Further investigations intending illucidate the mechanism of a newly discovered redox-alkylation reaction of azo dyes are presented. Preliminary results indicate that this reaction most probably proceeds via initial N-alkylation of the anion derived from an alpha-ketohydrazone. An investigation is continued to study the synthesis of macrocycle-carbohydrate-dye hybrids. The development of a modular approach to macrocycle assembly has enabled the synthesis of a library of pyridine-based macrocycles possessing multiple donor sites. A central dye scaffold, prepared from the SNAr reaction between halo-substituted azo dye and a disubstituted phenol, was decorated with a representative carbohydrate or macrocycle using Sharpless click chemistry. Also an "S3N-ligand azo-dye" conjugate has been synthesised with a view to the development of a sensor for heavy metal ions. Complexation of this system with Ag(I), Hg(II) and Cu(II) salts has been investigated. Complexation of the dye to metals results in a bathochromic shift in the absorption maximum of the azo dye, an effect which is most pronounced for Cu(II).The Kobayashi fragmentation has transformed the area of benzyne chemistry as it enables its generation from readily available precursors under mild reaction conditions. The controlled generation of benzyne in this manner has been utilised by many groups, allowing readily access to a variety of functionalised aromatic and heteroaromatic from simple precursors. During the course of a synthetic project, which was to utilise the Kobayashi fragmentation in a key intramolecular Diels-Alder reaction, we noticed that alternate modes of fragmentation/rearrangement accompanied the desired elimination reaction leading to benzyne generation. In particular, competing Fries or Smiles rearrangements became the major routes of fragmentation in appropriately functionalised substrates. The results of an investigation into the factors affecting the course of the Kobayashi fragmentation, together with the development of a novel bi-aryl synthesis are presented in this thesis.

In the Amazon region, Xylopia species are used to popular medicine, pharmacobotany and to produce wood and fibers. However, the knowledge about vegetative organ anatomy is not enough. Therefore, this work purposed to know leaf and wood anatomy of Xylopia henthamii R. E Fries and Xylopia nítida Dunal, and it is contributing to identify their. For this study usual techniques were used in plant and wood anatomy. The leaf anatomic characteristics is common like dorsiventral mesophyll, hipostomatic leaf, paracytic stomata, simple filiform trichomes, collateral vascular bundles, secretory cavities scattered in mesophyll and petiole, druse idioblastic in petiole and leaf vein is brochidodromous. But they were different about shape of epidermal cell walls in abaxial surface, papillose abaxial surface, invaginated adaxial surface of petiole, vascular bundles and chlorenchyma or fundamental parenchyma in leaf margin, invaginated stomata, striate cuticle and marginal vein. The wood anatomic characteristics presented uniformly in macro and microscopic levei with little distinct growth rings, multiples vessels of two to five, apotracheal axial parenchyma in thin lines and scalariform, simple perforated plates, alternate intervessel pits, rays were homogeneous, mainly three-seriate, with procumbents cells. The main differences between them were length and vessels tangencial diameter. It was concluded that leaf anatomy is efficient to taxonomy, but wood anatomy not, because the homogeneously between that species. / Espécies do gênero Xylopia, são usadas na região amazônica, na medicina popular, na farmacobotânica, no aproveitamento de madeira e das fibras. Contudo, o conhecimento sobre a anatomia dos órgãos vegetativos, não contemplam todas as espécies do gênero. Diante disso, visando o conhecimento científico das espécies de Xylopia, o presente trabalho teve como objetivo conhecer as estruturas internas das folhas e da madeira das espécies Xylopia henthamii R. E Fries e Xylopia nítida Dunal, contribuindo dessa maneira para a identificação das mesmas. Para a realização do trabalho, foram empregadas as técnicas usuais em anatomia vegetal e da madeira. Com relação à caracterização anatômica das folhas as espécies apresentaram características em comum como dorsiventralidade, lâmina hipoestomática, estômatos paracíticos, tricomas simples filiformes, feixes vasculares colaterais, cavidades secretoras dispersas no mesofilo e pecíolo, idioblastos em drusas no pecíolo e o padrão de venação foliar do tipo broquidódromo. Entretanto as espécies foram separadas com relação ao contorno das paredes anticlinais e periclinais na superfície adaxial, superfície abaxial papilosa, face adaxial do pecíolo invaginada, margem apresentando feixes no bordo foliar, margem terminando com parênquima paliçádico ou parênquima fundamental, estômatos posicionados abaixo do nível das células epidérmicas, estriamento cuticular e presença da nervura marginal. Em relação à caracterização anatômica da madeira as mesmas apresentaram grande uniformidade em nível macro e microscópico como camadas de crescimento poucos distintas, arranjo dos vasos múltiplos de dois a cinco, parênquima axial apotraqueal em linhas finas e escalariforme, placas de perfurações simples, pontuações intervasculares alternas, raios homogêneos, predominantemente trisseriados, constituídos de células procumbentes. As principais diferenças entre as mesmas estão relacionadas ao comprimento e ao diâmetro tangencial dos elementos de vasos ao diâmetro do lume do tecido fibroso. Com base nos resultados, conclui-se que tanto a anatomia foliar quanto a anatomia do lenho das espécies selecionadas neste trabalho foram eficientes para a separação dos taxa, mesmo as espécies apresentarem em sua organização estrutural interna grande homogeneidade entre si.

