894 resultados para IODE. Duke of Kent Chapter
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This thesis investigates the potential legal utility of neurotechnologies which measure correlates of impulsive behaviors. Chapter 1 explains my philosophical position and how this position compares to others in the field. Chapter 2 explores some of the technical concepts which must be understood for the discussion of neurotechnologies and their applications to be fruitful. These chapters will be important for both explaining the capabilities of a neuroscientific approach to neural abnormalities as well as how they relate to the kind of regulation in which the law is engaged. The purpose of Chapter 3 will be a descriptive account of Canadian law where I will begin to explore how to apply ideas and experiments from neuroscience to specific areas of law. Chapter 3 will look at actual examples of Canadian criminal law and will span topics from the creation of law to the construction of appropriate sentences. Chapter 4 will debate if and how we should apply the neuroscientific perspective to the law given the ethical concerns surrounding the applications described in Chapter 3. The thrust of the chapter is that the development of the law does not occur in a vacuum and any alteration either to the laws themselves, how they are interpreted, or the technologies used to provide evidence, must have an ethical justification, that is, a way in which the proposed change will better meet the needs of society and the ethical objectives of the law. Sometimes these justifications can be drawn directly from constitutional documents, such as the Charter, or from the Criminal Code, while at other times these justifications depend upon arguments about furthering meaningful responsibility and therapeutic outcomes.
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Background: Patients with lung and esophageal cancer often have surgery as a means of treatment. In Newfoundland and Labrador, patients with lung and esophageal issues are cared for on Six East, the General/Thoracic Surgery unit at St. Clare’s Mercy Hospital. These patients frequently require chest tubes, which are managed and assessed by Registered Nurses (RNs) on the unit. For nurses new to thoracic surgery, fulfilling their new role and caring for chest tube systems can be daunting. Purpose: The purpose of this practicum project was to develop a learning resource manual for nurses who are new to thoracic surgery. Via self-directed learning, the manual can increase the knowledge and self-efficacy of nurses who are caring for thoracic surgery clients and assessing chest tube systems. Methods: An informal needs assessment, integrated literature review, and several consultations via in-person interviews were conducted. Results: Based on the findings from these methodologies, Knowles’ Adult Learning Theory, and Benner’s Novice to Expert Model, a learning resource manual was created. The manual was divided into chapters covering various aspects of patient and chest tube system care and assessment. Conclusion: For the purpose of this practicum project, no evaluation was conducted. However, a plan for future evaluation of the learning resource manual has been developed to determine if the manual assisted with increasing the knowledge and self-efficacy of nurses new to thoracic surgery. “Test Your Knowledge” questions were included at the end of each chapter in the manual as well as case study scenarios to allow for participant self-evaluation.
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This dissertation presents a calibration procedure for a pressure velocity probe. The dissertation is divided into four main chapters. The first chapter is divided into six main sections. In the firsts two, the wave equation in fluids and the velocity of sound in gases are calculated, the third section contains a general solution of the wave equation in the case of plane acoustic waves. Section four and five report the definition of the acoustic impedance and admittance, and the practical units the sound level is measured with, i.e. the decibel scale. Finally, the last section of the chapter is about the theory linked to the frequency analysis of a sound wave and includes the analysis of sound in bands and the discrete Fourier analysis, with the definition of some important functions. The second chapter describes different reference field calibration procedures that are used to calibrate the P-V probes, between them the progressive plane wave method, which is that has been used in this work. Finally, the last section of the chapter contains a description of the working principles of the two transducers that have been used, with a focus on the velocity one. The third chapter of the dissertation is devoted to the explanation of the calibration set up and the instruments used for the data acquisition and analysis. Since software routines were extremely important, this chapter includes a dedicated section on them and the proprietary routines most used are thoroughly explained. Finally, there is the description of the work that has been done, which is identified with three different phases, where the data acquired and the results obtained are presented. All the graphs and data reported were obtained through the Matlab® routine. As for the last chapter, it briefly presents all the work that has been done as well as an excursus on a new probe and on the way the procedure implemented in this dissertation could be applied in the case of a general field.
