . . .
For non-polar gases at temperatures well removed from the normal boiling point, it is relatively easy to measure values of B with adequate accuracy for assessing the merits of various model intermolecular potential energy functions, However, at temperatures little above the normal boiling point, especially for the more polar gases, adsorption effects can prove troublesome.
The density balance method can, in principle, give Values of the second compressibility virial coefficient free from adsorption errors. In practice, there remain other drawbacks to such an approach, particularly the notorious instability of the density balance zero point, and the need for the molecular weight of the gas to be very precisely known, or at least constant within very small limits. The recent extensive development of vacuum micro- and ultramicro-balances suggests that the difficulty of instability should now be superable. A simple theoretical consideration of the treatment of data from such a balance shows that adsorption effects which are not compensated in the balance design may be corrected for, to a first order, and second virial coefficients obtained which are accurate to about +5 cm3 mole-1.
Continued in thesis ...

Keywords: virial
investigation
adsorption
gases
coefficients
virial coefficients
Advisor: Sutton, LE
Problems in stochastic analysis. Connections between rough paths and non-commutative harmonic analysis

The prevailing aim and flavour of this thesis, is to establish a link between Lyons' theory of Rough Paths and more conventional notions of non commutative harmonic analysis. Three different directions represent the lines of investigation. it
The first is a generalization of an algebraic formalism, pertaining to classical pictures of the analysis of functions on groups. The structures of Hopf algebras reveal an algebraic role of geometric rough paths in relation to the shuffle algebra of one-forms.
The second direction examines path-space on Lie Groups and a generalization of the notion of rough paths. It is shown how to approximate the length of a twice differentiable curve in two dimensions through the iterated integral sequence and an analysis of curves in two dimensional hyperbolic space. The formula is given in terms of the asymptotics of the iterated integral sequence.
The third and final direction, was motivated by an attempt to enlarge the definition of the Ito map to non-geometric rough paths. It is shown how random geometric rough paths can be used to interpret backward Ito multiplicative functionals. Some ideas regarding the extent to which the center of mass of a distribution on geometric rough paths actually determines the distribution itself, are presented.

Advisor: Lyons, TJ
Darwinism in global international thought, c.1859–1914

This thesis reinserts Charles Darwin into the history of international thought and excavates a distinctive idiom of ‘Darwinian internationalism’ inspired by his theory of evolution by natural selection—one widely influential across the globe in the latter half of the long nineteenth century, yet oddly overlooked in existing scholarship.
Part I of the thesis presents a portrait of Darwin as a thinker both created by and concerned with international politics. This is established through an exegesis of his corpus of scientific writings, which were in themselves produced by travel and encounter, and which also engaged with themes of war (transposed into nature as the ‘struggle for existence’) and intersocietal difference (with a focus on what ‘savagery’ reveals about evolution), foregrounded respectively in two major texts: the Origin of Species and the Descent of Man. I argue that we see Darwin caught between a mid-century liberal way of thinking about international politics and a radically new way of thinking latent at the heart of his theory, which others would more fully embrace.
An interlude pivots from Darwin to the Darwinians, where I define the distinctiveness of ‘Darwinian internationalism’ through its four core motifs: evolutionism, national selectionism, organicism, and naturalism.
Part II of the thesis then examines the spread of this idiom in a global reception history. I unpack the ideas of a broad cast of Darwinian internationalists in three ‘contexts of position’ in the late nineteenth century: the core, with a focus on late Victorian Britain; the semi-periphery, with a focus on the Eastern polities (China and Japan) and Latin America; and the periphery, with a focus on South Africa. It is shown how flexible Darwinism proved for articulating a myriad of strategies across the range of positionalities in late nineteenth-century international social space—becoming an accessible ‘weapon of the weak’ as much as of the strong—and how as a way of thinking about international relations it thus cut across the moral-cultural hierarchies of the period.
By ‘bringing Darwinism back in’, an alternative narrative of late nineteenth-century international society is found—one which dislocates the dominant notion of the period as wholly defined by the ‘standard of civilisation’, instead showing how infused the period also was with a competing ‘standard of nature’ which prophesised and produced conditions of holistic, ineliminable existential conflict, and which sowed the seeds of the catastrophes of the short twentieth century.