The Fries Fault, a 1.2-2.3 km wide zone near Riner, is a major tectonic discontinuity in the Blue Ridge geologic province, characterized by progressive stages of continuous ductile deformation. Trending northeast with a shallow to moderate southeast dip, this fault juxtaposes Little River Gneiss on the southeast against Pilot Gneiss and the Chilhowee Formation to the northwest. A 0.8-1.2 km wide subzone of protomylonite within the Little River Gneiss grades into a 0.5-1.0 km wide mylonite subzone, the latter containing narrow bands of phyllotactic ultramylonite ranging in width from centimeters to tens of meters. Mylonitization is reflected by a marked reduction in grain size, elongation of quartz and fracturing of feldspar, all concomitant with the development of a mylonitic foliation (S_m). Ductile deformation processes involving grain elongation, recovery and recrystallization, combined with chemical processes (primarily pressure solution), are the dominant strain-accommodation mechanisms in the formation of S_m. Rocks within the fault zone have undergone four phases of Paleozoic deformation. An early S₁ foliation has been nearly completely transposed by S_m(S₂), which dominates across most of the area. The development of S_m was accompanied by a retrogressive metamorphism that altered basement rocks from lower amphibolite to greenschist facies. Chilhowee Group rocks remained at lower greenschist facies. Post-faulting deformation produced an S₃ crenulation cleavage associated with northeast trending, overturned F₃ folds. Subsequent refolding produced open, northwest trending F₄ folds. Although the bulk deformation is progressive simple shear, flattening is increasingly dominant during the later stages of deformation. / Master of Science

The present PhD thesis describes the synthesis and characterization of novel planarchiral 1,2-P,O-ferrocenes and their application in the Pd-catalyzed Suzuki-Miyaura reaction. It was especially focused on the development of a new synthetic pathway to this type of substitution pattern by applying the anionic phospho-Fries rearrangement in ferrocene chemistry. Starting from hydroxy ferrocene, a high diversity of Fc–O–P- type (Fc = (n5-C5H5)(n5-C5H4)) compounds were synthesized, whereby the electronic properties of the phosphorus fragments were varied. The anionic phospho-Fries rearrangement successfully occurred subsequent to an ortho-lithiation with a non-nucleophilic base giving the 1,2-P,O-ferrocenes in up to quantitative yields. The usage of chiral pool-based alcohols for the synthesis of chiral ferrocenyl phosphates allowed a diastereoselective proceeding, giving single isomers in up to 95% de. Temperature-dependent investigations of mixed ferrocenyl-, phenyl- and Nheterocyclicphosphates revealed a limitation of ferrocenyl-based rearrangements per reaction step, contrary to phenyls. 1,2-P,O-ferrocenyl phosphonates could successfully be converted into phosphines by applying Stelzer P,C cross-coupling reactions on ferrocenes for the first time. Their usage as ligands for C,C cross-coupling reactions was confirmed by the synthesis of sterically hindered biaryls in high yields at 70°C with a low catalyst loading of 1 mol-% Pd. Functionalization of the 1,2-P,O -structural motif could be achieved by applying nucleophilic aromatic substitution reactions (SNAr) as an alternative pathway for the synthesis of ferrocenyl aryl ethers. Subsequent to a Fries rearrangement sterically-demanding 