No description available.

Introduit originellement par Katzenellenbogen en 1980 , les espaceurs auto-immolables sont définis comme des assemblages covalents capable de corréler la coupure de deux liaisons. La première coupure intervient au niveau du groupement protecteur A, générant un intermédiaire qui conduit spontanément à la rupture de la liaison entre l’espaceur et l’espèce B (par exemple, un composé bioactif). Katzenellenbogen avança que les espaceurs auto-immolables pourraient permettre d’outrepasser les limitations des thérapies classiques (administration directe de composés bioactifs, notamment) et conduiraient à l’émergence d’une nouvelle génération de prodrogues. Ayant effectivement amené une innovation considérable dans ce domaine, ces espaceurs ont depuis trouvé nombres d’applications dans des domaines plus variés (chimie analytique, matériaux, …) ; dont nous présenterons un aperçu.Nous avons taché également de décrire plus en détail les mécanismes d’auto-immolation, conduisant l’intermédiaire à se désassembler et à libérer la molécule B. En effet, chacun de ces mécanismes confèrent des propriétés particulières à l’espaceur en termes de cinétique d’auto-immolation et de compatibilités chimiques possibles principalement. Il est donc primordial d’établir les avantages et les inconvénients de chaque type d’espaceur afin de déterminer au mieux quel genre de structure employer pour l’utilisation choisie.Notre travail a consisté dans un premier temps à compléter certaines données de la littérature afin d’approfondir notre connaissance des espaceurs auto-immolables.De plus, si ces espaceurs ont été introduits pour dépasser les limitations des stratégies préexistantes, ils ne sont pas toujours aptes à répondre à certaines problématiques particulières (sélectivité et sensibilité de leurs activations notamment) ; ce qui nous a amené à proposer une nouvelle génération d’espaceurs auto-immolables capable de mieux répondre à ces attentes.Nos travaux ont permis de comparer la cinétique d’espaceurs cyclisants et de confirmer que les espaceurs basés sur un mécanisme d’élimination avaient une gamme plus étendue d’utilisations potentielles.Après avoir établi ce constat, nous avons développé des dérivés d’espaceurs reposant sur ce principe. Pour des utilisations particulières, deux séries ont été étudiées : - Les dérivés d’aniline bi-activables : ceux-ci ne libérant le groupement partant qu’après 2 stimuli spécifiques (contre un seul jusqu’à présents, tous types d’espaceurs considérés), nous pensons que cette nouvelle classe d’espaceurs pourra constituer une réelle innovation en terme de sélectivité, étant capable de mener à la libération de la molécules d’intérêt après 2 conditions. - Un dérivé triantenné : celui-ci étant capable de libérer la molécule qu’il porte par 3 voies d’éliminations, nous avons supposé qu’il serait bien plus sensible qu’un composé ne pouvant libérer que par une voie unique. Même si le composé n’a pu être obtenu, des avancées significatives ont eu lieu quant à sa synthèse : les résultats obtenus et l’intérêt qu’ils suscitent nous ont amené à proposer d’autres stratégies de synthèse pour aboutir à la création de cet espaceur ultra-sensible. / Originally introduced by Katzenellenbogen in 1981 , self-immolative spacers are defined as covalent assemblies that are able to correlate cleavage of two chemical bonds. First, the protecting group is cleaved, generating an intermediary which spontaneously leads to the rupture of the bond between the spacer and the released molecule (bioactive compound for instance). Katzenellenbogen planned that self-immolative spacers could allow to overcome limitations of classic therapies (especially direct administration of drugs) and constitute a novel and efficient alternative to actual prodrug strategies. Effectively, spacers have opened many possibilities in this field, but also in other domains (like analytical chemistry, material sciences, …) which will be presented in this manuscript.We also took care to detail self-immolation mechanisms (the step leading to the release of the leaving group from the intermediary): indeed, the mechanism is the most important factor of the spacer, determining its properties (kinetic of the process, chemical links allowed). Therefore, it is crucial to determine advantages and drawbacks of each mechanism in order to permit a rational choice of the spacer depending on the application we choose.Our work consisted to complete known kinetic data, leading us to acquire an overview of existing spacers.Self-immolative spacers have been introduced to overcome limits of actual strategies, but they are not always able to answer particular problems (sensitivity and selectivity of their triggering events principally): this leads us to propose a new generation of spacers capable of resolving these problematics.Our researches permitted us to compare kinetic of cyclizing spacers and to confirm that elimination based spacers show a larger scope for potential uses.Starting from this, we developed two series of derivatives using this mechanism: - Bi-triggered anilines: releasing the leaving group after two specific stimuli (only one for reported spacers actually). We are convinced that this new class of spacers can constitute a real innovation for selective treatments. - Three-branched phenol: able to release the compound by three different ways of elimination. This property can increase drastically the sensitivity of the spacer for its activation pathway, considering triggers are three-time more numerous. Even if the compound has not been obtained, significant results in its synthesis have been observed: these results on this interesting project leading us to propose new synthetic strategies in order to obtain this ultra-sensitive compound.

