Submitted by Marilene Donadel (marilene.donadel@unioeste.br) on 2018-11-13T19:40:32Z No. of bitstreams: 1 Alexandra_Amaral_2018.pdf: 6685905 bytes, checksum: ec13a764da46630f5757867d952330fd (MD5) / Made available in DSpace on 2018-11-13T19:40:33Z (GMT). No. of bitstreams: 1 Alexandra_Amaral_2018.pdf: 6685905 bytes, checksum: ec13a764da46630f5757867d952330fd (MD5) Previous issue date: 2018-07-31 / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior - CAPES / It is notable that with technological advances and scientific research, organic synthesis has provided the synthesis of several compounds that are essential to meet the needs of mankind. 3-Indolyl-glycine derivatives have been the subject of several studies, since they are precursors of non-proteinogenic amino acids that act as synthetic intermediates of compounds with important biological activity. However, the synthetic routes described in the literature for these compounds present disadvantages, since they use organic solvents, extreme temperatures, non-recoverable catalysts and long reaction periods. Thus, the search for the development of alternative methodologies has attracted great attention in Organic Synthesis in order to reduce environmental impact, reduce process costs and minimize waste formation. In view of this scenario, the proposal of a new methodology for the synthesis of 3-indolyl glycine derivatives, via a multi-component reaction (Aza-Friedel-Crafts) between indoles, ethylglyoxalate and anilines, which follow the principles established by Green Chemistry, are somewhat of great interest to be studied. After a systematic study of the reaction conditions, two synthetic methodologies were established. In the first methodology a catalyst and surfactant was used in the reaction, under ambient temperature, however this condition led to the formation of by-product from the rearrangement of the desired product. In addition, the catalytic system of this synthetic methodology presented potential to be recycled, but its (re) use showed a decrease in yields, and it is not feasible to use this methodology. Thus, another synthetic methodology was proposed, in which only surfactant was used without the use of the catalyst, with heating of 50 ºC. The second methodology was more feasible, since the yields of the products obtained with the variation of the indole substrate were excellent. The synthesized compounds were evaluated for their biological activity. Bioassays of phytotoxic activity on lettuce seeds (Lactuca sativa) were carried out, in which it was verified that these compounds interfere in seed germination and root growth. Compounds 4b, 4j and 4n showed remarkable germination inhibitory activity at the concentration of 25 ppm. In inhibition of growth, compounds 4a, 4l and 4n showed inhibitory activity already at concentrations of 10 ppm. Such compounds were as active as the glyphosate and atrazine herbicides tested. It is emphasized that compound 4n had inhibitory activity both for germination and for growth of the species studied. Thus, the compounds presented in this paper provide an experimental basis for future studies on pesticides based on 3-Indolyl-glycine derivatives, since it has potential applications for herbicidal activity. / É notório que com os avanços tecnológicos e com as pesquisas científicas, a síntese orgânica proporcionou a síntese de diversos compostos que são essenciais para suprir as necessidades da humanidade. Os compostos derivados de 3-Indolil-glicina tem sido alvo de diversos estudos, visto que são precursores de aminoácidos não proteinogênicos que atuam como intermediários sintéticos de compostos com importante atividade biológica. Entretanto, as rotas sintéticas descritas na literatura para estes compostos apresentam desvantagens, visto que as mesmas utilizam solventes orgânicos, temperaturas extremas, catalisadores não recuperáveis e longos períodos de reação. Desse modo, a busca pelo desenvolvimento de metodologias alternativas tem atraído grande atenção na Síntese Orgânica de modo a proporcionar a redução do impacto ambiental, reduzir custos do processo e minimizar a formação de resíduos. Diante desse cenário, a proposta de uma nova metodologia para a síntese de derivados de 3-indolil-glicina, via reação multicomponente (Aza-Friedel-Crafts) entre indóis, etilglioxalato e anilinas, que contemplam os princípios