1,3-di-orthosubstituted aryloxy ferrocenes could be obtained. Multi SNAr reactions of hydroxyferrocenes at polyfluorinated arenes gave up to pentaferrocenyl-functionalized aryl ethers, whose electrochemical properties were investigated. The reaction of CH2-enlarged ferrocenylmethanols gave α-ferrocenylcarbenium ions instead of phosphates, while treating them with chlorophosphates. Enantiopure 2-P(S)Ph2-substituted derivatives of these ions underwent a subsequent intermolecular “S2−“ migration, resulting in thioethers, for example (Sp,Sp)-(2-(P(S)Ph2)FcCH2)2S, in a unique mechanism. Instead, the presence of electronrich arenes gave electrophilic aromatic substituted benzenes bearing chiral ferrocenylmethyl backbones. These type of ligands gave biaryls with up to 26 % ee. / Die vorliegende Arbeit beschäftigt sich mit der Synthese und Charakterisierung von neuartigen planar-chiralen 1,2-P,O-ferrocenen sowie deren Anwendung in der Pd-katalysierten Suzuki-Miyaura Reaktion. Dabei lag der Focus in der Anwendung anionischer phospho-Fries Verschiebungen auf Ferrocene um dieses spezielle Substitutionsmuster erhalten zu können. Ausgehend von Hydroxyferrocenen wurde so eine Vielzahl neuer Verbindungen des Typs Fc–O–P (Fc = (n5-C5H5)(n5-C5H4)) synthetisiert, wobei die elektronischen Eigenschaften des Phosphor-tragenden Fragmentes variiert wurden. Die anionische phospho-Fries Verschiebung erfolgte im Anschluss einer ortho-Lithiierung mit einer nicht-nucleophilen Base, was 1,2-P,O-Ferrocene nahezu quantitative ergab. Durch die Verwendung von chiral-pool basierten Alkoholen für die Synthese chiraler Ferrocenylphosphate konnte eine diastereoselective 1,3-O->C Umlagerung mit Isomerenreinheiten von bis zu 95 % erreicht werden. Untersuchungen von gemischten Ferrocenyl-, Phenyl- und N-heterocyclischen Phosphaten bei verschiedenen Temperaturen zeigte eine Limitierung Ferrocenyl-basierter Umlagerungen pro Reaktionsschritt im Gegensatz zu denen von Phenylen. Die erhaltenen 1,2-P,O-Ferrocenylphosphate wurden erstmals mittels Stelzer P,C Kreuz-Kupplungsreaktionen erfolgreich in Phosphane umgesetzt. Deren Verwendung als Ligand in C,C Kreuz-Kupplungsreaktionen wurde am Beispiel der Synthese räumlich anspruchsvoller Biaryle in hohen Ausbeuten bei nur 70°C und niedrigen Katalysatorbeladungen von 1 mol-% Pd demonstriert. Die Funktionalisierung des 1,2-P,O-Strukturmotifes konnte durch die Anwendung von nucleophilen aromatischen Substitutionsreaktionen erreicht werden, die einen alternativen Zugang zu Ferrocenylarylethern bietet. Im Anschluss an eine Fries Umlagerung konnten so sterisch anspruchsvolle 1,3-di-ortho-substituierte Ferrocenylarylether erhalten werden. Durch mehrfache SNAr Reaktionen von Hydroxyferrocenen an polyfluorierten Aromaten wurden bis zu fünf-fach substituierte Ether erhalten, deren elektrochemischen Eigenschaften untersucht wurden. Die um eine CH2-Einheit verlängerten Ferrocenylmethanole gaben bei Reaktion mit Chlorophosphaten alpha Ferrocenylcarbeniumionen anstelle der gewünschten Phosphate. Enantiomerenreine 2-P(S)Ph2-substituierte Derivate dieser Ionen durchliefen anschließend einen intermolekularen ”S2–“ Transfer in einem einzigartigen Mechanismus, was bspw. in Thioethern des Typs (Sp,Sp)-(2-(P(S)Ph2)FcCH2)2S resultierte. In Anwesenheit elektronenreicher Aromaten wurden elektrophile aromatischen Substitutuionen und die Bildung chiraler ferrocenylmethyl-substitutuierter Benzene beobachtet. Deren Einsatz als Ligand ergab Biaryle mit bis zu 26 % ee.

