VictorJuiz/thesis huggingface dataset:
Discovery and development of novel enantioselective C(sp3)-H functionalisations
Keywords: catalysis
asymmetric
synthesis
chemistry
alkenylation
NMR
but-2-ynoate
thioamide
method
novel reaction
C-H functionalisation
organic
enantioselective
C(sp3)-H functionalisation
cobalt
methodology
HPLC
C-H activation
research

This thesis describes studies towards new enantioselective C–H activation reactions. In chapter 2 the investigation towards a novel enantioselective cobalt-catalysed C(sp3)–H alkenylation, directed by thioamides, with but-2-ynoates is described. In this method prochiral thioamides undergo asymmetric C(sp3)–H functionalisation with but-2-ynoates in presence of a [Cp*Co(MeCN)3][SbF6]2 complex and chiral carboxylic acid, which allows the formation of chiral thioamides. The method provides alkenylated products as single regioisomers in excellent yields (up to 85%) and high enantiomeric ratios (up to 91:9 er, or up to >99:1 er after single recrystallisation). The protocol is operationally very simple with mild reaction conditions, which is not very common for C–H functionalisations, because the activation of naturally inactive C–H bonds often requires high reaction temperatures. The applicability of this methodology can be found in diverse downstream derivatisations of products, delivering a broad range of enantiopure pharmaceutically and agrochemically relevant scaffolds, such as various substituted heterocycles. Mechanistic investigations and state-of-the-art DFT calculations carried out in collaboration with Ken Yamazaki, Prof Trevor A. Hamlin and Prof F. Matthias Bickelhaupt revealed that the pivotal C–H activation step is rate- and enantiodetermining step. DFT calculations explain the reaction mechanism, and stereochemical outcome of the products, as well as the unusual regioselectivity of the alkenylation reaction.
After successfully developing a novel thioamide-directed cobalt-catalysed enantioselective C(sp3)–H alkenylation reaction, in chapter 3 we investigated intramolecular variant of this new reaction. Taking into consideration the specific interactions between a Cp*CoIII complex, thioamides and but-2-ynoates, with suitable substrates the formation of cyclic products should be straightforward, and this project would be a viable follow-up of our completed study.
Symbolic techniques for parameterised verification
Keywords: automated synthesis
regular model checking
symbolic model checking
parameterized verification
automated reasoning

Parameterised systems are infinite-state systems comprising a parameterised number of components. The problem of verifying parameterised systems is both important practically and challenging theoretically: it is important because a wide range of real-world computer systems are parameterised in nature, and it is challenging because most relevant properties of parameterised systems are undecidable in general.
In this thesis, we study automated verification approaches using automata-based symbolic model checking (a.k.a. regular model checking) as a generic formalism for parameterised systems. Although this formalism is Turing powerful (i.e. it can simulate the computation of Turing machines), the nice closure and algorithmic properties of finite automata still allow us to design effective heuristics for practical applications. Our main proposal for regular model checking is to use first-order theories over regular relations to reason about correctness properties, and use regular language inference as a means of proof generation. We further develop powerful reduction and abstraction techniques to reduce difficult verification problems to simpler tasks for several classes of parameterised systems. These techniques include reductions from liveness properties to safety properties for regular systems, reductions from infinite data domains to finite alphabets for array systems, and reductions from quantitative reasoning to qualitative reasoning for probabilistic systems. All these reductions are performed in a uniform logical way based on decidable first-order theories.
We have implemented and evaluated our automated approaches against a nontrivial collection of examples covering concurrent systems, distributed algorithms, and cryptographic protocols. The promising experimental results confirm our hypothesis that regular languages and relations provide effective heuristics for parameterised systems verification.
Transnational knowledge transfer in the Enlightenment (c.1750-1790): the case of József Fogarasi Pap
Keywords: Dutch Republic
Transylvania
Berlin Academy
Prize contests
18th Century Intellectual Life
Enlightenment
Prize essay genre
Academies and societies

