VictorJuiz/thesis huggingface dataset:
Investigating rhodium-catalysed hydroacylation and carbon-carbon bond activation

The work described in this thesis documents the development of new rhodium(I)-catalysed methodologies within two areas of research. The first examines the use of carbonyls as chelating groups in hydroacylation to produce synthetically valuable ketones and enones. The second area explores new carbon-carbon bond activation methodologies.
Chapter 1 presents a literature review of the historical development of rhodium-catalysed hydroacylation, with a focus on chelating groups that can currently be used to suppress decarbonylation. A brief review of methodologies that avoid the requirement for a tether is also included.
Chapter 2 describes the development of a novel hydroacylation methodology employing carbonyl-based functional groups as tethers on aldehyde substrates.
The chapter begins with the optimisation studies for the hydroacylation of β-formyl amides with terminal and internal alkynes, allenes and terminal alkenes, and subsequently explores the substrate scope for each case. The chapter then outlines the investigations undertaken with 1,4-dicarbonyl and 1,5-dicarbonyl systems, N-formyl amides, β-formyl esters and finally β-formyl ketones. A detailed description of the routes undertaken to synthesise each starting material is also presented.
Chapter 3 presents a short review surveying the key milestones in the development of carbon-carbon activation methodologies. The chapter begins with a theoretical comparison to carbon-hydrogen activation and a discussion of the unique challenges that are faced. An overview of the major strategies employed to enact these processes is subsequently presented for both strained and unstrained substrates.
Chapter 4 outlines the attempts undertaken to develop a novel carbon-carbon bond activation methodology. The work evaluates sulfur-, nitrogen- and alkene-based chelating groups, known to be successful in hydroacylation, in analogous ketone substrates.
Chapter 5 discusses the conclusions from this work and the potential for further work.
Chapter 6 presents the experimental procedures and data.

Advisor: Willis, M
Advanced quantitative analysis of crack fields, observed by 2D and 3D image correlation, volume correlation and diffraction mapping

This thesis is concerned with the evaluation, in-situ, of the elastic strain energy release rate of cracks. This can define the criteria for crack propagation, and it is usually necessary to obtain this via calculation from the geometry and applied load. A new method is proposed, based on the conjoint use of digital image correlation to measure full-field displacements and finite element to extract the strain energy release rate of surface cracks. It has been extended to 3-D datasets with the use of digital volume correlation and tomographic imaging. A finite element model with imported full-field displacements measured by DIC/DVC acting as boundary conditions is solved and the J-integral is calculated. For linear elastic materials, modal contributions can be separated via the interaction integral.
The method has been benchmarked using synthetic datasets to assess its sensitivity to noise and experimental uncertainties. It is very robust to experimental noise and can be used without knowledge of the specimen geometry and applied loads. The application of the method in 2-D is demonstrated in an analysis of experimental data for a mode I fatigue crack, introduced to an aluminium alloy compact tension specimen. Analysis of mixed-mode cracks in 2-D is shown on a PMMA sample with the Arcan geometry. In 3-D, static loading of a fatigue crack in nodular graphite cast iron is studied and the results from the method are compared with those obtained via a field-fitting approach.
Diffraction analysis of polycrystalline materials can determine the full tensor of the elastic strains within them. Maps of elastic strains can thus be obtained typically using synchrotron X-rays or neutrons. A method is presented to calculate the elastic strain energy release rate of a crack from 2-D diffraction strain maps. The diffraction data is processed via a finite element approach to obtain the parameters required to calculate the J-integral. A validation is presented using a synthetic dataset from a finite element model. Its experimental application is demonstrated in an analysis of synchrotron X-ray diffraction strain maps of a propagating fatigue crack in a bainitic steel, before and after an overload.
Finally, a complex case study of stable fracture propagation in polygranular isotropic nuclear graphite is presented. Synchrotron X-ray tomography and strain mapping by diffraction were combined with DVC and image analysis to extract the full-field displacements and elastic crystal strains. The displacement fields have been analysed using the developed methods to extract the critical strain energy release rate for crack propagation. Non-linear properties described the effect of microcracking on the elastic modulus in the fracture process zone. The analysis was verified by comparison of the predicted and measured elastic strain fields.