estabelecidos pela Química Verde, são algo de grande interesse a ser estudado. Após um estudo sistemático das condições de reacão, estabeleceram-se duas metodologias sintéticas. Na primeira metodologia foi utilizado um catalisador e surfactante na reação, sob temperatura ambiente, entretanto essa condição levou a formação de subproduto oriundo do rearranjo do produto desejado. Além disso, o sistema catalítico dessa metodologia sintética apresentou potencial de ser reciclado, porém sua (re)utilização demonstrou um decréscimo nos rendimentos, não sendo viável o uso dessa metodologia. Desse modo foi proposta outra metodologia sintética, na qual só foi utilizado surfactante sem o uso do catalisador, com aquecimento de 50 ºC. A segunda metodologia se mostrou mais viável, visto que os rendimentos dos produtos obtidos com a variação do substrato indólico foram excelentes. Os compostos sintetizados foram avaliados quanto à sua atividade biológica. Bioensaios de atividade fitotóxica em sementes de alface (Lactuca sativa) foram realizados, nos quais se verificou que estes compostos interferem na germinação das sementes e no crescimento das radículas. Os compostos 4b, 4j e 4n mostraram notável atividade inibitória de germinação na concentração de 25 ppm. Na inibição do crescimento, os compostos 4a, 4l e 4n apresentaram atividade inibitória já nas concentrações de 10 ppm. Tais compostos foram tão ativos quanto os herbicidas glifosato e atrazina testados. Salienta-se que o composto 4n teve atividade inibitória tanto para a germinação quanto para o crescimento da espécie estudada. Desse modo, os compostos apresentados neste trabalho fornecem uma base experimental para futuros estudos sobre pesticidas à base dos derivados de 3-Indolil-glicina, visto que tem aplicações potenciais para atividade herbicida.

L’utilisation de méthodologies de synthèse toujours plus performantes et respectueuses de l’environnement est un axe de recherche majeur de la chimie moderne. L’apport de la catalyse, avec l’utilisation de superacides de Lewis, a permis d’améliorer de nombreux processus synthétiques. Nous avons pu développer dans ce manuscrit des réactions de cycloisomérisation de type réaction de Friedel-Crafts qui donnent accès à un ensemble de structures polycycliques intéressantes avec de bons rendements et sélectivités. L’utilisation d’une quantité catalytique, entre 1 et 10 mol% de Bi(OTf)3, permet l’activation d’oléfines et d’allènes non activés ainsi que de systèmes 1,3-diéniques. Ce type de méthodologie, à économie d’atomes maximale, a permis de limiter la formation de sous-produits, le catalyseur pouvant être recyclé et réutilisé sans perte d’activité. Des approches intra- et intermoléculaires, des réactions cascades et tandems ainsi qu’une étude mécanistique ont été effectuées afin de mieux comprendre la réactivité et ses limitations, et ainsi atteindre une plus large gamme de structures. Les méthodologies développées ont été appliquées au domaine des arômes et parfums pour la synthèse d’analogues de la Calone 1951®, de chromanes, d’indanes et de tétralines fonctionnalisés, posant les bases de travaux futurs pour une meilleur compréhension des relations structures-odeurs / Efficient and ecofriendly synthetic methodologies have always constituted an important area of research in modern organic chemistry. Lewis superacid catalysis has contributed in the improvement of many synthetic processes. We have developed some cycloisomerization reactions including Friedel-Crafts type reaction, giving access to a set of interesting polycyclic structures with good yields and selectivities. The use of a catalytic amount of Bi(OTf)3 (1 to 10 mol%), has allowed the activation of olefins, non-activated allenes and of 1,3-dienic systems. This atom economy methodology can prevent the formation of by-products and the catalyst can be recycled without loss of activity. Intra- and intermolecular approaches, tandem and cascades reactions, as well as mechanistic studies were conducted to enable a better understanding of the reactivity and its limitations to reach a wider range of structures. The developed methodologies were applied to the field of flavors and fragrances in the synthesis of Calone 1951® analogues, and for the preparation of chromans, indanes and tetralins type functionalized structures, for a better understanding of the structure/odor relationship.