Keywords: Darwinism
international relations
English school
international thought
intellectual history
Advisor: Keene, E
Oral-cavity platform for monitoring physiological signs during physically demanding activities

The focus of this research is the development of a platform to measure physiological signals in the oral cavity during real-world conditions. Starting from a literature review the current state-of-the-art for oral-cavity sensors was determined. No existing measurement system that could capture all relevant physiological data during physically demanding activities was found. A novel wearable oral-cavity measurement system was proposed to address this.
Respiration and fatigue data was obtained using the oral measurement system with a microphone. Recreational athletes completed physically demanding activities whilst wearing the device. Respiratory metrics derived from the oral system were strongly associated with perceived exertion. However, the data suggested that respiratory signals alone do not fully explain the variance in perceived exertion and additional metrics were needed.
A temperature sensor was added to the oral system, as it is important to monitor body temperature and prevent exertional heat exhaustion. The performance of the temperature sensors was assessed using lab bench and in-vivo tests. The steady-state errors of the oral-temperature measurement were determined to be within the clinical limit, indicating suitable performance of the system under these controlled conditions.
Finally, photoplethysmographic (PPG) sensors were included in the design to measure cardiac signals. The most appropriate sensor placement, light wavelength and signal intensity were explored through in-vivo experiments. The best-performing configuration was determined based on this data. Nonetheless, an additional study was needed to determine the impact of materials and manufacturing processes. A lab-bench investigation explored how the embedding materials affected the PPG’s signal-to-noise ratio, providing further avenues for optimisation of the system.
The findings from each phase of this research were used to design a new oral device for the study of physiological signals during demanding physical activities. The designed device could allow for insights into the performance and health during real-world applications.

Keywords: in-body wearables
athletic performance
intraoral sensing
biosensors
mouthguard
physiological assessment
physiological measurement
Advisor: Bergmann, J
Influence of spin-orbit coupling on solid-state NMR parameters

Nuclear magnetic resonance is a widely utilised spectroscopic technique for the structural determination of molecules and solids. The development of density functional theory methods have allowed for the computation of many nuclear magnetic resonance parameters, supporting experimental studies. Heavy atoms introduce additional difficulties, that currently, are typically ignored. They require a fully relativistic treatment to include the effects of spin-orbit coupling, which ultimately dictates the magnetic response of nearby light nuclei.
In this thesis, we develop the theory to accommodate the prediction of nuclear magnetic resonance properties in the solid-state, with the inclusion of spin-orbit coupling. We develop the planewave pseudopotential method, in its application to density functional theory, to account for relativistic effects. This involves the extension of the projector augmented-wave method for two-component spinor wavefunctions, and its gauge-including counterpart. This allows for the investigation of the electric field gradient and magnetic shielding parameters of inorganic compounds and molecular crystals.

Keywords: magnetic shielding
special relativity
electric field gradient
nuclear magnetic resonance
spin-orbit coupling
computational
density functional theory
Advisor: Yates, J
Structural and bioinformatic analysis of ADP-ribosylation, transcription, and splicing