Keywords: X-ray diffraction
Finite Element
Digital Volume Correlation
Tomography
J-integral
Fatigue
Simulation
Fracture
Digital Image Correlation
Advisor: Marrow, J
Reading the transformation: the relationship between literature and territory in contemporary Veneto

Reading the Transformation: The Relationship between Literature and Territory in Contemporary Veneto aims at investigating the interrelation between a geographically defined entity and the literary word. Placed in the context of a broader reflection on the dynamics of such relation, this thesis aims at outlining a specific set of theoretical references in order to analyse the case of contemporary Veneto through a close reading of some particularly relevant works by two authors from this region, Massimo Carlotto and Marco Paolini.
Developed from an interest in the literary tradition of Veneto and in the theme of landscape and territory representation in literature, this thesis is comprised of two parts: the first one is dedicated to tracing the theoretical, historical, and literary coordinates that define the scope and frame of reference for the thesis; the second one conducts an in-depth analysis of the context in which the works of Carlotto and Paolini are situated. Drawing on concepts pertaining geography, cultural anthropology, and landscape theory, the premise of this thesis is that territory is a complex geographic, historical, social, economic, and cultural entity of which landscape constitutes the visible stratum. Siding with arguments that sustain the centrality of the role of landscape in the process of formation of people's identity, this thesis adopts such concept and employs it as a key to understand the relation between territory and literature. Through the analysis of La verità dell'Alligatore and Nordest by Carlotto and Il Milione and Bestiario Veneto – Parole mate by Paolini, the objective of this thesis is, on one side, to provide an insight into how the transformation of a territory can shape the formation of a collective identity, on the other side, to shed light on the means through the reflection on territory enters the literary space.

Keywords: massimo carlotto
literature and territory
marco paolini
contemporary Italian literature
Advisor: Bonsaver, G
Adeno-associated virus mediated rhodopsin delivery in preventing secondary cone degeneration in rhodopsin knockout mice

Rhodopsin-linked retinitis pigmentosa (RP) is the most common form of autosomal dominant RP, an inherited retinal degeneration, in which rod degeneration is followed by secondary cone loss leading to loss of vision and blindness. The overall objective of this work was to develop an optimized gene replacement therapy, delivering the rhodopsin gene for rhodopsin- linked RP and establish whether secondary cone loss can be delayed.
A fast-acting single mutant serotype 8 self-complementary adeno-associated virus vector was produced containing the human rhodopsin promoter and the human rhodopsin coding sequence. In vivo studies in rhodopsin knockout mouse showed that the vector administration led to widespread and robust expression of the transgene.
Subretinal injection of the vector into three-week pups of rhodopsin knockout mice with cones expressing green fluorescent protein showed restoration of rod-derived electroretinogram (ERG) responses, and preservation of cone- driven ERG responses three months after injection. Similarly, the longitudinal follow-up with confocal scanning ophthalmoscopy found preservation of fluorescent cones up to three months after injection. Overall, these data provided evidence that the designed vector resulted in significant benefit to rod photoreceptors as well as in delay in secondary cone degeneration and built a basis for future use of this vector on dominant models of RP.

Keywords: rhodopsin associated retinitis pigmentosa
adeno-associated virus mediated gene therapy
Advisor: Maclaren, R
Britain and Revolutionary Iran 1906-1909 and 1976-1979: a comparative study

