No description available.

Thiol-ene radical coupling is increasingly used for the biofunctionalisation of biomaterials and the formation of 3D hydrogels enabling cell encapsulation. Indeed, thiol-ene chemistry presents interesting features that are particularly attractive for platforms requiring specific reactions of peptides or proteins, in particular in situ, during cell culture or encapsulation: thiol-ene coupling occurs specifically between a thiol (from cysteine residues for example) and a non-activated alkene (unlike Michael addition); it is relatively tolerant to the presence of oxygen; it can be triggered by light, to trigger dynamic systems or for patterning. Despite such interest, little is known about the factors impacting thiol-ene chemistry in situ, under biologically relevant conditions. Here we explore some of the molecular parameters controlling photo-initiated thiol-ene coupling chemistry with a series of alkenes and thiols, including peptides, in buffered conditions. 1H NMR spectroscopy and HPLC were used to quantify the efficiency of couplings and the impact of the intensity of UV exposure, pH of the buffer, as well as the molecular structure and local microenvironment close to alkenes and thiols to be coupled. Our studies demonstrate that molecular design should be carefully selected in order to achieve high biofunctionalisation levels in biomaterials with peptides.

Thiol-ene chemistry is versatile and efficient and can be used as a powerful tool in polymer synthesis. In this thesis, the concept of thiol-ene chemistry has been central, where it has been explored as a tool for the synthesis of well-defined hydrogels and dopa-functional materials towards biomedical applications; such as hydrogels, primers for adhesive fixation of bone fractures, self-healing gels, and micelles for drug-delivery. Using thiol-ene chemistry, well-defined hydrogels were realized in order to study how the structure influences properties such as swelling, stiffness and hydrolytic degradation. It was found that all these characteristics are related to each other, as a more loosely crosslinked hydrogel experiences higher swelling, lower stiffness and higher degradation rates. Dopa-functional materials have gained a lot of interest throughout the years due to the remarkable adhesive properties they possess in wet environments. In the pursuit of new primers towards thiol-ene functional crosslinked bone adhesives, compounds with dopa moieties were proposed. Primers derived from dopamine were found to enhance the adhesion towards bone, and it was concluded that addition of NaOH was essential to achieve good adhesion. The strongest adhesion was achieved when thiol and ene-functional primers were used in combination. Most synthetic routes to dopa-functional polymers involve several protection and deprotection steps and a more simplistic synthetic route is therefore desired. The possibility of using UV-initiated thiol-ene chemistry to produce dopa-functional polymers was therefore investigated. The resulting polymers were shown to exhibit self-healing properties upon complexation with Fe3+ ions. Finally, the developed synthetic route was used to produce dopa and allyl-functional triblock-co-polymers. These triblock-co-polymers were then used to form micelles and evaluated as drug-delivery vehicles for the cancer-drug doxorubicin. The micelles were found to have high drug-loading capacities and slow release profiles and showed promising results when evaluated against breast-cancer cells. / Reaktioner mellan tioler och omättade kemiska föreningar utgör ett mångsidigt och effektivt redskap inom polymersyntes. I denna avhandling har begreppet tiol-en kemi varit centralt och kemin har använts för syntes av såväl väldefinierade hydrogeler som dopa-funktionella material. Dessa material har sedan utvärderats mot biomedicinska tillämpningar såsom hydrogeler, primers för fixering av benfrakturer, självläkande geler och kontrollerad läkemedelsleverans. Tiol-en-kemi har i denna avhandling använts för att framställa väldefinierade hydrogeler som sedan utvärderats med avseende på hur strukturen påverkar egenskaper såsom svällningsgrad, styvhet och nedbrytningshastighet. Det visade sig att alla dessa egenskaper är relaterade till varandra och att lösare tvärbundna hydrogeler uppvisar högre svällning, lägre styvhet och högre nedbrytningshastigheter. Marina musslor har en exceptionell förmåga att fästa mot olika ytor och på grund av detta har det visats en hel del intresse för dopa-funktionella material genom åren. På jakt efter en primer för att öka vidhäftningen hos benlim proponerades därför föreningar med dopafunktionella grupper. Det visade sig att dopaminderivat kunde förbättra vidhäftningen mot ben och det visade sig även att tillsats av natriumhydroxid var viktigt för att uppnå god vidhäftningsförmåga. Den starkaste vidhäftning uppnåddes när derivat med tiol och omättade bindningar användes i kombination. Syntes av dopafunktionella material involverar ofta flera reaktionssteg och en förenklad syntesväg är därför att eftersträva. UV-initierad tiol-en-kemi undersöktes därför som en möjlig syntesväg för att framställa dopafunktionella polymerer. Polymererna visade sig ha självläkande egenskaper vid komplexbildning med järnjoner. Slutligen användes denna syntesväg för att framställa blocksampolymerer. Dessa blocksampolymerer användes sedan för att bilda miceller med lovande resultat vid utvärdering för leverans av läkemedel mot bröstcancer. / <p>QC 20160125</p>