ADP-ribosylation is a reversible chemical modification to proteins and nucleic acids. Although most widely studied for its role in signalling in the DNA Damage Response (DDR), ADP-ribosylation is further involved in many cellular processes across all domains of life, including transcription, RNA processing, apoptosis, bacterial nitrogen fixation, and viral infection. ADP-ribose (ADPr) is added to specific chemical groups by ADP-ribosyl transferases (ARTs) including poly ADP ribose polymerases (PARPs). Hydrolases from the macrodomain-containing family and ADP-ribosyl hydrolase (ARH) family remove ADPr to regulate signalling. The ARH family, consisting of ARH1, ARH2, and ARH3, has gained attention for their roles in DDR and cell death pathways. ARH1 hydrolyses arginine-linked mono-ADP-ribose (MAR), while ARH3 cleaves serine-linked MAR and poly-ADP-ribose (PAR). The macrodomain-containing hydrolase PARG cleaves PAR, and several other macrodomain-containing hydrolases cleave aspartate/glutamate-linked MAR.
Transcription by RNA Polymerase II (pol II) is a multi-step, tightly regulated process by which RNA molecules are synthesised in a DNA-template driven manner. The major steps are initiation, elongation, and termination, in conjunction with concomitant RNA processing reactions including 5’ end capping, splicing, and 3’ polyadenylation. The C-terminal domain (CTD) of pol II is dynamically phosphorylated on residues of its consensus repeat sequence Y1S2P3T4S5P6S7, providing a scaffold for recruitment of various transcription and processing factors.
This project was split between bioinformatic analysis of transcription by pol II, and structural and bioinformatic analysis of ADP-ribosyl hydrolases. Using X-ray crystallography and activity assays, the chemical specificities, and molecular mechanisms of members of the ARH family were further investigated, revealing differences in the substrate binding sites that inform their activity. Additionally, the protein C12orf4, containing a putative macrodomain potentially involved in ADP-ribosylation signalling, was the subject of attempted purification and in vitro characterisation. Using published datasets derived from HeLa cells, the coupling of RNA processing reactions, CTD phosphorylation, and mature messenger RNA (mRNA) fate was investigated, revealing that transcription of many protein-coding genes produces poorly processed mRNAs that remain chromatin associated and are sensitive to degradation by the nuclear RNA exosome. Finally, the transcription & RNA processing project, and the ADP-ribosylation project, were integrated through bioinformatic analysis of RNA-seq data related to the hydrolases ARH3 and PARG.

Keywords: RNA processing
transcription
ADP-ribosylation
Advisor: Murphy, S
Ahel, I
Carvalho, P
Measuring and explaining the intra-coalition dynamics of coalition governance

Coalition governance, the period between coalition formation and termination, is a critical, yet understudied aspect of a coalition cabinet’s life cycle. The opaque nature of multi-party governance poses significant challenges to understanding its day-to-day operations, and, as a result, existing literature is overly reliant on static, indirect, measurements. Since coalition governance is theorised to be variable and dynamic, this means significant details pertaining to party behaviour remain obscured. This thesis sets out to study the behaviour of political parties in coalition governance by capturing coalition differentiation. Whether coalition parties choose to defend distinct party goals, as opposed to the coalition consensus, marks a conscious departure from a public united front. Since unity is necessary for coalition effectiveness, this can have serious implications for coalition governance itself. The precise role of differentiation in coalition governance is established in three separate articles. The first article applies supervised text classification to measure, dynamically, coalition party differentiation in parliamentary speech. This results in a monthly party measure for 69 cabinets from ten European countries, making it the first comparative measure of differentiation. The second article employs this measure and establishes that differentiation is predominantly displayed by coalition parties with strong bargaining power. The final article considers the purpose of coalition differentiation and thus what one can infer about coalition governance from its variation. The resulting proposition is that parties differentiate to display bargaining power when navigating uncertain bargaining environments, and, in this way, influence coalition negotiations. By measuring differentiating behaviour dynamically, and subsequently establishing its prevalence and purpose in coalition bargaining, this thesis sheds light on the secretive process of coalition governance. Moreover, this novel comparative measure of coalition differentiation enables the dynamic testing of core assumptions which previously have eluded analysis regarding coalition party representation, accountability, electoral performance, and future coalition inclusion.