No description available.

Made available in DSpace on 2014-06-11T19:26:52Z (GMT). No. of bitstreams: 0 Previous issue date: 2009-12-16Bitstream added on 2014-06-13T18:30:46Z : No. of bitstreams: 1 santos_me_me_assis.pdf: 757864 bytes, checksum: 6228de78c6143bf23c2d70acb679a080 (MD5) / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES) / A produção intelectual do feminismo questionou as representações e os papéis sociais de gênero e também contribuiu para a evolução de uma perspectiva crítica acerca das múltiplas opressões que assolam as mulheres. Entre as minorias femininas que despontaram nesse cenário de articulação, as mulheres negras, com sua escrita engajada e muitas vezes marcada pela autorrepresentação, buscam se inserir no espaço acadêmico e conquistar o reconhecimento de sua obra literária. Nesse sentido, este trabalho pretende fazer uma reflexão crítica sobre a narrativa de memórias das escritoras negras Carolina Maria de Jesus e Maya Angelou, em suas respectivas obras: Diário de Bitita e I Know Why the Caged Bird Sings. Para tanto, levantamos questões relevantes do enredo e enfocamos o trajeto singular das protagonistas negras rumo à conscientização de uma realidade construída em torno das desigualdades de poder. Deste modo, num primeiro momento, refletimos sobre a condição dos afrodescendentes e sublinhamos a situação da mulher negra durante e depois do período escravocrata. Na sequência tratamos da questão da literatura confessional direcionando seu enfoque para as formas diário e memória, a fim de evidenciar suas congruências e diferenças no universo confessional. Por fim, empreendemos um trabalho de análise das obras, em que salientamos pontos importantes e discutimos as trajetórias de cada personagem rumo à autoaceitação. / The intellectual production of feminism questioned the representations and social roles of gender and contributed to an evolution of a critical perspective towards the oppression suffered by women. Among the minorities that emerged in this scenery of articulation, the black women with an engaged writing, and also marked many times by self- representation try to put themselves in the academic space and have the recognition of their work as well. In this sense, this work intends to make a critical reflection about the memoirs of the black writers Carolina Maria de Jesus and Maya Angelou, in their respective books: Diário de Bitita and I Know Why the Caged Bird Sings. For that we raised questions concerning the plot and emphasize the black protagonists´ peculiar course towards awareness of a reality built around unequal powers. So, we first consider the black people condition and underline the black women situation before and during slavery time. Secondly, we talk about the confessional literature focalizing the diary and memoir forms in order to make evident their similarities and differences in the confessional universe. At last we attempt to a work of analysis of the books where we point out important items and discuss the characters´ course towards self-acceptance.