Du fait de l'extrême acidité des milieux superacides, le comportement des composés organiques y est particulièrement singulier, et en particulier celui des composé azotés. Ces milieux permettent d'accéder par polyprotonation à des intermédiaires superélectrophiles polycationiques, capables d'être piégés par des nucléophiles faibles, comme les ions fluorures solvatés du milieu ou des aromatiques désactivés. L'activation superélectrophile permet en outre d'accéder à une régiosélectivité unique en rendant certains sites réactifs, insensibles dans les milieux acides plus classiques.Dans la première partie de ce travail est étudiée une réaction d'addition anti-Markovnikov sur des anilines N-allyliques dans le mélange HF/SbF5. Une étude mécanistique a été réalisée incluant la modélisation d'intermédiaires réactionnels, des expériences de RMN in situ ainsi que des réactions avec des substrats marqués. Grâce à cette étude, une nouvelle réaction de type Friedel-Crafts permettant d'accéder à des tétrahydroquinolines désactivées a été mise au point. De plus, en modifiant les conditions opératoires, la synthèse d'anilines β-fluorées a également pu être réalisée. Ces réactions ont ensuite été appliquées à la synthèse de nouveaux composés hétérocycliques.La deuxième partie est consacrée au développement d'une nouvelle réaction d'hydrofluoration dynamides dans l'acide fluorhydrique anhydre. Cette méthodologie permet d'accéder à des (E)-α-fluoroènamides orginales avec un excellente régio- et stéréo-sélectivité. Par analogie avec les fluorooléfines qui sont connues pour mimer les fonctions amides, ces composés sont potentiellement de nouveaux bioisostères rigides d'urées, avec des app / Thanks to the extrem acidity of superacid media, the behavior of organic compound in these conditions is especially original. These media provide access by polyprotonation to superelectrophilic polycationic intermediates able to be trapped by very weak nucleophiles such as solvated fluoride ions or deactivated aromatic. In addition, the superelectrophic activation allowed to access to a unique regioselectivity, making some classically unreactive sites very reacive in these conditions.In the first part of this work, an anti-Markovnikov addition of N-allyl anilines in the HF/SbF5 mixture is studied. A mechanistic study was performed including the modeling of reaction intermediates, in situ NMR experiments and reactions with labeled substrates. Through this study, a new Friedel-Crafts type reaction was perform and applied to deactivated tetrahydroquinoline synthesis. In addition, the synthesis of β-fluorinated anilines could also be performed. These reactions were then applied to the synthesis of new heterocyclic compounds.The second part deals with the developement of a new hydrofluorination reaction of yanmides using anhydrous fluorhydric acid. This methodology allowed the synthesis of original (E)-α-fluoroenamides with an excellent regio- and stereo-selectivity. By analogy with fluoroolefins which are known to be mimics of amides, these compounds are potentially new rigid bioisosters of ureas with further potent applications in medicinal chemistry.

Cette étude aborde la carrière et l’oeuvre de René-Yves Creston, artiste qui dans les années vingt, fonde le groupe Ar Seiz Breur. Impliqués dans la vie culturelle locale, les artistes du groupe participent au renouveau des arts décoratifs en Bretagne. Gravure, peinture, faïence, meuble sont autant de domaines dans lesquels ils influencent l’esthétique régionale de la première moitié du XXe siècle dans l’esprit des Arts and Crafts, de l’école de Zakopane et d’autres mouvements européens. Fréquentant les milieux intellectuels parisiens, René-Yves Creston devient un organisateur hors pair et permet à Ar Seiz Breur de participer à des expositions internationales d’envergure. Dans les années trente, son attrait pour le milieu maritime lui permet de participer à la campagne de 1933 au Groenland. Découvrant la pratique ethnographique, il s’inscrit à l’Institut d’ethnologie à la fin des années trente pour y suivre les cours de Marcel Mauss et intègre le musée de l’Homme pour lequel il effectue une mission aux Féroé. Durant la Seconde Guerre mondiale, il participe à la création du réseau du musée de l’Homme et continue ses recherches autour de l’ethnographie bretonne. Après guerre, Georges Henri Rivière l’introduit dans le milieu des musées de société. René-Yves Creston est à l’origine de nombreuses collections dans les musées bretons et au musée des Arts et Traditions populaires. Attaché à l’étude de la région bretonne, il continue néanmoins à s’investir dans l’ethnologie maritime européenne. De la fin du XIXe siècle à la deuxième moitié du XXe siècle, cette étude revient sur le parcours d’un artiste ethnologue dont les préoccupations se tournent sur l’étude de l’homme, de l’utilisation