VictorJuiz/thesis huggingface dataset:
Palladium-catalysed enolate arylation in the synthesis of isoquinolines
Keywords: palladium catalysis
protoberberines
natural products
total synthesis
isoquinolines
alpha-arylation
alkaloids
synthesis

Chapter 1. Introduction
Scientific background on the development of homogeneous palladium-catalysed cross coupling reactions, focusing on the α-arylation reaction of enolates and its application to the synthesis of heteroaromatic compounds. The classical syntheses of isoquinolines are discussed, followed by an account of modern methods for their synthesis, including the recent α-arylation-based methodology developed by the Donohoe group.
Chapter 2. Results and Discussion
2.1 Studies towards the development of a palladium-catalysed, C–H activation-based α arylation reaction of ketones, resulting in a C–H bromination/α-arylation sequence for the synthesis of isoquinolines and isoquinoline N-oxides.
2.2 The one-pot, four component coupling of a ketone, an acetal protected ortho-bromobenzaldehyde or ketone, an electrophile, and an ammonia source is described. This protocol, which ultimately provides C4 functionalised isoquinolines, is later extended to a novel α,α heterodiarylation protocol to furnish C4-aryl isoquinolines.
2.3 It is shown that the synthesis of 3 aminoisoquinolines can be achieved via the α arylation of nitriles. tert-Butyl cyanoacetate can act as a substitute for primary alkyl nitriles, with sequential α-arylation, in situ functionalisation, decarboxylation and cyclisation reactions provide C4 functionalised 3 aminoisoquinolines.
2.4 The synthetic utility of the α arylation based methodology for isoquinoline synthesis is exemplified by the total synthesis of the alkaloid berberine in 68% yield over five steps. This is followed by syntheses of pseudocoptisine, palmatine, dehydrocorydaline, and an unnatural fluorine containing analogue, in yields of 46%, 73%, 60% and 37%, respectively.
2.5 Finally, preliminary investigations demonstrate the utility of palladium-catalysed enolate arylation in the synthesis of β-carbolines.
Measurement and analysis of bubble pump and Einstein-Szilard single pressure absorption refrigeration system
Keywords: bubble pump
absorption refrigeration
refrigeration
single pressure absorption refrigeration
Einstein-Szilard refrigerator

The increasing demand for the domestic refrigeration system urges the development of greener form of refrigeration. The eighty-year-old single pressure absorption refrigeration system invented by Albert Einstein and Leo Szilard is attractive as it has no mechanical moving parts and can be driven by heat alone. However, the literature on either the refrigeration system or its components is scarce. The bubble pump is the crucial component of the refrigeration system, but it is poorly understood as its mass flow rate cannot be readily predicted. Two new time correlations in the mass flow rate prediction are presented to increase the accuracy when heat losses occur in the bubble pump. These time correlations are verified with the experimental results. When either the heat input or submergence ratio increases, the accuracy of the prediction increases. The percentage of error for the high heat input or submergence ratio is within ±10%. Working conditions and system dimension have a direct influence to the bubble pump performance. For instance, the bubble pump experimental results show that the mass flow rate of the bubble pump increases when either the submergence ratio or the concentration of ammonia increases. However, the performance of the bubble pump drops when the tube diameter or the system pressure increases.
The Einstein refrigeration system has only been rebuilt once since it invention. In order to redesign and rebuilt a practical Einstein refrigeration system, some challenges are revealed. With the combination of the good features of the designs of Einstein and Delano, a new prototype has been rebuilt and tested. The practical results obtained from the five experimental setups are the first set of experimental result that has ever been presented. The highest cooling capacity and coefficient of performance (COP) obtained are 5 W and 0.04 respectively.
Using non-linear vibration techniques to detect damage in concrete bridges
Keywords: dynamics
concrete

