VictorJuiz/thesis huggingface dataset:
Designing tandem catalytic reductive functionalisation strategies of carbonyl derivatives
Keywords: photoredox catalysis
reductive amide functionalisation
computational chemistry
asymmetric catalysis

Chapter 1 introduces tertiary amide-based reductive functionalisation strategies as attractive access points towards medicinally relevant α-branched tertiary amine building blocks. Within the scope of this synthetic transformation, Vaska’s complex is highlighted as a chemoselective transition metal catalyst that has come to the forefront for facilitating tertiary amide and lactam hydrosilylation in a mild and efficient manner in both small molecular systems and complex natural product synthesis.
Chapter 2 provides a brief description of the Density Functional Theory-based computational methods that were used in Chapters 3 and 5 to complement the corresponding experimental findings.
Chapter 3 describes the development of a dual catalytic umpolung reductive functionalisation strategy that enabled the generation of nucleophilic α-amino radical intermediates from robust tertiary amide starting points under a mild set of hydrosilylative/photocatalytic conditions. The work showcases how a tandem, dual catalytic approach can be utilised to enable reductive coupling of amides with electrophiles, previously inaccessible using Vaska’s complex-based hydrosilylative chemistry.
Chapter 4 demonstrates how a derivative of Vaska’s complex can facilitate the hydrosilylation of α,β-unsaturated ketones. This finding provided a new synthetic opportunity for the iridium (I)-catalysed reductive functionalisation strategy to be used with carbonyl functionalities beyond the established tertiary amide motif. Inspired by the dual catalytic methodology developed in Chapter 3, the hydrosilylation step was combined with a secondary, chiral catalytic cycle to access enantioenriched products from feedstock enones, which have been thus far unprecedented for Vaska’s catalyst-based methodologies.
Chapter 5 features a computational study that was undertaken to elucidate the mechanism and origins of stereoselectivity for a novel, organocatalytic, nucleophilic desymmetrisation of prochiral phosphonate ester reaction developed in the Dixon group. The systematic approach that was used to construct a computational model of the experimental conditions is presented. An analysis of the key, non-covalent interactions that governed both stereoselectivity and reactivity of the system is also provided.
Modular sulfondiimine and sulfondiimidamide synthesis using stable sulfinylamine reagents
Keywords: sulfondiimidamide
sulfondiimine

In this thesis, novel methods for the synthesis of sulfondiimines and sulfondiimidamides are described. The use of sulfinylamine linchpins in combination with commercially available organometallic reagents and amines provides access to a broad range of sulfondiimines and sulfondiimidamides.
Chapter 1 provides an overview of the properties of S(VI)-functionalities such as sulfoximines, sulfonimidamides, sulfondiimines and sulfondiimidamides, as well as synthetic strategies to access them.
Chapter 2 documents a novel strategy for the preparation of sulfondiimines. A stable sulfinylamine linchpin, N-sulfinyl-tert-octylamine (t-Oct-NSO), is selected as the starting reagent. The combination of two different organometallic reagents with t-Oct-NSO in the presence of Lewis acid generates the sulfilimine intermediate. This is followed by a rhodium-catalysed imination, providing a broad range of orthogonal N-protected sulfondiimines. Deprotection and various functionalisation reactions provide the most diverse range of sulfondiimines to date.
Chapter 3 describes the exploration of a novel functional group, sulfondiimidamides, which are the di-aza analogues of widely explored sulfonamides. The combination of t-Oct-NSO with LiHMDS, TMSCl and various organometallic reagents provides the corresponding N-t-Oct primary sulfinamidines. Protection with a nosyl group provides orthogonally N-protected sulfinamidines. Oxidative fluorination followed by Ca(NTf2)2-mediated amination converts the sulfinamidines to the corresponding sulfondiimidoyl fluorides and sulfondiimidamides, respectively. Imidazole-substituted sulfondiimidamides are also shown to be effective intermediates, allowing primary amines and challenging N-nucleophiles to be used. A series of deprotection and further functionalisation reactions using sulfondiimidamides are described, indicating the possible application of these interesting functional groups in the pharmaceutical industry. An analogue of the COX-2 inhibitor, Celecoxib, was prepared using this methodology.
Chapter 4 details the discovery of a novel sulfinylamine linchpin, N-sulfinyl-triisopropylsilylamine (TIPS-NSO). The reaction of the TIPS-NSO with LiHMDS, TMSCl and various organometallic reagents followed by N-protection and N-TIPS deprotection, enables the synthesis of N-substituted primary sulfinamidines. A robust sulfondiimidamide synthesis method is developed from these primary sulfinamidines via PhI(OAc)2-promoted amination. Celecoxib analogue is prepared using this methodology in only four steps, and a sulfondiimidamide analogue of Sildenafil is accessed in just two steps.
Chapter 5 discusses the conclusion of our research and future plans.
Chapter 6 presents the experimental procedures and data.
O Canto Precário: Epopeia, derrogação heróica e desumanização em Caramuru (1781)
Keywords: Luso-Brazilian Literature
natural goodness
colonial Brasil
indigenous representation
Arcadismo
Caramuru
epic poetry
Brazilian literature
Moema
sacrifice
Portuguese studies
Lusophone studies
Nativismo
Enlightenment
Santa Rita Durão
Barter

