Phenols are some of the most readily available and easily elaborated aromatic compounds, but the strength of the CAr-O bond hampers their conversion to highly sought CAr-N, CAr-S and CAr-C analogues. Attempts have therefore been made to establish new protocols for achieving such transformations by derivatising phenols with suitable CAr-O bond activating groups. In particular, investigations have focussed on the development of reactions with the potential to enable phenols to be conveniently converted to anilines. Towards this goal, the synthesis of O-aryl trihaloacetimidates was investigated with a view to probing their ability to rearrange to N-aryl trihaloacetamides via transition metal catalysis (Scheme 1). It was found that O-aryl trichloroacetimidates could be obtained from the base-catalysed reactions of phenols with trichloroacetonitrile, but only when electron-rich phenols were applied. In contrast, N-(4-methylphenyl)-O-aryl trifluoroacetimidates were generated in good yields from electron-rich and electron-poor phenols by their condensation with N-(4-methylphenyl)trifluoroacetimidoyl chloride. With these substrates in hand, a number of transition metal catalysts were screened for activity in the proposed rearrangement reactions, but the desired transformations were not achieved. As part of this screen, a novel mono-NHC palladium(II) precatalyst with the potential to be thermally activated was developed. Scheme 1 The proposed strategy for converting phenols to anilines. The hydroxide-catalysed rearrangement of O-aryl-N,N’-diisopropyl isoureas to N-aryl- N,N’-diisopropyl ureas was reported in 1983, but there have been no reported applications of this reaction to date. The reaction was therefore revisited with the intention of realising its unexplored synthetic potential. The reported hydroxide-catalysed rearrangement of O-phenyl-N,N’-diisopropyl isourea to N-phenyl-N,N’- diisopropyl urea was, however, discredited on the basis of 1H NMR and UV spectrometric analyses (Scheme 2). This isourea was instead, found to be converted to phenoxide and diisopropyl urea under the reported conditions. A detailed kinetic study revealed that the isourea was not directly hydrolysed, but underwent hydroxide-mediated elimination to produce phenoxide and diisopropyl carbodiimide. The hydrolysis of diisopropyl carbodiimide to diisopropyl urea then occurred in a slower, second step which was catalysed by hydroxide. Attempts to identify and synthesise N-heterocylcic isourea structures which were more disposed towards rearrangement were unsuccessful. Scheme 2 The reported and observed reactivity of O-phenyl-N,N’-diisopropyl isourea in aqueous base. Early attempts to use O-aryl-N,N’-dimethyl thiocarbamates as phenol-derived pseudohalides in palladium(0)-catalysed, CAr-C bond-forming cross-coupling reactions showed little promise due to the onset of their base-induced decomposition. However, the formation of a diaryl thioether side product was observed during these studies, leading to a preliminary investigation into the use of aryl thiocarbamates as hydrogen sulfide surrogates and thiophenol precursors in palladium(0)-catalysed C-S coupling reactions (Scheme 3). The promise of this approach was demonstrated by the synthesis of both symmetrical and unsymmetrical diaryl thioethers in the palladium(0)-catalysed couplings of O- and S-(4-trifluoromethyl)-N,N-dimethyl thiocarbamate with 1-bromo-4- fluorobenzene. Scheme 3 The preparation of diaryl thioethers from O-aryl thiocarbamates and aryl bromides via palladium(0) catalysis.

John Wilbur Chapman was one of the most prominent clergymen, church leaders and revivalists of the later nineteenth and early twentieth centuries. More than sixty million people attended his evangelistic campaigns worldwide. A study of his contributions shows that he dominated the evangelical landscape of America from 1906 to 1918. His campaigns in Canada and his subsequent world tours helped his fame spread internationally. The objective of the dissertation was to find out whether Chapman’s contributions to Evangelicalism were as strong as indicated by his reputation during his day and if he should be remembered only as a secondary figure in revivalism. Historians have treated Chapman mostly as one of Dwight L. Moody’s assistants and as a lesser colleague to some of Moody’s lieutenants. If Chapman was significant, why did his name disappear from historical research and why was he relegated to a lesser position than his accomplishments deserved? What were Chapman’s contributions and how far did he advance revivalism? The research conducted in this dissertation represents a decade of analysing archival materials, primary sources and secondary sources, including journals and newspaper articles. What was discovered was that J. Wilbur Chapman was more significant to the history of Evangelicalism than previously noted. An investigation of his work has reinforced an understanding of the concepts and techniques of later nineteenth-century evangelism and it has also revealed his contributions to the trajectory of revivalism. The study of Chapman's work also illuminates aspects of holiness, dispensationalism and social welfare during the Victorian and post-Victorian era.