There has been much work published in recent years on the use of vibration characteristics to detect damage in bridges. Almost all of this work has been based on the assumption that the vibration is linear, i.e. the natural frequencies are not dependent on the amplitude of oscillation. The aim of the work presented here was to investigate the possibility of using changes in the non-linear vibration characteristics to detect damage in reinforced concrete bridges. These changes in the non-linear vibration characteristics were studied by conducting impact excitation vibration tests o reinforced concrete beams. The non-linearities were detected by examining the changes in fundamental frequency over time (and hence over amplitude of vibration). Several time-frequency distribution estimation tools are discussed including the discrete Fourier Transform moving window, the auto-regressive model moving window, harmonic wavelets and examples of the Cohen class of bilinear time-frequency distributions. A detailed investigation into these various distribution predictors was conducted to assess which is most suitable for analysing the vibration signals to detect changes in frequency with time. To understand the non-linearities in the vibration characteristics, a time-stepping model was described. The model is capable of including damage in the form of a moment-rotation relationship over the cracked region. It was validated for linear vibrations against theoretical values and the representation of a non-linear mechanism using the model was compared with experimental data. Static load tests were also conducted on the beams at various damage levels. They involved the use of vibrating wire strain gauges to investigate the moment-rotation behaviour over the cracked region. Several possible non-linear crack mechanisms are discussed and two of them are assessed using the vibration and the static load tests. Future experimental work is proposed to study the possible non-linear mechanisms further. The beam tests demonstrated that there is a change in non-linear vibration behaviour with damage. The change is greatest at low levels of damage and after the beam has been loaded to 30% of the failure load in three-point loading there is a reversal in the trend and a slight reduction in non-linearity with further damage.
The consolidation behaviour of gassy soil
Keywords: gas
clay
consolidation

The consolidation behaviour of gassy soil has been studied in a programme of experimental and theoretical research. This research is of particular importance to the offshore geotechnical industry as the presence of gas in the seabed can have a dramatic effect on the material properties of a marine sediment. Initial numerical modelling based on existing unsaturated soil theory combining the gas and the water phase into a compressible fluid in the pores of compressible soil skeleton failed to simulate the soil behaviour previously observed experimentally at Oxford. Therefore, there was scope for further study in this field. Chapters 2 to 4 describe the experimental preparation, consolidation technique and experimental results of the two series of tests on artificially prepared gassy soil samples. The results of these tests indicated that the gas appeared to be affected by the total stress rather than the pore water pressure, with the saturated soil matrix outside the gas voids being controlled by the consolidation stress. Chapter 5 presents the one-dimensional numerical modelling of the experimental results. Poor simulations were again made using compressible fluid theory. Treating the gas as compressible solid inclusions embedded in a saturated soil matrix, however, resulted in excellent simulations of the observed pore water pressures and settlements. Chapter 6 attempts to explain the results of the experimental and numerical modelling in terms of elastic and plastic soil behaviour. This includes the introduction to the double compressibility model in which the deformation behaviour of the saturated matrix is governed by changes in consolidation stress, whereas that of the gas is governed by changes in total stress. Chapter 7 presents the development of the governing gassy soil consolidation equations under both plane strain and axisymmetric conditions. Chapter 8 describes the approximation of the governing consolidation equations using the Galerkin finite element method in terms of nodal displacements and pore water pressures. The resulting finite element approximation is subsequently formulated for rectangular elements under plane strain and axisymmetric conditions in Chapter 9. The remainder of the thesis describes the structure of the finite element model DCFEM2 and the constitutive relationships that are required for such a model. The code is verified with existing analytical solutions and then is used to simulate the observed gassy soil behaviour under laboratory and field conditions.
Fear and greed: financial crisis in the novel since 1850
Keywords: Financial Crisis
Novel
Literature and Economics
Bellow
Norris
Dickens
Dreiser
DeLillo
F. Scott Fitzgerald
Trollope
H.G. Wells
Amis

The financial crisis of 2008 has been the most significant global economic phenomenon of the new century. Sudden and largely unanticipated, this crisis nonetheless marks the latest in a series of financial panics that forms a welldocumented feature of finance capitalism stretching back to the Dutch Tulip Bubble of 1637 and beyond, including such notorious crises as the South Sea Bubble of 1720, the Railway Shares panics of 1837 and 1847, the Wall Street Crash of 1929, and Black Monday in 1987. These and other crises have fostered a complex and diverse intellectual response - particularly since the South Sea Bubble - that has included interventions not only from economists and economic historians, but poets, dramatists, novelists, and others. This raises the question of whether the novel’s contribution to our wider understanding of financial crises has been fully acknowledged and assessed. In this thesis, the complex and shifting relationship between literary and non-literary responses to financial crisis is explored through an examination of the ideas of political economists, philosophers, journalists, financiers, and others, including Adam Smith, David Ricardo, Lord Overstone, Walter Bagehot, Herbert Spencer, Thorstein Veblen, Joseph Schumpeter, and J.M. Keynes, that situates their theories alongside readings of novels of financial crisis from the 1850s onward...
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Factors affecting fish distribution in coastal habitats of the British Virgin Islands
Keywords: British Virgin Islands
fish
coral
habitat complexity
distribution
biodiversity
Caribbean
marine