The present PhD thesis describes the synthesis and characterization of novel planarchiral 1,2-P,O-ferrocenes and their application in the Pd-catalyzed Suzuki-Miyaura reaction. It was especially focused on the development of a new synthetic pathway to this type of substitution pattern by applying the anionic phospho-Fries rearrangement in ferrocene chemistry. Starting from hydroxy ferrocene, a high diversity of Fc–O–P- type (Fc = (n5-C5H5)(n5-C5H4)) compounds were synthesized, whereby the electronic properties of the phosphorus fragments were varied. The anionic phospho-Fries rearrangement successfully occurred subsequent to an ortho-lithiation with a non-nucleophilic base giving the 1,2-P,O-ferrocenes in up to quantitative yields. The usage of chiral pool-based alcohols for the synthesis of chiral ferrocenyl phosphates allowed a diastereoselective proceeding, giving single isomers in up to 95% de. Temperature-dependent investigations of mixed ferrocenyl-, phenyl- and Nheterocyclicphosphates revealed a limitation of ferrocenyl-based rearrangements per reaction step, contrary to phenyls. 1,2-P,O-ferrocenyl phosphonates could successfully be converted into phosphines by applying Stelzer P,C cross-coupling reactions on ferrocenes for the first time. Their usage as ligands for C,C cross-coupling reactions was confirmed by the synthesis of sterically hindered biaryls in high yields at 70°C with a low catalyst loading of 1 mol-% Pd. Functionalization of the 1,2-P,O -structural motif could be achieved by applying nucleophilic aromatic substitution reactions (SNAr) as an alternative pathway for the synthesis of ferrocenyl aryl ethers. Subsequent to a Fries rearrangement sterically-demanding 1,3-di-orthosubstituted aryloxy ferrocenes could be obtained. Multi SNAr reactions of hydroxyferrocenes at polyfluorinated arenes gave up to pentaferrocenyl-functionalized aryl ethers, whose electrochemical properties were investigated. The reaction of CH2-enlarged ferrocenylmethanols gave α-ferrocenylcarbenium ions instead of phosphates, while treating them with chlorophosphates. Enantiopure 2-P(S)Ph2-substituted derivatives of these ions underwent a subsequent intermolecular “S2−“ migration, resulting in thioethers, for example (Sp,Sp)-(2-(P(S)Ph2)FcCH2)2S, in a unique mechanism. Instead, the presence of electronrich arenes gave electrophilic aromatic substituted benzenes bearing chiral ferrocenylmethyl backbones. These type of ligands gave biaryls with up to 26 % ee. / Die vorliegende Arbeit beschäftigt sich mit der Synthese und Charakterisierung von neuartigen planar-chiralen 1,2-P,O-ferrocenen sowie deren Anwendung in der Pd-katalysierten Suzuki-Miyaura Reaktion. Dabei lag der Focus in der Anwendung anionischer phospho-Fries Verschiebungen auf Ferrocene um dieses spezielle Substitutionsmuster erhalten zu können. Ausgehend von Hydroxyferrocenen wurde so eine Vielzahl neuer Verbindungen des Typs Fc–O–P (Fc = (n5-C5H5)(n5-C5H4)) synthetisiert, wobei die elektronischen Eigenschaften des Phosphor-tragenden Fragmentes variiert wurden. Die anionische phospho-Fries Verschiebung erfolgte im Anschluss einer ortho-Lithiierung mit einer nicht-nucleophilen Base, was 1,2-P,O-Ferrocene nahezu quantitative ergab. Durch die Verwendung von chiral-pool basierten Alkoholen für die