The aim of this master’s thesis was to study the portrayal of discrimination that occurs because of multiple factors in Maya Angelou’s book I Know Why the Caged Bird Sings. The analysis has been conducted through the lens of Critical Race theory as the theory draws on the affiliation between race, racism and power. The main focal point of this essay was the intersectionality of race, gender and social class. The results of this study showed recurring events in which the characters in the book are marginalized. However, the study also showed the resilience and resistance the characters manifests in their exertion for an equal society. Additionally, this Master’s thesis addressed how the English as a Foreign Language classroom with the inclusion of Caged Bird and the usage of Critical Race pedagogy can start a development of fundamental values such as equality and gender roles whilst diminishing prejudice.

No description available.

Two experiments were conducted with caged layer waste. In the first experiment fresh waste was treated with: no additive, 2% formaldehyde, 3% sodium metabisulfite, 1% formaldehyde and 2% propionic acid, 3% formic and 2% propionic acids and stored in polyethylene lined 208 liter metal drums. In experiment II waste treated with 2% formaldehyde, 1 % formaldehyde and 2% prop ionic, 3 % formic and 2% propionic (w/w), stored for at least 42 d, used in a metabolism trial as N supplements to a basal diet fed to sheep. The formaldehyde, formaldehyde/propionic and formic/propionic treatments eliminated the bacterial decomposition of the waste and no undesirable fermentation was observed on the stored material. Waste treated with no additive or sodium metabisulfite underwent putrefaction. Nitrogen supplementation of a basal diet with treated caged layer wastes improved apparent digestibility of crude protein and N retention in sheep fed these diets. Supplementation of a basal diet with chemically treated caged layer waste improves the nutritional value of the diet which suggests that caged layer waste is efficiently utilized as a N source by ruminants when used as a protein supplement. / Master of Science

The cellular operators (Vodacom, Cell C, MTN and now Virgin Mobile) market has over 39-million mobile phone subscribers and the fixed operator (Telkom) has almost 5 million subscribers [13]. Although the telecommunication sector has been experiencing this significant growth (in terms of numbers), monopolisation of the local loop by Telkom has also resulted in communication prices that are not affordable to the majority of South Africans. The government of South Africa has identified cost of telecommunication services as one of the key initiatives that must be addressed to improve equal levels of access to ICT services in general. Local Loop Unbundling (or LLU for short) has been identified by the South African government as a tool that will minimise control that Telkom has over the copper cable connecting exchanges to customers whilst at the same time driving down the costs of Telecommunication in the country. Although some countries have successfully implemented local loop unbundling, some have not been so successful [3]. This dissertation proposes ICT Systems and processes South Africa needs to have in place to become one of the few success stories. The proposed model was validated against the different models adopted in countries like France, Portugal, United Kingdom and Austria. This dissertation develops a model for implementing local loop unbundling in the South African ICT sector. Local loop unbundling (in short LLU) has been successfully (and unsuccessfully) implemented in a number of countries around the world [3]. The model being proposed recommends best practices to be followed by all stakeholders to ensure successful deployment of local loop unbundling. The research takes a closer look at the South African ICT sector and makes recommendations on processes and systems that are necessary to ensure successful deployment of local loop unbundling in South Africa. The dissertation is written from the view of Telkom (The incumbent Operator), competitors (existing ones and new entrants) and the Regulator (ICASA) and focuses mainly on:  Technical Processes and Challenges that must be addressed  Regulatory Process and Challenges that must be addressed  Economic Challenges that must be addressed  Comparison to international ICT Markets and  Recommendations and Conclusions. The dissertation also covers the development of the Local loop unbundling model charter, Local Loop Management website and processes (Annexure A and B) developed (using HTML) used for the management of the unbundling process. Keywords: o Local loop o Caged Co-location / Thesis (M.Ing. (Development and Management Engineering)--North-West University, Potchefstroom Campus, 2009.