This dissertation is a comparative case study of British policy towards and perceptions of Persia/Iran during the latter's two modern revolutions, 1906-1909 (Constitutional) and 1976-1979 ('Islamic'). The study covers both official perceptions and policy, meaning that of the Foreign Office and Diplomatic Service and the perceptions of the press, civil society, Parliament and wider public opinion; thus it is not a traditional exercise in diplomatic history. It explores British views of both the Shah/government and opposition forces during these two periods in detail and presents these views in a comparative perspective. The research paints a broad social and historical picture of how changes in both British and Iranian government, society and global status affected their mutual relations. Key themes relate to how the decline of (Edwardian) Liberalism, the transformation of the Left in the twentieth century and Britain's decline as an imperial power affected its perceptions and policy-making in Iran; how civil society and public opinion exerted a disproportionately strong influence in the earlier period before Britain was even a fully democratic society; how notions of Orientalism and Aryanism shaped official and public perceptions; and how changing geopolitics impacted perceptions, particularly in the case of Tsarist Russia versus the Soviet Union. This study has revealed numerous counter-intuitive points about the foreign relations and perceptions of British government and society vis-à-vis Iran and prompts a reconsideration of the evolution of British public and official attitudes during the twentieth century as manifested in the case of Iran at two critical historical junctures.

Keywords: Iran
Anglo-Iranian relations
Britain
Advisor: Cronin, S
Probing the evolution of galaxies since z ~ 1 with the Tully-Fisher relation

In this thesis we use the Tully-Fisher relation (TFR), the correlation between a galaxy's luminosity and its rotation velocity, to probe the luminous and dark matter in galaxies over the last ≈ 8 Gyr. First, we use samples of galaxies spatially resolved in Hα emission with integral field unit observations from the K-band Multi-Object Spectrograph (KMOS) Redshift One Spectroscopic Survey (KROSS) at z ≈ 1 and the Sydney-Australian-Astronomical-Observatory Multi- object Integral-Field Spectrograph (SAMI) Galaxy Survey at z ≈ 0. We match the data quality, analysis methods and sample selection between the two surveys to conduct a direct comparison of the absolute K-band magnitude (MK) and stellar mass (M*) TFRs at z ≈ 1 and z ≈ 0, free of any difference in biases between them. We measure no evolution of the MK TFR zero-point for star- forming disk-like galaxies since z ≈ 1, but an increase by 0.2 ± 0.2 dex of the M* TFR zero-point for the same galaxies over the same period. This implies the total mass-to-stellar mass ratio of those galaxies has decreased by a factor of ≈ 0.4 since z ≈ 1 at fixed rotation velocity, whilst their K-band stellar mass-to- light ratio has increased by a factor of ≈ 1.6. Moderate rates of star formation in galaxies and continued gas accretion since z ≈ 1 can explain these changes. Second, we take a step toward an independent measure of the TFR evolution over the same period using carbon monoxide (CO) emission from galaxies as an alternative kinematic tracer. We present the M* and Wide-Field Infrared Survey Explorer absolute Band 1 magnitude (MW1) TFRs for galaxies from the CO Legacy Database for the Galex Arecibo SDSS Survey (COLD GASS) as z ≈ 0 benchmarks that are pre-requisites to extend the CO TFR to z &gsim; 1. We find no significant offsets between the COLD GASS TFR zero-points and those of similar z ≈ 0 studies. The slope of the M* COLD GASS TFR agrees with those of similar z ≈ 0 studies, but the MW1 TFR slope is slightly shallower than previous studies at a similar redshift. We attribute this to the fact that the COLD GASS sample comprises galaxies of various (late-type) morphologies. Nevertheless, our work provides a robust reference point with which to compare future CO TFR studies.

Keywords: galaxy evolution
galaxies
galaxy kinematics
Advisor: Bureau, M
Laser diagnostics for spatially resolved thermometry in combustion and flows