The present thesis offers the first comprehensive study of the intellectual career of Transylvanian philosopher József Fogarasi Pap (1744-1784), analysing the context, influences, and reception of the metaphysical essays submitted by him to Enlightenment prize contests in the Dutch Republic and in Berlin. A contextual intellectual biography, this thesis combines a transnational methodology with a textual analysis of the essays, and highlights the importance of the prize essay qua genre in the institutionalisation and democratisation of eighteenth-century knowledge networks. Fogarasi Pap’s remarkable success in philosophical competitions serves as a case study for underscoring three arguments. Firstly, religious discourse did not belong to a separate religious Enlightenment, but was a consistent feature of early modern philosophy. Secondly, Fogarasi Pap’s eclectic negotiation of various ideas and influences was a common method employed by thinkers to answer prize competitions’ questions, representing an Enlightenment philosophical and literary genre. Lastly, the philosophical endeavours of Fogarasi Pap and his competitors must be understood in the context of an institutional framework of philosophical production, namely the societies and academies that sponsored the competitions.
The first two chapters of the thesis follow the transnational knowledge networks of which Fogarasi Pap was a part: the Transylvanian Protestant peregrinatio academica, and the prize contests proliferating in eighteenth-century Europe. The following three chapters focus on four different essays submitted to three contests: the University of Leiden’s Legatum Stolpianum, the Haarlem-based Teylers First Society contest, and the Berlin Academy’s Speculative Class. Each chapter analyses the institutional context, Fogarasi Pap’s entries, and those of other competitors, in order to recover the intellectual microcosm of the everyday, mid-level, now unduly-forgotten practitioners of Enlightenment philosophy. Finally, in terms of thematic analysis, the thesis covers the broad spectrum of topics that represented the interests of eighteenth-century mainstream philosophy, from moral aesthetics, to the uniqueness of God, providence, and force of matter.
Women's relationships in classical Attika
Keywords: classical Athens
women's relationships
social history
women's history
ancient Greece
athenian women
attic women
women

This thesis offers a new assessment of the relationships of fifth- and fourth-century Attic women, of citizen and metic status. Chapter 1 demonstrates women’s capacity to build and use relationships through and against the vicissitudes of their lives, particularly their transitions between marriages and households. Chapter 2 argues for women’s ability to shape formal and informal kinship structures in response to their own affective relationships. Chapter 3 suggests that women could use their relationships with enslaved people, particularly enslaved women, either to confirm or challenge their other roles and relationships within the household. Chapter 4 shows how income-generating work expanded women’s social networks, gave them opportunities publicly to present themselves in terms and contexts independent of their family relationships, and enabled them to redefine their roles within their families. Chapter 5 shows how women formed, used, and defined their friendships, considering in particular the role of the neighbourhood and of religion as contexts within which women could shape their social landscapes.
The thesis weighs up different approaches to writing women’s history. Chapter 1 argues for the value of reconstructive biography. Later chapters focus on re-reading narratives about men to draw out the experiences of women, without attempting complete biographies, and on understanding epigraphic testimonies that women were involved in authoring as instances of women’s self-writing—not autobiographies but women’s brief portraits of themselves and others.
The thesis argues that women’s formal and circumstantial relationships did not necessarily commit them to fixed roles or social behaviours but provided a framework within which they could develop and shape their affective relationships and negotiate their own roles. It demonstrates the potential breadth of women’s networks, affiliations, and relationships; how they were formed and changed across the course of women’s lives, and how they cross-cut other groupings and divisions in Attic society. It argues that women were more able to shape their lives and relationships than has previously been thought, and therefore played a more dynamic role in the social history of classical Attika.
Decoding the role of the RNA binding activity of p53
Keywords: RNA binding proteins
p53
cancer

p53 is a key tumour suppressor, mutated in over half of cancers. p53’s ability to form extensive protein interactions, along with its function as a sequence-specific transcription factor, are well documented due to their roles in canonical p53 tumour suppressor functions. Still lacking is clarity regarding p53’s ribonucleic acid (RNA) binding activity. Previously reported, predominantly acellular and in vitro results provide little in regards to the physiological relevance, biological function and underlying mechanisms of p53-RNA interactions. Here I demonstrate p53 binds polyadenylated RNA in living cells using RNA interactome capture. Further investigation of p53-RNA interactions using conventional immunoglobulin G (IgG) antibody-based approaches proves problematic. I therefore generated an inducible cell line expressing green fluorescent protein conjugated p53 (GFP-p53), enabling highly specific purification of GFP-p53. Utilising CLIP-seq, I identified a defined subset of messenger RNAs (mRNAs) bound by p53, representing a translational programme distinct from p53's transcriptional targets. Additionally, RNase coupled proteomic analysis reveals the importance of RNA in p53's protein interaction network, including the DNA damage response. This work provides evidence of a p53 post-transcriptional regulatory layer, which warrants further investigation.
In-group bias in human cooperation: insights from the contrade of Siena, Italy
Keywords: Siena
group relations
Italy
third-party punishment
economic game
field experiment
competition
in-group bias
cooperation
common enemy