Dissertação (mestrado) - Universidade Federal de Santa Catarina, Centro Tecnológico. Programa de Pós-Graduação em Engenharia Mecânica. / Made available in DSpace on 2012-10-20T00:39:29Z (GMT). No. of bitstreams: 1 241551.pdf: 755978 bytes, checksum: 7a86bbf486f9fdec5cc61339710e48c6 (MD5) / O método de Boltzmann para redes tem obtido grande êxito na simulação de problemas hidrodinâmicos à temperatura constante. Entretanto, apesar dos diversos modelos propostos na literatura, este método foi incapaz de descrever escoamentos não isotérmicos de forma satisfatória, devido, principalmente, à presença de instabilidade numérica e de discrepâncias nas equações macroscópicas que descrevem a dinâmica do fluido. Neste contexto, o presente trabalho estuda uma série de modelos derivados como formas discretas da equação de Boltzmann. O estudo compreende uma análise multiescala, de modo a averiguar a concordância entre o comportamento macroscópico dos modelos e as equações de Navier-Stokes, e uma análise da estabilidade linear, com o objetivo de obter os limites de aplicabilidade dos modelos. Por fim, são apresentadas medições numéricas dos coeficientes de transporte, com a finalidade de corroborar os resultados da análise multiescala.

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In the opening years of the 20th century, a furor of new and experimental techniques swept the architectural field. The materials and methods of building altered so rapidly that standards of architectural representation and the acts of construction they choreographed appeared for a time to exist without history or precedent. In chaotic times chaos seems all consuming; yet standards are soon established and modes of practice formalized. So it was with the advent of architectural modernity. The beginning of the century was a time of great experimentation and innovation, not only in architectural materials but in the tools and representations of architects, and the methods of building they described. In this exploration of the relationship between material innovation and architectural representation, we examine the case of the Pennsylvania artisan-scholar Henry Chapman Mercer (1856-1930), and his development of a unique method for construction in reinforced concrete and ceramic tiles of his own design. In the years between 1907 and 1916, Mercer built three buildings of increasing complexity and scale, using methods of fabrication he developed over the course of these constructions. His approach was experimental, innovative, and yet quite different from the prevailing currents in engineering and industry at that time. While Mercer has been studied as a decorator of tiles, as an archaeologist, and as a curator of one the first and finest collections of early American material culture, very little work has been completed on Mercer as architect-builder. In Mercer's building projects we see a scientific mind and an artistic maker explore and experiment freely, building a bridge between his seemingly disparate worlds: from the Arts and Crafts-inspired Moravian Pottery he founded, to the archaeologically rigorous collection of pre-industrial tools. Mercer focused with great intensity on implements and evidences of traditional craft activities, and it is his particular sensitivity to the traditions and forms of craft activity that renders his architectural activity unique, and pertinent to the question of innovation in method. At the center of his architectural activities, Mercer's construction notebooks, in which he worked out plans, details, and many of his most unique procedural innovations, illustrate a novel comportment of architect to architectural representation, and offer a story of how the making of architecture is, itself, made. / PHD / In the opening years of the 20th century, a furor of new and experimental techniques swept the architectural field. The materials and methods of building altered so rapidly that standards of architectural representation and the acts of construction they choreographed appeared for a time to exist without history or precedent. In chaotic times chaos seems all consuming; yet standards are soon established and modes of practice formalized. So it was with the advent of architectural modernity. The beginning of the century was a time of great experimentation and innovation, not only in architectural materials but in the tools and representations of architects, and the methods of building they described. In this exploration of the relationship between drawing and building, we examine the case of the Pennsylvania artisan-scholar Henry Chapman Mercer (1856-1930), and his development of a unique method for construction in reinforced concrete and ceramic tile of his own design. Mercer has been studied as a decorator of tiles, as an archaeologist, and as a curator of one the first and finest collections of early American tools. Yet very little work has been completed on Mercer as architect-builder. In Mercer’s building projects we see a scientific mind and an artistic maker explore and experiment freely, building a bridge between his seemingly disparate loves: from the Arts and Crafts-inspired Moravian Pottery he founded, to the archaeologically rigorous collection of pre-industrial tools. Mercer focused with great intensity on implements and evidences of traditional craft activities, and it is his particular sensitivity to the traditions and forms of making that renders his architectural activity unique, and pertinent to the question of innovation in method. At the center of his architectural activities, Mercer’s construction notebooks, in which he drew plans and worked out many of his most unique procedural innovations, illustrate a novel comportment of architect to drawing, and offer a story of how the making of architecture is, itself, made.

Akademisk avhandling--Engelsk litteratur--Lund, 1982. / Bibliogr. p. 260-265.