Keywords: party behaviour
coalition parties
legislative speech
coalition differentiation
computational text analysis
coalition conflict
Advisor: Schleiter, P
Students’ academic self-formation in local and international higher education: evidence from South Korean students  


The dominant notions of higher education derived from human capital theory have been accused of disregarding the active agency of students and diminishing the significance of knowledge. Meanwhile, the emerging concept of higher education as student self-formation places emphasis on student agency (Marginson, 2014, 2023a). The process of self-formation within the context of higher education is distinctive by its academic nature, as it highlights deep engagement with knowledge (Ashwin, 2020). While the idea of self-formation has drawn favourable reactions within the discipline, its comprehensive and normative nature has constrained empirical inquiries. To lay the groundwork for self-formation research, the present study aims to develop a theory that can explain what academic self-formation is (RQ1), and how students engage in it (RQ2). While previous researchers have so far almost exclusively focused on international students, the present study expands the self-formation discourse by examining academic self-formation in both local and international higher education (RQ3).
Based on Archer’s (1995) realist social theory, I devised a research design that enables building a conceptually sound and empirically supported theory. On the one hand, the conceptual phase of this study critically reviewed theories/concepts that are relevant to academic self-formation. On the other hand, the study also collected and analysed ethnographic data from thirteen first-year South Korean graduate students, seven being local students in Korean universities and six being international students in the UK. Findings from the conceptual and empirical research reflexively interacted with each other, as a theory emerged.
The findings reveal that the individual students followed unique self-formation journeys. Three themes emerged as key elements in theorising academic self-formation. First, student agency was found to operate in a mediating mechanism, with four manifestations: effort, self-criticism, active conformity, and mobility. Second, academic self-formation was revealed to include the development of disciplinary agency, as seen in students’ repositioning of the self in their perceived self-knowledge-society relationship. Third, the role of mobility in academic self-formation was explained in terms of its link with the multiplicity of the self. The study concludes by integrating these themes into a theory of academic self-formation, and then by summarising the similarities and differences between self-formation in local and international higher education. The theory can contribute to advancing the research programme of self-formation by providing methodological and theoretical tools for future researchers.

Keywords: international student mobility
South Korea
reflexive agency
self-formation
disciplinary knowledge
Advisor: Marginson, S
Puttick, S
Applying intersectionality to the adjudication of persecution in the International Criminal Court 

This thesis conducts a theoretical, doctrinal, and normative analysis of the features, role, legal basis, and potential normative value of intersectionality theory in the adjudication of the crime against humanity of persecution in the International Criminal Court (ICC). It summarises the features of intersectionality theory developed in domestic discrimination law and international human rights law, and provides an intersectional framework for the international criminal law context. It identifies and assesses ICC case law implicating intersectionality, concluding that the theory has growing relevance in the arrest warrant, confirmation of charges, trial, sentencing, and reparations decisions of the ICC Chambers. It argues that a defensible legal basis for intersectionality can be found in Article 21(3) of the Rome Statute of the ICC, based on an interpretation of this provision as a human rights consistency test. Finally, it argues that intersectionality brings benefits to the contextual elements of crimes against humanity, actus reus, mens rea, sentencing, and reparations stages of persecution cases, as well as expressive value, that outweigh the potential limitations of the proposal. The thesis concludes that intersectionality has significant potential as a legal tool in persecution cases and should be further explored by the ICC.

Keywords: International Criminal Law
international human rights law
Rome Statute
International Criminal Court
intersectionality
persecution
Advisor: Urs, P
Benzyltetrahydroisoquinoline and bis-benzyltetrahydroisoquinoline alkaloids as anti-parasitic agents