The development of Laser-Induced Thermal Grating Spectroscopy (LITGS) for diagnostics of combusting and non-combusting flows is described. The first use of LITGS to provide in situ calibration of 2-Dimensional temperature distributions generated using Two-Colour Planar Laser-Induced Fluorescence (TC-PLIF) is reported. Time-resolved measurements of temperature distributions in a firing GDI optical engine obtained by TC-PLIF were made during the compression stroke and calibrated to the absolute temperature scale by simultaneous LITGS measurements. The accuracy and precision of the temperatures derived from LITGS data are evaluated using alternative methods of data analysis – Fast Fourier Transform and Fitting to theoretical models of the experimental data. The relative merits of the two methods are examined for analysis of weak LITGS signals obtained under engine conditions of low pressure and high temperature. The combined TC-PLIF and LITGS system was demonstrated by performing repeated single-shot measurements for 1 in every 10 four-stroke cycles showing excellent correlation of the temperatures derived from both techniques. Direct measurement of the effect of 'charge cooling', of order 5 K, for operation with direct injection is reported. Inhomogeneous temperature distributions were observed during the compression stroke for fired operation with Port Fuel Injection (PFI) and also with Gasoline Direct Injection (GDI). The effects of varying the relative concentrations of toluene and iso-octane in the two-component fuel were investigated.
Extension of the LITGS technique to multi-point measurements along a 1-D line is described. By recording signals from 4 points on separate detectors using a fibre-coupled photodiode array the limitations of Streak Cameras used previously for 1-D LITGS measurements were overcome. Demonstration of principle experiments are reported in which simultaneous 4-point measurements were made with 1 mm spatial resolution and a precision of 0.7 % in temperature gradients in gas flows and in boundary layers at surfaces.

Keywords: Planar Laser Induced Fluorescence
PLIF
LIGS
LITGS
Laser Induced Grating Scattering
Advisor: Ewart, P
Developmental regulators of Kranz anatomy

The C4 biochemical pathway is the most efficient form of photosynthesis in warm environments and introducing this system into globally significant, but less efficient, C3 photosynthetic crops could bring major yield increases. The most photosynthetically efficient C4 grass species have a specialised leaf anatomy characterised by high vein density with two distinct cell types radially arranged around the vascular bundles (Kranz anatomy). Although this anatomy was first described in 1882, the genetic regulators controlling Kranz development are still not known. In recent years, transcriptomic analysis has allowed researchers to identify candidate Kranz regulator genes, and a model for Kranz development has been proposed, however, this model has not been experimentally validated.
This study used in situ hybridisation to visualise expression patterns for a set of candidate Kranz regulator genes in maize and the orthologous genes in rice. Further, morphological analysis of rice lines with constitutive expression of the candidate Kranz regulator genes AINTEGUMENTA 1 and DAG-LIKE 1 and 2 were used to characterise protein function during C3 monocot leaf development. The function of maize AINTEGUMENTA in the C3 eudicot arabidopsis was also investigated.
The results of the in situ hybridisation experiments led to the refinement of the Kranz model and identified potential roles for the candidate regulators during leaf development. The constitutive expression experiments highlighted the regulatory differences between eudicot and monocot leaf development and implicated the regulation of auxin-cytokinin homeostatis as a key factor in Kranz development. Ultimately, this work can be used to guide research into Kranz development and has direct implications for engineering C4 photosynthesis into rice.

Keywords: Vein development
C4 photosynthesis
Kranz anatomy
Leaf development
Advisor: Langdale, J
Neutron scattering and thermodynamic studies of the magnetic material Yb2Ti2O7 at mK temperatures

The frustrated pyrochlore magnet Yb2Ti2O7 has been proposed as a candidate "quantum spin ice" material. This thesis reports extensive inelastic neutron scattering measurements of the spin dynamics and complementary specific heat measurements to map the phase diagram in magnetic fields applied along the cubic [001] direction, not explored experimentally in detail before. The high quality of the single crystals is evidenced by a sharp specific heat anomaly near 215 mK in zero field. In field heat capacity measurements show that the heat capacity peak is completely suppressed by very small magnetic fields (μ0Hint &Tilde; 0.018 T), and the opening of an excitation gap upon increasing field in the form of a broad hump in the data. Inelastic neutron scattering measurements at the highest magnetic fields probed (9 T), in addition to dominant one-magnon excitations, also show a broad scattering continuum at higher energies, not detected in previous neutron scattering studies, which is attributed to two-magnon excitations. The evolution of the spectrum upon lowering field is characterised in detail, showing how high-energy magnons decay when they overlap with the high-energy continuum (B &LT; 3 T) and the low-energy magnons have their dispersion bandwidth suppressed upon lowering field, and disappear altogether at zero field, where the scattering spectrum consists of a gapless continuum extending over a broad energy range. Through fits of the dispersion relations at high field a re-evaluation of the spin Hamiltonian is proposed to consistently explain quantitatively all existing spin dynamics data for different field directions. A theoretical mean-field calculation indicates that the spin Hamiltonian is very close to a phase boundary line between distinct magnetic orders, and this may be the reason for the unconventional magnetic behaviour, where magnons cannot propagate coherently at any of the energy scales probed.