Synthese chiraler Ferrocenylphosphate konnte eine diastereoselective 1,3-O->C Umlagerung mit Isomerenreinheiten von bis zu 95 % erreicht werden. Untersuchungen von gemischten Ferrocenyl-, Phenyl- und N-heterocyclischen Phosphaten bei verschiedenen Temperaturen zeigte eine Limitierung Ferrocenyl-basierter Umlagerungen pro Reaktionsschritt im Gegensatz zu denen von Phenylen. Die erhaltenen 1,2-P,O-Ferrocenylphosphate wurden erstmals mittels Stelzer P,C Kreuz-Kupplungsreaktionen erfolgreich in Phosphane umgesetzt. Deren Verwendung als Ligand in C,C Kreuz-Kupplungsreaktionen wurde am Beispiel der Synthese räumlich anspruchsvoller Biaryle in hohen Ausbeuten bei nur 70°C und niedrigen Katalysatorbeladungen von 1 mol-% Pd demonstriert. Die Funktionalisierung des 1,2-P,O-Strukturmotifes konnte durch die Anwendung von nucleophilen aromatischen Substitutionsreaktionen erreicht werden, die einen alternativen Zugang zu Ferrocenylarylethern bietet. Im Anschluss an eine Fries Umlagerung konnten so sterisch anspruchsvolle 1,3-di-ortho-substituierte Ferrocenylarylether erhalten werden. Durch mehrfache SNAr Reaktionen von Hydroxyferrocenen an polyfluorierten Aromaten wurden bis zu fünf-fach substituierte Ether erhalten, deren elektrochemischen Eigenschaften untersucht wurden. Die um eine CH2-Einheit verlängerten Ferrocenylmethanole gaben bei Reaktion mit Chlorophosphaten alpha Ferrocenylcarbeniumionen anstelle der gewünschten Phosphate. Enantiomerenreine 2-P(S)Ph2-substituierte Derivate dieser Ionen durchliefen anschließend einen intermolekularen ”S2–“ Transfer in einem einzigartigen Mechanismus, was bspw. in Thioethern des Typs (Sp,Sp)-(2-(P(S)Ph2)FcCH2)2S resultierte. In Anwesenheit elektronenreicher Aromaten wurden elektrophile aromatischen Substitutuionen und die Bildung chiraler ferrocenylmethyl-substitutuierter Benzene beobachtet. Deren Einsatz als Ligand ergab Biaryle mit bis zu 26 % ee.

Throughout the nineteenth century, walking for leisure and for spiritual endeavor in America correlated with the rise of literary romanticism. This burgeoning fashion of pedestrian travel, coupled with an impulse to experience the ever expanding nation, spawned a new and enduring subgenre in American letters – the walking text. Many scholars consider Henry David Thoreau and John Muir to be the century’s greatest literary amblers and naturalists; while their catalogs of walking literature are foundational, they are not exclusive. “Beautiful Day. Pleasant Walk: Walking and Landscape in Works of Estwick Evans, John D. Godman, Elizabeth Fries Ellet, and Bradford Torrey” aims to establish the importance of several underappreciated nineteenth century American pedestrians and landscapes. In addition to analyzing the development and importance of walking texts throughout the century, this dissertation also considers the geographies over which the authors traveled. The northern grounds of Ohio’s forgotten Great Black Swamp (Evans) and Philadelphia’s bucolic Wissahickon Creek (Godman), team with the southern worlds of rural Antebellum landscapes (Ellet) and Civil War battlefields (Torrey) to create a compelling map of nineteenth century America. Finally, through first-hand, authorial accounts this study discusses each terrain’s historical contexts as well as their current conditions.