This thesis reframes the relevance of "Caramuru" (1781) in the contemporary field of literary and cultural studies in Portuguese. Responding to and revisiting the critical reception of the work, I consider that its circumstance in literary history falls short of the poem that Friar José de Santa Rita Durão wrote. What I call the fragility of the epic singing of the author is the vanishing point of my argument, which is extracted from the ambiguous character of the poetic configuration of the indigenous subject in the epic and consequent production of interpretative meaning. Aware of the overlook of the period within the literary studies in Portuguese, I intend "Caramuru" to be recognised as a pivotal work of the Portuguese-speaking world, written right after the gold extraction from Brazil and just before the dawn of the Brazilian nation. This period offers a rich questioning platform on several aspects that are present in today’s discussions on works and media in Portuguese, which is the case of how slave trade alongside racialized subjects are at the very foundation of the idea of the Portuguese Empire. Through its epic Durão shows partial evidence of this critique in a work meant to, paradoxically, glorify his fatherland. To get here, I discuss through "Caramuru" the Brazilian literary neoclassicism, the epic design of its hero, the poetic representation of the figure of the Brazilian indigenous peoples according to the Portuguese colonial system, the subsequent canonical derogation from the lyric and epic modes, the 18th century conception of nature and the idea of natural goodness, and how the enlightenment thought contaminated the relationship with the Amerindian peoples, interfering with the Brazilian identity at the time of its independence.
Augmented reality for the sight impaired
Keywords: Augmented reality
Sight loss

Vision loss is rarely absolute; most people referred to as blind have some form of residual vision. This residual vision can create a confusing view of the world. In this thesis, I explore how a camera system and a wearable display can augment an image of the word to improve its visibility and understanding to a visually impaired wearer. I focus on two crucial parts of life; recognising faces and reading.
In the first part of this thesis, I design and validate a new face perception test to assess different image enhancement forms. I used this new test to measure the impact of image enhancement on a visually impaired population (n=64). The results found that approximately 40% of participants showed a significant improvement in test scores. Performance was related to reading acuity and lower spatial frequency loss. I then develop and integrate a complete real-time image processing solution for face perception enhancement with an augmented reality display, demonstrating a practical application of the image enhancements.
The second part of this thesis's focus is reading. I compare paper-based reading performance against reading with a virtual reality (VR) display with a visually impaired population (n=53). I further assess the impact of different colours on reading with the VR display. The results found no difference in reading performance, comparing VR to paper- based. The colour of text and background had a significant effect, with 75% of participants having a preferred colour combination. A participant with a higher overall magnitude of colour vision loss is more likely to benefit from white text on a black background than black text on a yellow background.
Augmenting an individual's residual vision can improve the quality of information they receive about the visual world. While not universal, this improvement has the potential to enhance a visually impaired person's quality of life significantly.
Taste shaping natures: a multiplied ethnography of translated fermentation in the New/er Nordic Cuisine
Keywords: innovation
New Nordic Cuisine
microbes
fermentation
multispecies
domestication
taste