Few studies of tropical fish communities compare fish distributions across the full range of near-shore tropical marine habitats. As a result, our understanding of tropical marine fish communities is often biased towards habitats preferred by researchers.
The distribution and habitat preferences of all 136 fish species occurring at 106 stations in three bays off Tortola in the British Virgin Islands were assessed. At a species level, habitat type was often the key factor influencing fish distribution. Of the 44 species occurring at more than 10 stations, 3 were sand specialists, 5 were strongly associated with mangroves, 7 were dependent on seagrass and algal beds and 14 were found only on the forereef. Eleven species were widely distributed both on the forereef and in bays, and 9 of them showed clear evidence of ontogenetic partitioning. The juveniles all preferred bay habitat types and moved onto the forereef as they approached sexual maturity.
At a community level, five distinct fish assemblages were found. The assemblage types were classified according to their distribution: 1) forereef, 2) reef flat, 3) non-mangrove associated seagrass, 4) mangrove associated seagrass and 5) eutrophic areas. Forereef stations were the most species-rich with 24 species per station while eutrophic stations had the most depauperate communities with only 4 species per station.
Variation in fish species richness at each station was largely explained by a simple habitat complexity index. It accounted for 70% of the variation in fish species richness and 21% of the variation in fish abundance. Rugosity and variety of growth forms were the most important predictors of species richness, but the height of the habitat architecture was the most useful predictor of fish abundance. Artificial reefs were constructed to test the effects of each habitat complexity variable experimentally. Increasing rugosity, variety of growth forms and percentage hard substrate increased the observed number of species but increasing the variety of hole-sizes, and height had no effect. The only complexity variable that had a significant effect on fish abundance was percentage hard substrate. In addition to the static substrate structure, long-spined sea urchins Diadema antillarum affected fish distribution because small fish shelter from predators in their spines. The urchins increase species richness and abundance in low complexity seagrass beds, but on artificial reefs, where shelter was not a limiting factor, the effect was less pronounced.
Organic pollution is another factor that negatively affects the fish community by reducing fish species richness and abundance. Poor water quality often alters the natural habitat, confounding observations, but fish species richness was reduced in polluted areas even when artificial reefs were used as habitat controls.
The applications of these findings to the management and conservation of fish in the British Virgin Islands are discussed.
Texture determination from ultrasound for HCP and cubic materials
Keywords: cubic
wave propagation
crystallographic texture
ultrasound
HCP
non-destructive testing

Crystallographic texture in polycrystalline HCP and cubic materials, often developed during thermomechanical deformations, has profound effects on properties at the macroscopic or component level. Given the respective natures of current detection techniques, a non-destructive, three-dimensional bulk texture detection method for these materials has not yet been developed. This thesis aims to achieve this goal through systematic studies on the relationship between ultrasonic wave velocity and texture.
The feasibility of such development is firstly reviewed via the combination of computational and experimental studies on exemplary HCP materials. Numerical results obtained via a representative volume element (RVE) methodology reveal that the wave speed varies progressively and significantly with changing texture, and experimental ultrasound studies combined with EBSD characterisation demonstrate distinguished velocity profiles for samples with different textures. Thus the possibility of the development is demonstrated from these combined results.
A novel convolution theorem is then presented, which couples the single crystal wave speed (the kernel function) with polycrystal orientation distribution function to give the resultant polycrystal wave speed function. Firstly developed on HCP and then successfully extended to general anisotropic materials, the theorem expresses the three functions as harmonic expansions thus enabling the calculation of any one of them when the other two are known. Hence, the forward problem of determination of polycrystal wave speed is solved for all crystal systems with verifications on varying textures showing near-perfect representation of the sensitivity of wave speed to texture as well as quantitative predictions of polycrystal wave speed. More importantly, the theorem also presents a solution to the long-standing inverse problem for HCP and cubic materials, with proof of principle established where groups of HCP and cubic textures are recovered solely from polycrystal wave velocities through the theorem and the results show good agreements with the original textures. Therefore the theorem opens up the possibility of developing a powerful technique for bulk texture measurement and wave propagation studies in HCP, cubic materials and beyond.
Time-of-flight secondary ion mass spectrometry - fundamental issues for quantitative measurements and multivariate data analysis
Keywords: principal component analysis
topography
instrumentation
cluster ions
SIMS
secondary ion mass spectrometry
ToF-SIMS
organic depth profiling
multivariate analysis
sputtering