Advisor: Coldea, R
Hyperbolic volume estimates via train tracks

In this thesis we describe how to estimate the distance spanned in the pants graph by a train track splitting sequence on a surface, up to multiplicative and additive constants. If some moderate assumptions on a splitting sequence are satisfied, each vertex set of a train track in it will represent a vertex of a graph which is naturally quasi-isometric to the pants graph; moreover the splitting sequence gives an edge-path in this graph so, more precisely, our distance estimate holds between the extreme points of this path. The present distance estimate is inspired by a result of Masur, Mosher and Schleimer for distances in the marking graph. However, we can apply their line of proof only after some manipulation of the splitting sequence: a rearrangement, changing the order the elementary moves are performed in, so that the ones producing Dehn twists are brought together; and then an untwisting, which suppresses the majority of these latter moves to give a new sequence, which does not end with the same track as before, but does not include any portion that is almost stationary in the pants graph. The required distance is then, up to constants, the number of splits occurring in the untwisted sequence. A consequence of our main theorem together with a result of Brock is that, given a pseudo-Anosov self-diffeomorphism ψ of a surface S, the maximal splitting sequence introduced by Agol gives us an estimate for the hyperbolic volume of the mapping torus built from S and ψ. There are also some interesting consequences for the hyperbolic volume of a solid torus minus a closed braid, via a machinery employed by Dynnikov and Wiest.

Keywords: Surfaces
Hyperbolic 3-manifolds
Pants graph
Train tracks
Advisor: Lackenby, M
Segmentation of magnetic resonance images for assessing neonatal brain maturation

In this thesis, we aim to investigate the correlation between myelination and the gestational age for preterm infants, with the former being an important developmental process during human brain maturation. Quantification of myelin requires dedicated imaging, but the conventional magnetic resonance images routinely acquired during clinical imaging of neonates carry signatures that are thought to be associated with myelination. This thesis thus focuses on structural segmentation and spatio-temporal modelling of the so-called myelin-like signals on T2-weighted scans for early prognostic evaluation of the preterm brain.
The segmentation part poses the major challenges of this task: insufficient spatial prior information of myelination and the presence of substantial partial volume voxels in clinical data. Specific spatial priors for the developing brain are obtained from either probabilistic atlases or manually annotated training images, but none of them currently include myelin as an individual tissue type. This causes further difficulties in partial volume estimation which depends on the probabilistic atlases of the composing pure tissues.
Our key contribution is the development of an expectation-maximisation framework that incorporates an explicit partial volume class whose locations are configured in relation to the composing pure tissues in a predefined region of interest via second-order Markov random fields. This approach resolves the above challenges without requiring any probabilistic atlas of myelin. We also investigate atlas-based whole brain segmentation that generates the binary mask for the region of interest. We then construct a spatio-temporal growth model for myelin-like signals using logistic regression based on the automatic segmentations of 114 preterm infants aged between 29 and 44 gestational weeks. Lastly, we demonstrate the ability of age estimation using the normal growth model in a leave-one-out procedure.

Keywords: Myelination
Brain segmentation
Neonatal brain MRI
Brain atlas
Markov random fields
Advisor: Kuklisova-Murgasova, M
Schnabel, J
Noble, J