Cette thèse porte sur le développement de modèles multi-échelles et de méthodes de calcul pour les applications aérothermodynamiques. Le travail de recherche sur les modèles multi-échelles met l’accent sur l’excitation énergétique et la dissociation. L’objectif était double : mieux comprendre la dynamique des processus d'excitation énergétique et dissociation et développer des modèles réduits en diminuant la résolution d’un modèle détaillé de collisions rovibrationnelles. Les résultats obtenus ont montré que les modèles réduits permettent de reproduire avec précision la dynamique d’écoulement prédites par le modèle détaillé de collisions rovibrationnelles. Le travail de recherche sur les méthodes de calcul a porté sur les écoulements raréfiés. L’objectif était de formuler une méthode numérique de type déterministe pour résoudre l’équation de Boltzmann dans le cas de gaz à plusieurs composants y compris l’énergie interne. La méthode numérique est basée sur la structure de convolution pondérée de la transformée de Fourier de l’équation de Boltzmann. La précision de la méthode numérique proposée a été évaluée en comparant les moments extraits de la fonction de distribution de vitesse avec les prédictions de la méthode de simulation directe Monte Carlo (DSMC). Dans toutes les applications étudiées, un excellent accord a été trouvé. / This thesis aimed at developing multi-scale models and computational methods for aerother-modynamics applications. The research on multi-scale models has focused on internal energy excitation and dissociation of molecular gases in atmospheric entry flows. The scope was two-fold: to gain insight into the dynamics of internal energy excitation and dissociation in the hydrodynamic regime and to develop reduced models for Computational Fluid Dynamics applications. The reduced models have been constructed by coarsening the resolution of a detailed rovibrational collisional model developed based on ab-initio data for the N2 (1Σ+g)-N (4Su) system provided by the Computational Quantum Chemistry Group at NASA Ames Research Center. Different mechanism reduction techniques have been proposed. Their appli-cation led to the formulation of conventional macroscopic multi-temperature models and vi-brational collisional models, and innovative energy bin models. The accuracy of the reduced models has been assessed by means of a systematic comparison with the predictions of the detailed rovibrational collisional model. Applications considered are inviscid flows behind normal shock waves, within converging-diverging nozzles and around axisymmetric bodies, and viscous flows along the stagnation-line of blunt bodies. The detailed rovibrational colli-sional model and the reduced models have been coupled to two flow solvers developed from scratch in FORTRAN 90 programming language (SHOCKING_F90 and SOLV-ER_FVMCC_F90). The results obtained have shown that the innovative energy bin models are able to reproduce the flow dynamics predicted by the detailed rovibrational collisional model with a noticeable benefit in terms of computing time. The energy bin models are also more accurate than the conventional multi-temperature and vibrational collisional models. The research on computational methods has focused on rarefied flows. The scope was to formu-late a deterministic numerical method for solving the Boltzmann equation in the case of multi-component gases with internal energy by accounting for both elastic and inelastic collisions. The numerical method, based on the weighted convolution structure of the Fourier trans-formed Boltzmann equation, is an extension of an existing spectral-Lagrangian method, valid for a mono-component gas without internal energy. During the development of the method, particular attention has been devoted to ensure the conservation of mass, momentum and en-ergy while evaluating the collision operators. Conservation is enforced through the solution of constrained optimization problems, formulated in a consistent manner with the collisional in-variants. The extended spectral-Lagrangian method has been implemented in a parallel com-putational tool (best; Boltzmann Equation Spectral Solver) written in C programming lan-guage. Applications considered are the time-evolution of an isochoric gaseous system initially set in a non-equilibrium state and the steady flow across a normal shock wave. The accuracy of the proposed numerical method has been assessed by comparing the moments extracted from the velocity distribution function with Direct Simulation Monte Carlo (DSMC) method predictions. In all the cases, an excellent agreement has been found. The computational results obtained for both space homogeneous and space inhomogeneous problems have also shown that the enforcement of conservation is mandatory for obtaining accurate numerical solutions.