du réalisme dans sa pratique artistique à l’étude des peuples en ethnologie. / This study approaches the career and work of René-Yves Creston : this artist, who, in the twenties co-created the group of Seiz Breur. Strongly involved in local cultural life, the group-artists took part in the revival of decorative crafts in Brittany: engraving, painting, earthenware, furniture, so many areas in which they affect the regional aesthetics of the first mid-twentieth century, in the same spirit as Arts and Crafts or Zakopane school or other european movements. Taking part in parisian intellectual life, René-Yves Creston became a leader, without equal organiser so he leaded Seiz Breur to take part in famous international exhibitions. In the thirties, his own interest for the maritim world leads him to take part in 1933 in a trip to Greenland. He then discovered the ethnographic practice. He joins then the ethnological institute and at the end of thirties follows Marcel Mauss’s lessons and fit in “musée de l’Homme” for which he was involved in a mission in Feröe islands. During the world war two, he took part in setting up the “Réseau du musée de l’Homme”. He then follows on his searches about breton ethnography. After the war, Georges Henri Rivière introduced him in thesociety-museums circles. René-Yves Creston leaded to many collections in breton museums and Arts and popular Traditions museum. Deeply involved in the study of brittany, he carries on taking part in european maritim ethnology studies. From the end of 19th century to second part of 20th, this work reads the process of this man, starting as an artist, who becomes an ethnologist using his realism in art as a tool for his study of man.

Les polymères sont à l’heure actuelle étudiés dans de nombreux domaines comme la chimie, la biochimie, les nanotechnologies, l'électronique, la médecine ou encore les sciences des matériaux et trouvent des applications dans des domaines comme l’industrie automobile, la chimie fine. L’objectif de cette thèse est de réaliser la fonctionnalisation de polymères et de modifier les propriétés de ces matériaux afin d’envisager des nouvelles applications. Nous nous sommes intéressés à des polymères de la famille des poly(aryle éther) et plus particulièrement au poly(éther éther cétone) (PEEK). Ce polymère est connu pour ses propriétés mécaniques, thermiques, électriques ou encore pour sa résistance aux produits chimiques. Dans le premier chapitre, il est question de la fonctionnalisation des différents polymères de départ par des fonctions chlorures de sulfonyle, acides sulfoniques et sulfonamides. Le second chapitre est consacré à la synthèse et à l’étude électrochimique de nouveaux électrolytes polymériques et à de nouvelles membranes pour d’éventuelles applications dans le domaine des batteries au lithium et au sodium, ainsi que dans le domaine des piles à combustible. Dans un troisième chapitre, la préparation de nouveaux catalyseurs métalliques dérivés d’acides sulfoniques polymériques est discutée. Une étude de l’activité catalytique de ces différents catalyseurs a été réalisée sur la réaction d’acylation de Friedel-Crafts. Le quatrième chapitre est consacré à la préparation de nouveaux matériaux ayant des propriétés optiques intéressantes. Enfin dans un cinquième chapitre, la préparation et l’étude de nouveaux matériaux ayant des propriétés antibactériennes sont exposées. / Polymers are now being studied in many fields such as chemistry, biochemistry, nanotechnology, electronics, medicine or material science and have applications in areas such as automotive industry, food industry, fine chemistry. The objective of this thesis is to achieve the functionalization of polymers and modify the properties of these materials in order to consider new applications. We were interested in polymers with the poly(aryl ether) motif, more particularly poly(ether ether ketone) (PEEK). This polymer is known for its mechanical, thermal, electrical properties and for its resistance to chemicals. In the first chapter, we present the functionalization of different polymers by sulfonyl chloride, sulfonic acid and sulfonamide functions. The second chapter is devoted to the synthesis and electrochemical study of novel polymeric electrolytes and new membranes for potential applications in the field of lithium and sodium batteries, as well as in the field of fuel cells. In the third chapter, the preparation of new metal catalysts derived from polymeric sulfonic acids is discussed. A study of the catalytic activity of these different polymeric catalysts was carried out on the Friedel-Crafts acylation reaction. The fourth chapter is devoted to the preparation of new materials with interesting optical properties. Finally, in the fifth chapter, the preparation and the study of new materials with antibacterial properties are reported.