Culinary innovators in Copenhagen are combining far-flung fermentation techniques with Nordic ingredients to yield products and flavours that have not existed before. This flavour-oriented ‘translated’ fermentation is also having broader cultural and material consequences, for these culinary practitioners as well as for their microbial partners’ biogeography, ecology, and likely their evolution. To account for these novelties, I bring together critical scholarship on nature, more-than-human geographies and multispecies studies, theories of taste, and STS, to develop the concept of a ‘taste shaping nature’: a nature shaping and shaped by taste. Employing a novel combination of multispecies multisensory ethnography, collaborative microbiological experiments, and DNA sequencing—an approach I shorthand as ‘multiplied ethnography’—I conducted fieldwork around two sites in Copenhagen, Restaurant Noma and Empirical Spirits, leaders in the culinary movement sometimes known as the ‘New Nordic Cuisine’ (NNC). Linking my fieldwork and the literature, I develop each part of ‘taste shaping natures’ across four analytic chapters: on ‘Nature’, ‘Consipience’, ‘Experiment’, and ‘Interest’. ‘Nature’ investigates how the NNC has mixed ‘wild’ and ‘postpastoral’ natures, how these ‘multinatures’ have shifted over time, and how they have shaped and been shaped by different approaches to fermentation. ‘Consipience’ articulates how humans and microbes—or any creatures—come to know each other through taste and smell, within and across species, as a contribution to STS, multispecies studies, and sensory ethnography. ‘Experiment’ examines the role of technoscience in how humans and microbes know and shape each other in translated fermentation, and proposes a model of experiment as a contribution to STS. ‘Interest’ brings together the aesthetics, ethics, politics, and biological consequences of translated fermentation’s taste shaping natures, and suggests the supporting concept of ‘micro-governmentality’ as a complement to ‘microbiopolitics’. In conclusion I reflect on fermentation politics, and consider how fermentation contributes to ongoing debates around domestication.
The Attic elite beyond the polis in the sixth and fifth centuries BC
Keywords: Cleruchy
Athenian Empire
Athenian Economy
Athenian Elite

This thesis concerns the extra-polis activity and relationships of elite Athenians in the sixth and fifth centuries BC. It studies the range and character of the economic opportunities outside Attica in which elite Athenians participated, arguing that in the late archaic period as well as afterwards the most successful individuals and families prospered at home not (or not only) because they happened to be the largest landowners in Attica, but because they best exploited the extra-polis opportunities afforded by their particular freedom of movement and by their privileged access to productive relationships of xenia.
Such activities and relationships have often been construed, indeed were often presented by those involved, as driven by philotimia (the desire to be valued in and by a community). My thesis emphasises the importance of philochrēmatia (the desire for property) and alignments and tensions between these twin motivations. It seeks to characterize the Attic elite across both centuries, rather as Thucydides’ Corinthian characterized the Athenians collectively, as ἀποδημηταὶ πρὸς ἐνδημοτάτους: οἴονται γὰρ οἱ μὲν τῇ ἀπουσίᾳ ἄν τι κτᾶσθαι (1.70.4). Elite Athenians were part of a thriving economy above and beyond the polis, and this needs to be a central part of our picture of late archaic and early classical Athens, not least because successful participation in that economy was a major component of what constituted them as an elite.
"Especially the poor": The London City Mission, 1835-1914
Keywords: a study of nineteenth century working-class religion and evangelical mission in London