Cooperation in humans shows an in-group bias, with individuals more likely to benefit members of their own in-group than members of other out-groups. This thesis explores the effects of inter-group competition, group relationship, and shared identity on in-group bias, by conducting field experiments among communities in a historic Italian city, namely the contrade of Siena.
In Chapter 1, I review the literature on the evolution of cooperation and in-group bias. I then describe how field experiments that employ economic games can help elucidate in-group bias in the real world, before outlining how I conducted field experiments with the contrade. I describe the contrade in greater detail in Chapter 2, using research from my fieldwork among these communities to demonstrate the importance of group relationship in the Sienese context.
In experiment 1 (Chapter 3), I compare in-group and out-group cooperation during a period characterised by low competition vs. high competition. There is no evidence for an effect of competition. However, there is a significant effect of group relationship, with more cooperation among neutral out-groups compared to rival out-groups. In experiment 2 (Chapter 4), I analyse third-party punishment decisions and participants’ interpretations of the experiment, to assess whether cooperation within and between contrade is supported by social norms. There is limited support for third-party punishment sustaining norms governing either in-group or out-group behaviour. In experiment 3 (Chapter 5), I explore the effect of shared identity on in-group bias, by seeing if a “common enemy” encourages out-group cooperation. The common enemy neither increases the perceptions of shared identity nor decreases in-group bias.
I conclude with a meta-analysis in Chapter 6, which reveals an overall strong in-group bias among the contrade. The bias is influenced by the relationship between the groups, but is unaffected by the level of competition and attempts to induce a shared identity. This thesis shows that symbolic group identities in the real world have a significant impact on social behaviour.
On the motivic Galois theory of some families of Feynman integrals
Keywords: Modular forms
Motivic Galois group
Feynman integrals

Feynman integrals are the building blocks of scattering amplitudes in quantum field theory, and are therefore central to comparing theory with experiment in high-energy physics. Following the work of Brown, we can canonically associate a family of motivic periods to any convergent Feynman integral viewed as a function of the kinematic variables. Moreover, the action of the motivic Galois group is conjectured to be closed on the space of motivic periods arising from Feynman integrals, factoring through a subquotient referred to as the cosmic Galois group. Brown's "small graphs principle" implies that it is possible to deduce strong constraints on Feynman integrals to all loop orders from results on graphs with a small number of edges. This serves as motivation for explicitly computing this group action, or, dually, the coaction of the Hopf algebra of functions on the motivic Galois group.
In this thesis, we find an explicit formula for the coaction on the 'motivic lifts' of Feynman integrals associated to one-loop Feynman graphs, as well as the two-loop sunrise graph, which is known to evaluate, in the equal-mass case, to a value of the elliptic dilogarithm. We also study the coaction in some cases when the underlying geometry degenerates. It is conjectured in the physics literature that dimensional regularization is compatible with the motivic Galois coaction. We show that computations in twisted cohomology reflect the expected effect of expanding the space of motivic Feynman integrals by introducing the 'motivic lifts' of dimensionally regularized Feynman integrals.
We find a new class of single-valued periods associated to the functions on the de Rham realization of the motivic Galois group arising in the coaction on the elliptic dilogarithm, which generalize Brown's non-holomorphic modular forms with two weights. Finally, we apply the theory of the relative completion of the torsor of paths on a modular curve, due to Hain and Brown to find a new proof that the sunrise Feyman integral can be expressed in terms of integrals of modular forms.
The bridge, insurance and the fund: Building uncertain city futures in Dar es Salaam
Keywords: world city
Tanzania
insurance
social security
uncertainty
insurance urbanism
temporality
urban imaginaries
people as infrastructure
pensions
welfare
providential fund
Dar es Salaam
worldliness
infrastructure
popular insurance
futurity