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“Spaces of Order” argues that the African novel should be studied as a revolutionary form characterized by aesthetic innovations that are not comprehensible in terms of the novel’s European archive of forms. It does this by mapping an African spatial order that undermines the spatial problematic at the formal and ideological core of the novel—the split between a private, subjective interior, and an abstract, impersonal outside. The project opens with an examination of spatial fragmentation as figured in the “endless forest” of Amos Tutuola’s The Palmwine Drinkard (1952). The second chapter studies Chinua Achebe’s Things Fall Apart (1958) as a fictional world built around a peculiar category of space, the “evil forest,” which constitutes an African principle of order and modality of power. Chapter three returns to Tutuola via Ben Okri’s The Famished Road (1991) and shows how the dispersal of fragmentary spaces of exclusion and terror within the colonial African city helps us conceive of political imaginaries outside the nation and other forms of liberal political communities. The fourth chapter shows Nnedi Okorafor—in her 2014 science-fiction novel Lagoon—rewriting Things Fall Apart as an alien-encounter narrative in which Africa is center-stage of a planetary, multi-species drama. Spaces of Order is a study of the African novel as a new logic of world making altogether.
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Urban problems have several features that make them inherently dynamic. Large transaction costs all but guarantee that homeowners will do their best to consider how a neighborhood might change before buying a house. Similarly, stores face large sunk costs when opening, and want to be sure that their investment will pay off in the long run. In line with those concerns, different areas of Economics have made recent advances in modeling those questions within a dynamic framework. This dissertation contributes to those efforts.
Chapter 2 discusses how to model an agent’s location decision when the agent must learn about an exogenous amenity that may be changing over time. The model is applied to estimating the marginal willingness to pay to avoid crime, in which agents are learning about the crime rate in a neighborhood, and the crime rate can change in predictable (Markovian) ways.
Chapters 3 and 4 concentrate on location decision problems when there are externalities between decision makers. Chapter 3 focuses on the decision of business owners to open a store, when its demand is a function of other nearby stores, either through competition, or through spillovers on foot traffic. It uses a dynamic model in continuous time to model agents’ decisions. A particular challenge is isolating the contribution of spillovers from the contribution of other unobserved neighborhood attributes that could also lead to agglomeration. A key contribution of this chapter is showing how we can use information on storefront ownership to help separately identify spillovers.
Finally, chapter 4 focuses on a class of models in which families prefer to live
close to similar neighbors. This chapter provides the first simulation of such a model in which agents are forward looking, and shows that this leads to more segregation than it would have been observed with myopic agents, which is the standard in this literature. The chapter also discusses several extensions of the model that can be used to investigate relevant questions such as the arrival of a large contingent high skilled tech workers in San Francisco, the immigration of hispanic families to several southern American cities, large changes in local amenities, such as the construction of magnet schools or metro stations, and the flight of wealthy residents from cities in the Rust belt, such as Detroit.
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This thesis describes a systematic investigation of the mechanistic and synthetic aspects of intramolecular reactions of a series of α-diazo-β-oxo sulfone derivatives using copper and, to a lesser extent, rhodium catalysts. The key reaction pathways explored were C–H insertion and cyclopropanation, with hydride transfer competing in certain instances. Significantly, up to 98% ee has been achieved in the C–H insertion processes using copper-NaBARF-bisoxazoline catalysts, with the presence of the additive NaBARF critical to the efficiency of the transformations. This novel synthetic methodology provides access to a diverse range of enantioenriched heterocyclic compounds including thiopyrans, sulfolanes, β- and γ-lactams, in addition to carbocycles such as fused cyclopropanes. The synthesis of the α-diazosulfones required for subsequent investigations is initially described. Of the twenty seven diazo sulfones described, nineteen are novel and are fully characterised in this work. The discussion is subsequently focused on a study of the copper and rhodium catalysed reactions of the α-diazosulfones with Chapter Four concentrated on highly enantioselective C–H insertion to form thiopyrans and sufolanes, Chapter Five focused on C–H insertion to form fused sulfolanes, Chapter Six focused on C–H insertion in sulfonyl α-diazoamides where both lactam formation and / or thiopyran / sulfolane formation can result from competing C–H insertion pathways, while Chapter Seven focuses on cyclopropanation to yield fused cyclopropane derviatives. One of the key outcomes of this work is an insight into the steric and / or electronic factors on both the substrate and the catalyst which control regio-, diastereo- and enantioselectivity patterns in these synthetically powerful transformations. Full experimental details for the synthesis and spectral characterisation of the compounds are included at the end of each Chapter, with details of chiral stationary phase HPLC analysis and assignment of absolute stereochemistry included in the appendix.