This dissertation considers the work of the London City Mission (LCM) between 1835 and 1914. It presents an analysis of the evangelical faith, agency, and achievements of LCM’s working-class missionaries as they lived and worked among people whom many have believed to have been religiously ignorant and indifferent. This was not the case. This dissertation is not a study of LCM’s success measured by the details of new evidence of working-class churchgoing and churchgoers, but an analysis of the way in which LCM’s missionaries’ undenominational religious teaching became available to substantial numbers of those whom they sought to reach in anything they might be doing, and everywhere they might be met. It is a dissertation whose perspective is different. It is a discussion of working-class Christian faith that was experienced at a significant distance from the sacraments and structures of institutional and denominational religion. Its evidence is drawn from the hitherto unknown eye-witness accounts of LCM’s missionaries that are contained within LCM’s extraordinary archive. This study details the fundamental principles of LCM, identifies its unique character, and reveals the unrecognised scale and scope of their evangelical mission. It discusses LCM’s working-class missionaries, their backgrounds, their motivation in their work, and illustrates the way in which their spiritual imperative in mission was inseparable from their deep social concern. It explores the diversity and creativity of the missionaries’ agency. It demonstrates how over generations, in their districts and fields of special mission, because of their mutual understanding, and support, LCM’s evangelical mission thrived and was accepted as an integral part of everyday life by hundreds of thousands of working-class people.
Chemically modified guide RNAs to expand CRISPR functionality
Keywords: Imaging
sgRNA
CuAAC
Click chemistry

CRISPR-Cas, a bacterial adaptive immune system against viruses, has been repurposed into a biological research tool that is invaluable due to its simplicity and programmability. Composed of a Cas endonuclease that is directed to its nucleic acid target by a guide RNA (gRNA), CRISPR has been used for genome editing, live-cell imaging and even diagnostics. In this work, the goal is to chemically modify gRNAs to expand CRISPR functionality. A ‘split-and-click’ strategy for generation of Cas9 gRNAs via CuAAC ‘click’ ligation of shorter oligonucleotides is developed. The approach provides a simple and cost-effective route to individual or pools of single guide RNAs (sgRNAs), while providing scope for further chemical modification to improve sgRNA activity. The click sgRNAs are functional both in vitro and in cells, demonstrating artificial linkages can be tolerated in functionally critical regions of sgRNA. To illustrate the capabilities of the system, work towards an on-field forensic analysis of Short Tandem Repeats (STR) is described using CRISPR, Ramified Rolling Circle Amplification (RAM) and Oxford Nanopore sequencing. sgRNAs were also tagged with small molecule fluorophores to provide greater flexibility in colour choice and expand the colour range for live-cell imaging. Imaging of repetitive elements of telomeres is feasible with these constructs if GFP-tagged dCas9 is used for cross validation; due to high cytoplasmic background fluorescence, methods to turn on fluorescence in the nucleus are also explored. Finally, two CRISPR-AsCas12a gRNAs are chemically ligated to yield a 3'-3' dual gRNA with the aim of altering the DNA cleavage pattern of the Cas12a protein. Chemical ligation in this context impaired gRNA activity in vitro, however unexpected single-stranded DNase activity is described for AsCas12a.
Micro-mechanical testing of the hex-BN interphase in SiCf/SiC composites for aero-propulsion
Keywords: ceramic matrix composites
materials science
fibre push-out
aerospace
composites
silicon carbide
micromechanics