Visceral leishmaniasis and Chagas disease are protozoan neglected tropical diseases that have a significant impact in developing countries. Current therapies are limited and suffer from poor safety profiles, creating a dire need for novel drug leads. Bis-benzyltetrahydroisoquinoline (BBI) alkaloids have shown promising anti-parasitic activity, but have yet to be evaluated as potential leads. Questioning whether the structural complexity of BBIs is vital to the bioactivity, this thesis describes the studies towards simplified analogue 1. Key strategic steps include an Ullmann coupling to form the diaryl ether linkages and a Bischler-Napieralski cyclisation/Noyori asymmetric transfer hydrogenation to build the tetrahydroisoquinoline units (Chapter 2). To further simply the scaffold, the diaryl ether linkages are removed sequentially leading to the synthesis of linear BBI and benzyltetrahydroisoquinoline (BI) alkaloids. The acyclic BBIs were made from the individual BIs using a seven- or nine-step modular, convergent, and enantioselective strategy using the same key reactions. This enabled access to four natural and ten non-natural BI alkaloids and five BBI natural products and seven analogues. All diastereomers were synthesised to assess the effect of stereochemistry on bioactivity (Chapter 3). These compounds were tested against Leishmania infantum and Trypanosoma cruzi, and mammalian cytotoxicity was evaluated (Chapter 4). While acyclic BBI alkaloids were found to be cytotoxic and unfit as drug scaffolds, the lead BI (–)-laudanidine showed an IC50 of 2.60 ± 0.31 µM against T. cruzi amastigotes and SI >77 compared to current gold standard benznidazole (IC50 of 5.00 ± 1.53 µM, SI >40), thus promisingly meeting the DNDi’s criteria for a hit against Chagas Disease.

Keywords: benzyltetrahydroisoquinoline
bis-benzyltetrahydroisoquinoline
DNDi
neglected tropical diseases
Chagas Disease
leishmaniasis
alkaloids
Flash sintering of silicon carbide with boron and carbon sintering aids

The aims of this doctoral thesis were to assess the feasibility of using flash sintering to manufacture silicon carbide and to understand how the technique affects its density, microstructure and mechanical properties.
An experimental apparatus was developed that allowed silicon carbide bar shaped specimens with boron and carbon sintering aids to be flash sintered to 96% density (with an average grain size of 4 µm) in 16 minutes in an alumina tube furnace at 1500 °C. Compared with samples of similar density that were conventionally sintered using the powder’s recommended sintering schedule, the production time of the flash sintered samples was reduced by more than 6 hours and with a furnace temperature lower by 700 °C. Both methods sintered silicon carbide it in the liquid phase. Of the investigated flash sintering parameters, higher power limits, higher furnace temperatures, slower power ramp rates, and longer hold times were all found to increase the bulk density and the average grain size of specimens. The addition of carbon sources in the furnace tube during sintering was beneficial for sample densification, but could be detrimental if in close proximity to the sample. The additions also retarded grain growth in specimens and increased the time that samples could be flash sintered before fracturing from 16 minutes to 1.5 hours.
The Vickers hardness of most of the silicon carbide samples in this work was ∼24 GPa. The inclusion of carbon additions in the furnace tube during sintering significantly increased the Vickers hardness of silicon carbide: 27.8 GPa ± 0.4 GPa. This increase in hardness was independent of density, grain size and polytype concentration but is suggested to be related to a carbon concentration threshold in the sintering atmosphere. Atom probe tomography analysis indicated that the super-hard silicon carbide samples had a greater concentration of boron rich clusters than silicon carbide of regular hardness. These clusters are suggested to cause dispersion hardening in these samples. Flash sintering did not degrade the strength or the fracture toughness of silicon carbide. If flash sintered silicon carbide was successfully scaled up, the material may outperform traditional silicon carbide armour plates in ballistic trials.
The flash event in a non-oxide ceramic was shown to be phenomenologically similar to that found in oxide ceramics: characterised by a rapid rise in sample temperature followed by densification and a decrease in sample resistivity. This behaviour was shown to be consistent with thermal runaway; the origin of which was found to be the early stages of sintering.

Keywords: mechanical characterisation
silicon carbide
boron and carbon sintering additives
microstructure
flash sintering
Advisor: Todd, R