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The primary focus of this thesis was the development of a novel chiral tether that could be used to control axial chirality around a newly formed aryl-aryl bond, and the extension of this methodology to the model synthesis of gomisin M1. In chapter 1, a review detailing the use of chiral tethers in the synthesis of atropisomers is discussed. The use of a variety of chiral molecules including 1,2-diols, 1,3-diols and other diol-based tethers, as well as amine-based and miscellaneous tethers are detailed. In chapter 2, the rationale behind the design of our novel molecular tethers, along with the subsequent synthesis of three chiral 1,3-diol-based tethers, is outlined. The method by which the enantiopurity of these diols was determined is also reviewed. This chapter also includes the attempted Mitsunobu and intramolecular couplings in the model synthesis of BINOL. Chapter 3 discusses the synthesis of suitable aryl halide substrates, and their employment in the attempted tether-controlled asymmetric model synthesis of gomisin M1. A comprehensive investigation into the attempted intramolecular biaryl coupling of these tethered substrates is also included. The non-stereoselective model synthesis of gomisin M1 is outlined in chapter 4. The installation of the desired biaryl linkage and the subsequent attempted intramolecular McMurry couplings are discussed. The impact of different protecting groups in the molecule on the intramolecular McMurry reaction is also outlined. Chapter 5 details the full experimental procedures, including spectroscopic and analytical data for the compounds prepared during this research.
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Rural areas are facing demographic transformation. Some localities have experienced significant levels of (internal and international) immigration in recent decades. In other rural places, a shifting minority: majority ratio (arising mainly from increased minority fertility and decreases in the majority population) is altering the rural landscape. It is this context of increasingly diverse rural societies that frames this chapter. It begins by examining inequalities arising from ethnicity in a rural context. The review proceeds by identifying how different factors, including recent patterns of international migration and historical legacies of ethnic diversity, intertwine to produce multi-cultural rural areas. First of all an overview of the significance of the ‘ethnic’ label is presented, recognizing its limitations and also its usefulness. Having established this context the chapter proceeds by highlighting the way in which rural ethnic inequalities are measured and also the particular challenges of measuring rural poverty. The processes that produce inequalities among ethnic groups are examined, with particular attention on migration and space and place, but mindful of historical legacies along with economic transformations and associated recent migration patterns. Finally, the conclusion of the chapter highlights gaps and identifies areas for future research agendas.
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Nitrones or azomethine-N-oxides are important precursors for the synthesis of several heterocyclic systems. They belong to the allyl anion type 1,3-dipoles and possess unique structural features which make them extraordinarily useful synthons. They behave as 1,3-dipoles in 1,3-dipolar cycloaddition reactions and as electrophiles in reactions with organometallic reagents. These are the two basic reactions given by nitrones. Nitrones also act as ‘spin traps’ in which they react with short-lived radicals to furnish stable nitroxide radicals which can be detected and identified by electron paramagnetic resonance (EPR) spectroscopy. Recently SmI2 catalysed reductive cross-coupling reactions of nitrones have gained significant interest in which the reactions are initiated by single electron transfer (SET) to nitrones. Apart from these reactions, nitrones are also known to participate in reactions which are initiated by the nucleophilic attack of nitrone-oxygen. In our group, we have also explored the nucleophilic character of nitrones through various reactions. The results obtained enabled us to develop a novel two-step one-pot strategy for quinolines and indoles - the heterocycles renowned for their pharmacological applications, from nitrones and electron deficient acetylenes. Using dibenzoylacetylene and phenylbenzoylacetylene as dipolarophiles, we could introduce a desired