This thesis provides an overview of micro-level mechanical testing of the BN interphase in SiCf/BN/SiC composites, in the context of lifing models for aero-engine components. A wide number of variables were tackled in the development of both traditional and novel techniques to assess micro-level properties of the composites. The latter included the interfacial shear strength (varied), modulus (25.9 ± 5.4 GPa), hardness (1.3 ± 0.1 GPa), fracture toughness (6.7 ± 2.4 MPa.m1/2), debonding toughness (13.3 J.m-2), and frictional sliding resistance (4 ± 1 MPa) of the interphase, alongside other composite constituents where applicable.
The use of a nanoindentation apparatus was central to this work – both Berkovitch and flat-punch tip geometries were made use of. Established techniques were assessed in their viability for probing the properties of the BN interphase on its own: these included the fibre push-out, push-in and push-back. Due to the sheer volume of data, the significance of results was assessed statistically.
Upon completion of method development, material-dependent variables and their effects on the change in micro-mechanical behaviour were subsequently investigated. The parameters tackled included the variability in measurements from tow location at weave-architecture level (inter-tow), tow level (intra-tow), BN interphase thickness, nature of fibre type, cyclic testing, interphase doping levels and neighbouring fibre geometry; where it was found that a need for intra-tow variability was to be stressed over the importance of inter-tow variability in measurements of mechanical properties, although both were found to be statistically relevant.
The ceramic-matrix composites were subsequently exposed to high relative humidity and elevated temperatures; and tests repeated. The degradation from intermediate-to-high temperatures showed little to no change in mircromechanical performance (strength retention ratio of 79.1%) when compared to low-temperature high humidity exposure (strength retention ratio of less than 50% after 500 hours exposure). Despite results from these chapters, a further understanding of the dominating failure mechanism needed to be understood. This led to the development of miscellaneous micro-mechanical techniques performed in-situ (both in SEM, micro and nano-XCT), including the novel trench push-out which imaged mixed-mode failure (simultaneous inside and outside debonding) and defective interphases leading to linking of smaller cracks before push-out.
In the context of work by Rolls-Royce plc, the body of results yields both quantitative and qualitative information, for incorporation in coupon-level lifing models. The academic merit of this work lies in the investigation of variability in measurements of composite interphase properties, as well as micromechanical-technique development for a clearer understanding of the damage mechanisms at hand.
Learning new words via reading: the influence of context and diversity

Keywords: Semantic Diversity
Anchoring
Reading
Contextual variation
Word learning

From mid-childhood onwards, the majority of new words are incidentally acquired via independent reading. Numerous studies have shown that the linguistic contexts in which a new word appears influences the ease with which the word is processed and acquired. Some contextual characteristics (e.g., high topic familiarity) are more beneficial to learning than others. The focus of this thesis is a relatively new contextual characteristic, known as semantic diversity, defined as the degree to which a word’s surrounding contexts overlap in terms of semantic content. The overarching aim of this thesis is to investigate how semantic diversity influences the learning of novel words in young adults. This thesis comprises a total of four word-learning experiments and three computational simulations. They all contrasted two learning conditions: high semantic diversity (multi-themed) and low semantic diversity (single-themed). Both Experiment 1 and Simulation 1 demonstrated that novel words experienced multiple times in one familiar topic (i.e., low semantic diversity) were advantaged in initial learning, a finding attributed to what I refer to as “anchoring”, a process of securing novel words onto long-term memory. On the other hand, Simulation 2 and Experiment 2 showed that novel words that had an anchoring opportunity were better placed to take advantage to high semantic diversity, suggesting that anchoring may benefit initial but not later learning. Simulation 3 used word vectors to mathematically simulate how semantic diversity influences the learning of meanings across Experiments 1 and 2. The simulation results showed that high-diversity words tend to have sparser semantic spaces, potentially indicative of weaker integration into pre-existing knowledge. In order to consolidate the results from Experiment 2, Experiment 3 monitored participants’ eye movement during reading. The results suggest that novel words appearing in high-diversity contexts are encoded more strongly during reading and tend to have more context-independent representations. Finally, while Experiments 2 and 3 showed that experiencing a novel word multiple times in a repeated topic could serve to anchor, Experiment 4 demonstrated that an explicit definition could also achieve the same effect, enabling the novel words to be better placed to take advantage of high semantic diversity. Together, this research demonstrated that initially restricting a novel word’s semantic diversity (i.e., starting small) and capitalizing on learners’ prior knowledge can support anchoring, which can facilitate subsequent learning in more diverse contexts.