Time-of-flight secondary ion mass spectrometry (ToF-SIMS) is a powerful technique for the analysis of organic surfaces and interfaces for many innovative technologies. However, despite recent developments, there are still many issues and challenges hindering the robust, validated use of ToF-SIMS for quantitative measurement. These include: the lack of metrology and fundamental understanding for the use of novel cluster primary ion beams such as C60n+ and Ar2000+; the need for validated and robust measurement protocols for difficult samples, such as those with significant micron scale surface topography; the lack of guidance on novel data analysis methods including multivariate analysis which have the potential to simplify many time-consuming and intensive analyses in industry; and the need to establish best practice to improve the accuracy of measurements. This thesis describes research undertaken to address the above challenges. Sample topography and field effects were evaluated experimentally using model conducting and insulating fibres and compared with computer simulations to provide recommendation to diagnose and reduce the effects. Two popular multivariate methods, principal component analysis (PCA) and multivariate curve resolution (MCR), were explored using mixed organic systems consisting of a simple polymer blend and complex hair fibres treated with a multi-component formulation to evaluate different multivariate and data preprocessing methods for the optimal identification, localisation and quantification of the chemical components. Finally, cluster ion beams C60n+ and Ar500-2500+ were evaluated on an inorganic surface and an organic delta layer reference material respectively to elucidate the fundamental metrology of cluster ion sputtering and pave the way for their use in organic depth profiling. These studies provide the essential metrological foundation to address frontier issues in surface and nanoanalysis and extend the measurement capabilities of ToF-SIMS.
Model-based segmentation methods for analysis of 2d and 3d ultrasound images and sequences
Keywords: optimisation
subdivision surfaces
segmentation

This thesis describes extensions to 2D and 3D model-based segmentation algorithms for the analysis of ultrasound images and sequences.
Starting from a common 2D&plus;t "track-to-last" algorithm, it is shown that the typical method of searching for boundary candidates perpendicular to the model contour is unnecessary if, for each boundary candidate, its corresponding position on the model contour is optimised jointly with the model contour geometry. With this observation, two 2D&plus;t segmentation algorithms, which accurately recover boundary displacements and are capable of segmenting arbitrarily long sequences, are formulated and validated.
Generalising to 3D, subdivision surfaces are shown to be natural choices for continuous model surfaces, and the algorithms necessary for joint optimisation of the correspondences and model surface geometry are described. Three applications of 3D model-based segmentation for ultrasound image analysis are subsequently presented and assessed: skull segmentation for fetal brain image analysis; face segmentation for shape analysis, and single-frame left ventricle (LV) segmentation from echocardiography images for volume measurement. A framework to perform model-based segmentation of multiple 3D sequences - while jointly optimising an underlying linear basis shape model - is subsequently presented for the challenging application of right ventricle (RV) segmentation from 3D&plus;t echocardiography sequences. Finally, an algorithm to automatically select boundary candidates independent of a model surface estimate is described and presented for the task of LV segmentation.
Although motivated by challenges in ultrasound image analysis, the conceptual contributions of this thesis are general and applicable to model-based segmentation problems in many domains. Moreover, the components are modular, enabling straightforward construction of application-specific formulations for new clinical problems as they arise in the future.
The passions of power politics: how emotions influence coercive diplomacy
Keywords: coercive diplomacy
emotions

In coercive diplomacy, actors employ the threat of force to get targets to change their behavior. The goal is to achieve the opponent's compliance without waging war. In practice, however, the strategy often falls short-even when coercers enjoy substantial military superiority. This finding inspires the central question of this thesis: What prompts leaders to reject coercive threats from stronger adversaries, and under what conditions do they yield? I argue that target leaders' affective reactions can help to explain why coercive diplomacy succeeds in some cases but not in others. Combining insights from psychology and social constructivism, this thesis presents a theory of emotional choice to analyze how affect enters into target leaders' decision-making. Specifically, it makes the case that preferences are not only socially but also emotionally constructed. The core of the theoretical framework outlines how five key emotions-fear, anger, hope, pride, and humiliation-help to constitute target leaders' preferences. This represents the first attempt to explore how a spectrum of emotions influences leaders' foreign policy decision-making. To test the analytic utility of emotional choice theory, the thesis examines nine major decisions by Nikita Khrushchev during the Cuban missile crisis in 1962 and ten main decisions by Saddam Hussein in the course of the Gulf conflict in 1990-91. The analysis yields mixed results: In the case of about a third of all decisions, the five key emotions exerted only minor effects or no impact at all. Another third of the decisions were influenced by one or more of these emotions to a degree similar to the impact of other factors. In the case of the final third of decisions, however, some of these emotions became the primary forces shaping the construction of preferences. Overall, emotional choice theory has thus advanced our understanding of the target leaders' decision-making in the missile crisis and the Gulf conflict, offering a more comprehensive explanation of why coercive diplomacy succeeded in one case but not in the other.