functional group at a predetermined position of the quinolines or indoles to be synthesised. In this context, the thesis entitled “NUCLEOPHILIC ADDITION OF NITRONES TO ELECTRON DEFICIENT ACETYLENES AND RELATED STUDIES” portrays our attempt to expand the scope of our x novel synthetic protocol using ester functionalised acetylenes: dimethyl acetylenedicarboxylate (DMAD) and methyl propiolate. The thesis is organised in to five chapters. The first chapter briefly describes the different classes of reactions that nitrone functionality can tolerate. The research problem is defined at the end of this chapter. The second chapter describes the synthesis of different nitrones used for the present study. The optimisation and expansion of scope of the novel strategy towards quinoline synthesis is discussed in the third chapter. The fourth chapter portrays the synthesis of indole-3-carboxylates using the novel strategy. In the fifth chapter, the reaction of N-(2,6-dimethylphenyl) and N-(2,4,6-trimethylphenyl)nitrones are discussed. Here we also discuss the mechanistic reinvestigation of Baldwin’s proposal in the isoxazoline-oxazoline rearrangement. The major outcome of the work is given at the end of the thesis. The structural formulae, schemes, tables and figures are numbered chapter-wise since each chapter of the thesis is organized as an independent unit. All new compounds (except two compounds reported in fourth chapter) are fully characterised on the basis of spectral and analytical data and single crystal X-ray analysis on representative examples. Relevant references are included at the end of individual chapters.
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Stealth Visor for the Duke of Wellington Project HATWALK The 2012 Cultural Olympiad would not have been representative of London's creative industries without fashion design. Sponsored by the Mayor of London brought milliners to organise an alternative to the catwalk format , the designers brought together a Hatwalk, uniting landmark heritage statues, classical and modern, to be crowned with a new bespoke design piece each. Together forming a pedestrian navigation through the Jubilee city, the hats also invited twenty one milliners to consider the specificity of working for the great outdoors. Rigorously tested in wind tunnel laboratory to withstand hurricane wind speeds and squally shows the designs aim to bring the 'exclusive' culture of fashion accessories to the inclusive culture of international festival. Working with new technologies of engineering, such as laser measuring tools, and crane for assemblage and fitting, McLean brings new meaning to the familiar figures of national public authority. Since the storming of the Bastille in revolutionary France it has been traditional for the new order to symbolize change through attacking public statuary. In a similar vein, Hatwalk, invites spectators to reconsider the relationship between distant and lofty personages of power and the sartorial insignia through which their power is signified. Crowned with a revolutionary red ' large plexi punk neon number' the Duke of Wellington, at Wellington arch is the first in the Hatwalk exhibition. The originality of this research consists in the effects of surprise and Brechtian 'de familiarisation' resulting from the unexpected. The effects of this structural carnivalesque inversion of authorities can involve a range of reactions from the disdain of the offended to the laughter and pleasure of the surprised. This strategy of bringing the ludic element of play to the formalised authority of legitimised power is also signified through the conscious use of materials and colour in a monochrome and uniform culture of statuary. Here the difference in materials and visible surface of the design signifies the differences that need to be included within a socio political order before it may takes its place in history as being representative of the people it is entrusted to lead. This research output continues the work that led to the Hat Anthology exhibition (output 1), the Fifty Hats that Changed the World (output 2), the Jamaican Olympic team headwear design ( output 4), and is continued in the design, merchandise, accessories and avant garde artefacts of the House of Flora ( see website). The iterative process of the research brings innovation within continuity to McLean's work. It is difficult to theorise the 'rigour' that is undeniably present in a creative design praxis except in that McLean;s research outputs are always surprising and unexpected.