The cellular operators (Vodacom, Cell C, MTN and now Virgin Mobile) market has over 39-million mobile phone subscribers and the fixed operator (Telkom) has almost 5 million subscribers [13]. Although the telecommunication sector has been experiencing this significant growth (in terms of numbers), monopolisation of the local loop by Telkom has also resulted in communication prices that are not affordable to the majority of South Africans. The government of South Africa has identified cost of telecommunication services as one of the key initiatives that must be addressed to improve equal levels of access to ICT services in general. Local Loop Unbundling (or LLU for short) has been identified by the South African government as a tool that will minimise control that Telkom has over the copper cable connecting exchanges to customers whilst at the same time driving down the costs of Telecommunication in the country. Although some countries have successfully implemented local loop unbundling, some have not been so successful [3]. This dissertation proposes ICT Systems and processes South Africa needs to have in place to become one of the few success stories. The proposed model was validated against the different models adopted in countries like France, Portugal, United Kingdom and Austria. This dissertation develops a model for implementing local loop unbundling in the South African ICT sector. Local loop unbundling (in short LLU) has been successfully (and unsuccessfully) implemented in a number of countries around the world [3]. The model being proposed recommends best practices to be followed by all stakeholders to ensure successful deployment of local loop unbundling. The research takes a closer look at the South African ICT sector and makes recommendations on processes and systems that are necessary to ensure successful deployment of local loop unbundling in South Africa. The dissertation is written from the view of Telkom (The incumbent Operator), competitors (existing ones and new entrants) and the Regulator (ICASA) and focuses mainly on:  Technical Processes and Challenges that must be addressed  Regulatory Process and Challenges that must be addressed  Economic Challenges that must be addressed  Comparison to international ICT Markets and  Recommendations and Conclusions. The dissertation also covers the development of the Local loop unbundling model charter, Local Loop Management website and processes (Annexure A and B) developed (using HTML) used for the management of the unbundling process. Keywords: o Local loop o Caged Co-location / Thesis (M.Ing. (Development and Management Engineering)--North-West University, Potchefstroom Campus, 2009.

Submitted by Samuel Guimarães Filho (samuelgf@gmail.com) on 2017-03-07T01:39:40Z No. of bitstreams: 1 tese_samuel_revisao_1.pdf: 2212736 bytes, checksum: eef717244d02ccf54ceb936354c64525 (MD5) / Approved for entry into archive by Renata de Souza Nascimento (renata.souza@fgv.br) on 2017-03-07T23:43:25Z (GMT) No. of bitstreams: 1 tese_samuel_revisao_1.pdf: 2212736 bytes, checksum: eef717244d02ccf54ceb936354c64525 (MD5) / Made available in DSpace on 2017-03-08T15:56:07Z (GMT). No. of bitstreams: 1 tese_samuel_revisao_1.pdf: 2212736 bytes, checksum: eef717244d02ccf54ceb936354c64525 (MD5) Previous issue date: 2017-02-10 / This work aims to test if the use of Google Trends as an exogenous variable improves the prediction of the monthly data for Brazilian Formal Job Creation (CAGED) compared to a model that uses only the lags themselves. For the selection of the model was used the algorithm Autometrics and for model comparison the Model Confidence Set. In addition, the model that uses Google Trends data will be compared with some market analyst’s forecasts. The results show that the model the uses the Google data as an exogenous variable is superior to the model that only uses the lag itself. However, this model was not able to overcome the market analysts. / Este trabalho tem como objetivo testar se o uso do Google Trends como variável exógena melhora a previsão do dado mensal do CAGED em relação a modelos que usam apenas as próprias defasagens. Para a seleção do modelo foi utilizado o algoritmo Autometrics e para comparação de modelos o utilzado o Model Confidence Set. Além disto, o modelo que utiliza o Google Trends foi comparado com previsões dos analistas de Mercado. Os resultados encontrados apontam que o modelo que utliza o Google Trends como variável exógena é superior ao modelo que utiliza apenas a própria defasagem. No entanto, este modelo, não foi capaz de superar os analistas de mercado.