Textiles may be used as a vehicle to penetrate and exemplify a society's customs and traditions. This dissertation concentrates on the Kuba cloths from Zaire and particularly focuses on the social and political implications associated with these textiles. Part One explores the economic aspects of the cloths and the values of work, wealth, status and titleholding among the Kuba. The Kuba's aesthetic preference for pattern and design will be contemplated in relation to the cloths and as an illustration of this culture's concern with decoration and display. Part Two of this study examines the occasions for which these cloths are adorned. It will be observed that these celebrations and rituals, in conjunction with their ceremonial modes of dress, not only underline the importance of the nation and its ideologies and customs (as examined in Part One) but serve to acknowledge ethnic identity, as well as maintain and perpetuate the social and political order of the Kuba. / Art History, Visual Arts and Musicology / M.A. (History of Art)

Poverty alleviation is a key item on the agenda of both government and non-governmental organisations. The use of indigenous knowledge to embark on small and medium size enterprises (SMEs) such as handicraft making has shown that it has a potential to yield the desired outcome in many areas. The research addressed the question: to what degree are handicrafts made in the Lowveld region of Swaziland and to what extent do these handicrafts contribute towards the livelihood of rural households? The data was collected using questionnaires and observations. Findings revealed that the production of handicrafts is the second most important livelihood activity for most respondents. Even though the income received from these activities is small, its significance lies in the timing at which it is received; and on its role in supporting existing livelihood activities. Sustainability of the business is, however, threatened by inaccessibility of resources, lack of organisation and trading challenges There is a need to promote the cultivation of natural resources, continuous training workshops and for women to form cooperatives or groups. Further research is needed that would focus on the following areas: a comparative study done in urban areas which shall also investigate the impact of handicraft on urban poor households; a study which will focus on handicraft marketing and consumption and lastly on the youth and handicraft. / Agriculture, Animal Health and Human Ecology / M.Sc. (Human Ecology)

This dissertation examines the process of domestication of American Indian children in government-controlled schools through art education. At the end of the nineteenth century, Thomas J. Morgan, Commissioner of Indian Affairs (1889-1893), and Estelle Reel, Superintendent of Indian schools (1898-1910), brought changes to the curriculum of Indian schools by introducing the teaching of elementary art and instruction in "Native industries" such as pottery, weaving, and basketry. I claim that art education was as an instrument for the `colonization of consciousness,' that is, for the redefinition of Indigenous peoples' minds through the instilment of values and ideals of mainstream society and thus for the maintenance of a political, economic, social, and racial hierarchy. Art education served the needs of the late-nineteenth century assimilationist agenda. I consider Morgan's and Reel's national mandates at the turn of the twentieth century and examine their rationales for including drawing and Native crafts in the Indian schools' curriculum. This knowledge of educational programs crafted at the bureaucratic level is applied to an analysis of art instruction in two selected institutions, the Albuquerque Indian School in New Mexico and the Sherman Institute in Riverside, California, from 1889 to 1917. I examine local responses to government policies and daily practices of Indian education at the micro level in order to provide specific information as to the organization, structure, and pedagogy of art instruction within a school day in these particular localities. Finally, I discuss how students' artworks were displayed in the context of exhibitions and national conventions as exemplary evidence of the progress toward civilization, but also of the instrumentality of an Anglo education in reaching this goal. As Indian policy changed, so did the art curriculum of Indian schools; while drawing continued until the mid-1910s Native arts and crafts began to disappear and were eventually discontinued. As activities that promoted independence and individual creativity, they began to undermine the government's agenda. From the early 1890s when it was first introduced into Indian schools to the mid-1910s when it lost its significance, art education was a tool for the assertion of America's hegemonic power.