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Thesis (Ph.D.)--University of Washington, 2016-06
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Thesis (Ph.D.)--University of Washington, 2016-08
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This thesis outlines a more environmentally benign approach to diazo transfer, and the investigation of the reactivity of -diazocarbonyl compounds when subjected to transition metal and lanthanide catalysis. Extensive studies were carried out to find the optimum conditions for a greener diazo transfer methodology, and this was also applied to a continuous process for the synthesis of -diazo--ketoesters. The first chapter includes a literature review of the synthesis and subsequent reactivity of -diazocarbonyl compounds. An overview of the applications of flow chemistry for the synthesis of hazardous intermediates is also included. The applications of lanthanide catalysts in organic synthesis is also discussed. The second chapter outlines the extensive studies undertaken to determine the optimum conditions for a greener diazo transfer methodology, including base and solvent studies. Use of water as a viable solvent for diazo transfer was successfully investigated. Diazo transfer to a range of -diazo--ketoesters was achieved using 5 mol% triethylamine or DMAP in water with high conversions. Polystyrene-supported benzenesulfonyl azide as an alternative diazo transfer reagent was also explored, as well as investigations into cheaper generation of this safer reagent. This polymer-supported benzenesulfonyl azide was used with 25 mol% of base in water to achieve successful diazo transfer to a range of -diazo--ketoesters. The third chapter describes the application of the new methodology developed in Chapter 2 to a continuous processing approach. Various excellent conditions were identified for both batch and flow reactions. A series of -diazo--ketoesters were synthesised with excellent conversions using 25 mol% triethylamine in 90:10 acetone water using flow chemistry. Successful diazo transfer was also achieved using a polymer-supported benzenesulfonyl azide in water under flow conditions. The fourth chapter discusses the reactivity of -diazo--ketoesters under transition metal and lanthanide catalysis. This chapter describes the synthesis of a range of -ketoesters via transesterification, which were used to synthesise a range of novel -diazo--ketoesters that were used in subsequent decomposition reactions. A novel route to dioxinones via rhodium(II) catalysis is reported. Attempted OH and SH insertion reactions in the presence of various lanthanide(II) catalysts are outlined, leading to some unexpected and interesting rearrangement products. The experimental details, including spectroscopic and analytical data for all compounds prepared, are reported at the end of each chapter.
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Introduction For a long time, language learning research focusing on young learners was a neglected field of research. Most empirical studies within the broad area of second/foreign language acquisition were instead carried out among adults in tertiary education and it was not until in the 1990s that the scope of research broadened to include also young learners, then loosely defined as children in primary and/or secondary education (see, for example, Hasselgreen & Drew, 2012; McKay, 2006; Nikolov, 2009a). In fact, some agreement upon how to define ‘young learners’ was not properly discussed until in 2013, when Gail Ellis (2013) provided some useful clarifications as regards how to label learners within the broad age-span that encompasses both primary and secondary school. In short, based on a literature overview, she concludes that the term young learners is most often used for children between the ages of five and eleven/twelve, which in most countries would be equivalent to learners in primary school. Thus, since young learners did not catch much scholarly attention until fairly recently, research volumes on the topic have been scarce. However, with a rapidly growing interest in examining how small children learn foreign languages, there has been a sudden increase in terms of the number of books available targeting young language learners. A first, major contribution was Nikolov’s (2009b) Early learning of modern foreign languages, in which 16 studies of young language learners from different countries are accounted for. Another important contribution is the edited book that will be reviewed here, which specifically targets studies about various aspects of second/foreign language learning among young (mainly Norwegian) learners. Bearing in mind that Norway and Sweden are very similar countries in terms of schooling, language background, and demographics – only to give three examples of similarities between these two nations – it is particularly relevant for Swedish scholars within the fields of education and second language acquisition to become familiar with research findings from the neighboring country. In this review, the editors and the outline of the book are first described, then brief summaries of each chapter are provided, before the text closes with an evaluation of the volume.
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Musicians, rhetoricians and crossbowmen, all of them employed by the city of Brussels, acted, sang and played instruments during the "Ommegang" procession in the 15th century in the main square, some of them during other processions, too. In Bruges, instrumentalists and singers took part in the representation of biblical scenes on street corners, which were part of the entry of Philip III the Good, Duke of Burgundy, into the city around the year 1440. The members of the clergy who knew music sang plainchant in all of these three roles, and independent musicians probably participated, too, even though the documents don't name them or describe their function. Except for the disabled, who marched in a procession on their own, the "common people" were only spectators of these events, which were planned in advance. The evidence that remains indicates that the voices of the "common people" remained hidden in these events, which were intended to promote civic unity.