Drawing upon eighteen months of fieldwork between 2016 and 2018, this thesis provides an ethnographic account of culturally mediated and materially founded emergent forms of urban life in Dar es Salaam. The fieldwork was mainly conducted in close proximity to two ‘field sites’: the Nyerere Bridge, popularly known as the Kigamboni Bridge; and East Africa’s largest pension fund, a parastatal pay-as-you-go pension scheme whose investments financed the building of the bridge together with the Tanzanian government. The thesis begins by setting out on a short journey some 680 meters across Kurasini Creek, the tidal creek stretching through central Dar es Salaam that divides the dense downtown neighbourhoods from the lofty Kigamboni district in the south. As we venture over the Nyerere Bridge, however, we are embarking on a much longer journey, one of insurance, of how risky urban futures are negotiated, based on participant observation, mapping and archival work, extended interviews and conversations with operators, bureaucrats, managers, politicians, worker, engineers, and residents, all implicated in ‘city-making’.
The thesis is divided into four parts. Part I consists of the first three chapters: introduction, theoretical outline, and methodology. The three middle parts are ethnographically driven and structured by a tripartite engagement, each part of which - the bridge, insurance and the fund - includes two chapters each. The thesis ends with a concluding chapter.
Confession and cartography: religion and the mapping of Poland-Lithuania
Keywords: paganism
Jews
Polish-Lithuanian Commonwealth
Marian devotion
18th century
Protestant
bishops
confessionalisation
pilgrimage
16th century
Georg Braun
religion
Reformation
cartography
Erik Dahlbergh
counter-reformation
Catholic
Lithuania
prayer
forest
wood
deluge
hierophany
civitates orbis terrarum
17th century
Poland
sacred space
maps

The religious aspect of early modern cartography remains under-appreciated, and little-understood. It has been overlooked, above all, because of a tenacious assumption: that cartography was secularised by the Ptolemaic revolution. In recent years this assumption has been challenged, but our knowledge remains severely limited; this is particularly true with regard to the great religious changes of the period: the Reformation, Counter-Reformation, and confessionalisation – a gap which this thesis is intended to fill. It approaches this issue through the lens of a case study, the cartography of the Polish-Lithuanian Commonwealth, from the later-16th to the early-18th century, and is guided by the question: ‘how did cartography respond to the religious changes within early modern Europe?’. In five chapters, it approaches this question from different angles: (1) the changing border of Europe (and continuing fear of paganism), (2) the idealised purification of Christendom in Georg Braun’s Civitates Orbis Terrarum (1572-1617), (3) the struggle to map confessional diversity (approached through a deconstruction of the mapping of the bishop) (4) the response to confessionalisation in the cartography of the Deluge (1655-60), (5) the place of cartography within Counter-Reformation Marian devotion.
Cartography proved highly responsive to the religious changes of the age, responding in a multiplicity of ways, that were much more diverse and complex than the Catholic/Protestant binary that has often defined our understanding. It was much more sensitive to changes in people’s minds, however, to their beliefs, fears and agendas, than to changes on the ground – and its response was also limited by the nature and deficiencies of the cartographic medium, which inhibited, in particular, its ability to depict religious diversity. It was an important cultural space where these religious issues were engaged with, and it is argued that cartography could, therefore, serve as a unique and valuable source for historians of religion.
The colloidal liquid-gas interface: kinetics of phase separation, confinement and optical manipulation
Keywords: physical chemistry
optical tweezing
colloid
polymer
phase separation

In this thesis, the colloidal liquid-gas interface is studied. First, the evolution of colloidal gas-liquid phase separation in a colloid-polymer mixture through nucleation and growth is addressed. Using confocal microscopy, different statepoints are observed and three different mechanisms are found in distinct regions of the phase diagram: at low polymer concentration the colloidal liquid droplets coalesce until they fill the field of view, at higher polymer concentration, the colloidal liquid droplets stick to each other continuously throughout the entire observation period, and at the highest polymer concentration probed, the droplets stick to each other until a certain point where their size remains constant. Growth laws are computed and compared to theoretical predictions. The structure of the patterns formed as phase separation takes place and the motion of the growing droplets are analysed for each mechanism. Next, the thermal capillary waves of the colloidal liquid-gas interface in confinement are observed with confocal microscopy. The line tension as well as the dispersion relation are measured. The relaxation times of the modes of the fluctuations are measured and compared to theoretical predictions. Then, a tightly focused beam of laser light is used to nucleate a droplet of colloidal liquid into the colloidal gas phase for different laser powers and different heights above the colloidal liquid-gas interface. The kinetics of the growth and final size of the droplet were found to be unaffected by laser power and height above the colloidal liquid-gas interface. The kinetics of the growth of the droplet reveal that the growth is driven purely by electrostrictive effects and not by thermal gradients induced by the laser light. Finally, the evaporation of liquid droplets nucleated with optical tweezers is studied through fluorescence microscopy after the laser used for tweezing was switched off. From solving the diffusion equation, the diffusion coefficient of the colloids into the gas phase is measured. It is found not to vary with the height above the liquid-gas interface or the laser power used to nucleate the droplets. For droplets grown at a height of 20 microns, droplets sink at a constant velocity as they evaporate and interact with the liquid-gas interface below them.