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / The aim of this work was to employ the microwave radiation in the processes of frying potatoes (Solanum tuberosum L.), and evaluate of the impact on lipids oxidation parameters and mass transfer in the product. The potatoes (Asterix CV.) were cut in stick form and subjected to conventional system of fry (CF) and adapted microwave system (MW) in soybean oil (SO) and vegetable fat (VF), under the same conditions of mass, volume, time and temperature of process. Physico-chemical quality parameters of the potatoes and SO/VF were determined. The results of the moisture content indicated that dehydration in potatoes was 45% higher in microwave system, and in addition a greater absorption of lipids was observed. The contents of total polar compounds in SO were greater than 25% in MW and CF after 5 and 7 days of frying, respectively, while the VF systems did not exceed 19.5% at 20 days of use. The peroxide values presented higher values for SO in MW system. High values of conjugated dienes parameters, peroxide values, total polar compounds and refractive index in treatments with MW. Possibly the major loss of water from the product in these system has favored the hydrolytic and oxidative reactions. Regarding the SO fatty acids a decreased was observed of monounsaturated 4.0 and 2.0%, and poly-unsaturated 6.3 and 3.6%, respectively for MW and CF, and VF presented an opposite behavior in both systems. The MW frying process provided a higher inside temperature of the potatoes in both fats, SO and VF. When OS was only heated with MW radiation observed, based on the results, a similar behavior to the conventional system in almost all parameters. The application of MW for frying potato in chips form showed favorable values of mass transfer and heat, obtaining a product with similar characteristics to the reference product. Thus it was demonstrated a potential use of MW radiation in the frying potato process and its use only as a heating source for the OS and VF. / O objetivo deste trabalho foi empregar a radiação micro-ondas em processos de fritura de batata (Solanum tuberosum L.) e avaliar o impacto sobre a oxidação dos lipídios e a transferência de massa no produto. As batatas da cultivar Asterix foram cortadas na forma de palito e submetidas à fritura em fritadeira convencional (FC) e micro-ondas adaptado (MW), em óleo de soja (OS) e gordura vegetal (GV), nas mesmas condições de massa, volume, tempo e temperatura. Foram feitas análises dos aspectos físico-químicos das batatas e da qualidade do OS e da GV. Os resultados do teor de umidade indicaram que a desidratação das batatas foi 45% maior em micro-ondas, proporcionando uma maior absorção de lipídios. O teor de compostos polares totais em OS foram maiores do que 25% para MW e FC, a partir de 5 e 7 dias de fritura, respectivamente, enquanto da GV não passou de 19,5% em 20 dias de uso. O índice de peróxidos apresentou maiores valores para OS em MW. Foram observados maiores valores dos parâmetros dienos conjugados, índice de peróxidos, compostos polares e índice de refração nos tratamentos com MW. Possivelmente a maior perda de água do produto tenha favorecido as reações hidrolíticas e oxidativas. Em relação aos ácidos graxos do OS houve uma redução dos monoinsaturados de 4,0 e 2,0%, e de 6,3 e 3,6% dos poli-insaturados, respectivamente para MW e FC. Para a GV o comportamento foi inverso, sendo a redução maior no sistema convencional. O processo de fritura em MW proporcionou maior temperatura no interior das batatas fritas tanto em óleo quanto em gordura. No experimento em que o OS foi somente aquecido com radiação MW observamos, com base nos resultados, um comportamento semelhante ao sistema convencional em quase todos os parâmetros avaliados. A aplicação de MW para fritura de batatas chips apresentou valores favoráveis de transferência de massa e calor, obtendo um produto com características semelhante ao produto de referência. Dessa forma foi evidenciado um potencial de uso da radiação MW no processo de fritura de batata, bem como o seu uso apenas como uma fonte de aquecimento para o OS e a GV.

The diploma work deals with the analysis of the logistic chain of the company Friall s.r.o., which is a producer of frozen potato specialities. Based on this analysis I wanted to discover weak points in functionality of the logistic chain and find suitable precautionary measures as well as solutions leading to an improvement of the current situation. The diploma work is focused on the raw material entry and self-production of the products.

Master of Visual Arts / This Dissertation explores the metaphor of Ariadne’s thread in terms of interconnection, when an element from the everyday is used as a locus linking broader concepts of time and space. Such experiences and associations are reflected in the work of Louise Bourgeois, Eva Hesse, Doris Salcedo, Lucio Fontana, Richard Tuttle, Mona Hatoum, Simone Mangos, Anya Gallaccio and Yoshihiro Suda. In relation to my own work, the metaphor of interconnecting thread allows a sense of freedom and journey of discovery. My studio and related research are closely aligned in developing my understanding of interconnection, through my studio process of making and continuing experiences of looking at and interpreting others artists’ work.

Master of Visual Arts / This Dissertation explores the metaphor of Ariadne’s thread in terms of interconnection, when an element from the everyday is used as a locus linking broader concepts of time and space. Such experiences and associations are reflected in the work of Louise Bourgeois, Eva Hesse, Doris Salcedo, Lucio Fontana, Richard Tuttle, Mona Hatoum, Simone Mangos, Anya Gallaccio and Yoshihiro Suda. In relation to my own work, the metaphor of interconnecting thread allows a sense of freedom and journey of discovery. My studio and related research are closely aligned in developing my understanding of interconnection, through my studio process of making and continuing experiences of looking at and interpreting others artists’ work.