Kärleksrelationer är en betydande del av många människors liv. En viktig del för en välfungerande relation är att visa varandra kärlek, förslagsvis genom olika kärleksspråk. De fem kärleksspråken utformades av Chapman (1992) och innefattar tjänster, fysisk beröring, bekräftande ord, kvalitetstid och gåvor. Kärleksspråk har visat sig vara en bidragande faktor för kvalitativa kärleksrelationer. Personlighetsdraget vänligheten från femfaktormodellen är bland annat kopplat till kärleksfulla och empatiska karaktärsdrag. Denna studie har som syfte att studera sambandet mellan vänlighet och kärleksspråk. Studien undersökte även om det fanns någon skillnad på vilket kärleksspråk man har beroende på om man är singel eller i en relation. Detta undersöktes genom en enkätstudie med 417 deltagare som skapades utifrån de validerade mätverktygen Dimensioner för kärleksspråk (Love Language Subscales) och Mini-IPIP (Mini International Personality Item Pool-Five-Factor Model). Data analyserades med hjälp av en korrelationsanalys samt ett t-test. Resultatet från korrelationsanalysen visade ett signifikant positivt samband mellan vänlighet och alla fem kärleksspråk. Med andra ord tyder detta på att personer som skattar högt på vänlighet även skattar högt på Chapmans fem kärleksspråk. T-testet visade endast en svagt signifikant skillnad mellan olika relationsstatus och fysisk beröring samt bekräftande ord, där de i relation skattade högre på båda. Relationsstatus tycks alltså kunna indikera personers kärleksspråk till viss del. / Romantic relationships are a significant part of many people's lives. An important part of a well-functioning relationship is showing love to each other, preferably through different love languages. The five love languages were developed by Chapman (1992) and include Acts of Services, Physical Touch, Words of Affirmation, Quality Time and Gifts. Love languageshave been shown to be a contributing factor to high quality romantic relationships. The personality trait Agreeableness from the Five-factor model is linked to loving and empathic traits, among others. This study aims to study the relationship between Agreeableness and love language. The study also investigated if there was any difference in love language depending on whether you are single or in a relationship. This was done through a survey study with 417 participants that was created using the validated measurement tools Love Language Subscales and Mini-IPIP (Mini International Personality Item Pool-Five-Factor Model). The data were analyzed using a correlation analysis and a t-test. The results of the correlation analysis showed a significant positive correlation between Agreeableness and all five love languages. In other words, this indicates that people who score high on Agreeableness also score high on Chapman's five love languages. The t-test showed only a weak significant difference between relationship status and Physical Touch and Words of Affirmation, with those in relationships scoring higher on both. Thus, relationship status seems to be able to indicate love language to some extent.

À partir de définitions empruntées à la philosophie antique (Platon, Aristote), à la littérature païenne (Ovide), à la théologie chrétienne (Augustin, Thomas d’Aquin), ou encore à la médecine (de Galien à Robert Burton), cette thèse étudie les représentations du désir dans la poésie narrative élisabéthaine des années 1590, en particulier chez Shakespeare (Venus and Adonis), Marlowe et Chapman (Hero and Leander) et Spenser (The Faerie Queene, II et III). Le postulat de départ est que le désir détermine les conditions de sa représentation : il est ainsi à la fois objet poétique et principe de création littéraire. L’approche rhétorique cible les figures de style associées au mouvement : la métaphore et la métonymie, mais aussi les figures de construction qui jouent sur l’ordre des mots et les figures de pensée qui se dévoilent progressivement, comme l’allégorie. Si le désir fonctionne comme un lieu commun dans les textes de la Renaissance anglaise, le recours à une rhétorique commune et le partage d’un même lieu physique ne garantissent pas nécessairement le rapprochement des corps. C’est face à face que sont envisagés le corps désiré, caractérisé par sa fermeture et considéré comme une œuvre d’art intouchable, et le corps désirant, organisme vivant exposé à la contamination. La perméabilité gagne le poème lui-même, dans son rapport à son environnement politique et social, dans son utilisation de ses sources et dans sa composition. Parce qu’il joue un rôle en tant que mécanisme de progression du récit, notamment dans la relation entre description et narration, le désir invite à envisager la mimésis comme un processus réversible. / Starting from definitions of desire borrowed from ancient philosophers (Plato, Aristotle), classical poets (Ovid), Christian theologians (Augustine, Thomas Aquinas), and physicians (from Galen to Robert Burton), this dissertation studies the representations of desire in Elizabethan narrative poetry from the 1590s, and more particularly in Shakespeare’s Venus and Adonis, Marlowe and Chapman’s Hero and Leander, and Spenser’s Faerie Queene (II and III). The guiding hypothesis is that desire determines the terms and images in which it is represented; it is therefore both a poetical object and a principle of literary creation. Using a rhetorical approach, I focus on stylistic devices linked with motion: metaphor and metonymy, but also figures of construction which play on word order, and figures such as allegory, which progressively unravel thought. Although desire does act as a commonplace in Early Modern texts, sharing the same language and the same locus does not necessarily entail physical communion for the bodies involved. The body of the beloved, enclosed upon itself and depicted as an untouchable work of art, is pitted against the lover’s organism, alive and exposed to contamination. The poem itself becomes permeable in relation to its social and political environment, in its use of sources, and in its compositional procedures. Desire articulates description and narration, leading the narrative forward but also backward, which suggests that mimesis can be a reversible process.