Kandidatuppsats i Företagsekonomi C, Ekonomihögskolan vid Linnéuniversitetet i Växjö, Ekonomistyrning, 2FE13E, VT 2014. Författare: Robin Arnefjord, Erik Davidsson & Alexander Persson Handledare/Examinator: Petter Boye Medbedömare: Jan Alpenberg Titel: Capellagården –Hur samarbeten och nätverk kan bidra till ökade intäkter   Bakgrund: Capellagården är en fristående internatskola på södra Öland som likt många andra skolor av detta slag brottas med knappa resurser. Detta har lett till att Capellagården eftersökt alternativa sätt att effektivisera användningen av tillgängliga resurser samt genom nya samarbeten och nätverk hitta nya intäkter. Syfte: Syftet är att beskriva hur samarbeten och nätverk kan öka intäkternaför en skola som Capellagården. Detta görs i tre steg där vi inleder med att beskriva dagens situation för att sedan studera liknande skolor och slutligen identifiera utvecklingsmöjligheter. Metod: I studien så har vi använt oss av ett abduktivt angreppssätt samt en kvalitativ forskningsstrategi. Empirin har huvudsakligen hämtats från intervjuer med företrädare för tre hantverksskolor. Slutsats: Vi kan konstatera att Capellagården kan dra lärdom av andra skolors sätt att arbeta med samarbeten och nätverk för att öka intäkterna.Exempelvis genom att användning av benchmarking. Samarbetena leder också till synergieffekter i form av kompetens- samt resursdelning. Ett ökat kommunalt samarbete samt en utveckling av arbetet med studenternas nätverk hade stärkt skolan. / Bachelor Thesis Business Administration III, School of Economics at Linnaeus University of Växjö. Management Accounting, 2FE13E, Spring 2014. Authors: Robin Arnefjord, Erik Davidsson & Alexander Persson Examinator/Advisor: Petter Boye Second Examiner: Jan Alpenberg Title: Capellagården – How co-operation and networks can contribute to increased revenues   Background: Capellagården is a stand-alone boarding school located in the southern part of Öland and like many other schools they struggle with scarce resources. This has led to that Capellagården have sought alternative ways to make the usage of available resources more effective as well as through new co-operations and networks find new revenue. Purpose: The purpose is to describe how co-operation and networks can help with the development of a school like Capellagården and increase revenues. This is done in three steps where we start with a description of the present-day situation then study similar schools and finally identify potential development opportunities. Method: We have used an abductive approach and a qualitative research strategy in this study. The empirical material has primarily been collected through interviews with relevant parties of three Craft schools. Conclusion: We can conclude that Capellagården can learn from the way other schools work with co-operation and networks to increase revenues. For example through the usage of benchmarking. Co-operations will also lead to synergy effects in the shape of sharing competence and resources. An increase in the municipal co-operation and a development of the students network would have strengthened the school.

Taxidermy specimens and displays have become increasingly liminal features in contemporary society. Viewed variously as historical curios, obsolete relics or more malignantly as ‘monstrosities’, they can be a source of discomfort for many. Taxidermy objects have become uncomfortable reminders of past scientific and colonial practices which have sought to capture, order and control animated life and as such have become increasingly problematic items for their owners. As a result many taxidermy displays have been dismantled and mounts relegated to ‘backstores’ to gather dust. The paradox is that taxidermy as a practice is a quest for ‘liveness’, to impute life back into the dead. Much like the taxidermist, my goal in this thesis is to revive and restore: to renew interest in and reassert the value of taxidermy collections by recovering what I shall term as the ‘biogeographies’ of their making and continued maintenance. Considerable academic attention has been paid to the ‘finished’ form and display of taxidermy specimens inside cabinets, behind glass – in other words, to their representation. By way of contrast, this thesis recovers the relationships, practices and geographies that brought specimens to their state of enclosure, inertness and seeming fixity. These efforts are aligned with work in cultural geography seeking to counteract ‘deadening effects’ in an active world through a prioritisation of practice (Dewsbury and Thrift 2000), and elsewhere draw on research arguments and approaches originating in historical geography, and the history of science. The thesis firstly investigates historical developments in the scientific and craft practice of taxidermy through the close study of period manuals, combined with ethnographic observations of a practicing taxidermist. Critical attention to practice then facilitates the recovery of the lifeworlds of past taxidermy workshops and the globally sited biogeographies behind the making of individual specimens and collections. The thesis required the purposeful assemblage and rehabilitation of diffuse zoological and historical remains to form unconventional archives, enabling a series of critical reflections on the scientific, creative and political potentials of taxidermy.