No description available.

Este trabalho teve como objetivo geral analisar de que modo a articulação entre os atores sociais envolvidos no Encontro Nacional de Educação (ENE) contribui para a constituição de um sujeito sociopolítico para disputar a produção de um projeto de educação para o Brasil. Para realizar este estudo, aproximei-me do grupo que construiu as etapas do RS e de POA frequentando, no período de março de 2016 a maio de 2017, reuniões e trabalhado na realização dessas duas etapas no mês de abril de 2016. Posteriormente, participei da etapa nacional do Encontro realizada entre os dias 16 e 18 de junho de 2016 na cidade Brasília - DF. Para realizar a análise proposta neste estudo, busquei na Teoria da Produção Social, elaborada pelo chileno Carlos Matus, e nas elaborações teóricas da argentina Isabel Rauber, a respeito da articulação entre atores e da constituição do sujeito sociopolítico, os elementos teóricos que pudessem contribuir no atingimento do objetivo deste trabalho. Assim, a articulação produzida entre os atores sociais envolvidos no ENE para disputar a produção de um projeto de educação para o Brasil foi o caso estudado. Como resultados desta pesquisa, observei que os atores sociais partiram de estratégias interativas predominantemente cooperativas para se articular em torno do ENE na Coordenação Nacional das Entidades em Defesa da Educação Pública e Gratuita (CONEDEP). A predominância da cooperação ao interagirem ocorreu porque os atores identificam problemas relacionados, partem de situações em comum e perseguem objetivos semelhantes em relação às políticas educacionais brasileiras. Essa articulação construiu uma unidade de ação de atores articulada nacionalmente e que pode ser fortalecida através da articulação das bases regionais dos atores. Com essa coordenação das ações e manutenção de práticas permanentes de trabalho nacionais e regionais, os atores poderão produzir o projeto de educação que almejam e constituir o sujeito sociopolítico. Esse sujeito atua como uma unidade de ação dos atores orientada pelo projeto produzido, podendo acumular poder e ter, assim, a força necessária para disputar a produção de um projeto de educação para o Brasil. / This study aimed to analyze how the articulation among social actors involved in the Encontro Nacional de Educação (ENE) contributes to the constitution of a sociopolitical subject to compete for the production of an education project for Brazil. In order to carry out this study, I approached to the group that built the RS and POA stages, attending meetings between March 2016 and May 2017 and worked on these two stages in April 2016. Later, I participated of the national stage of the Encontro held between June 16 and 18, 2016 in the city of Brasília - DF. In order to carry out the analysis proposed in this study, I sought in the Theory of Social Production, elaborated by the Chilean Carlos Matus, and in the theoretical elaborations of the Argentine Isabel Rauber, regarding the articulation between actors and the constitution of the sociopolitical subject, the theoretical elements that could contribute in the objective of this work. Thus, the articulation produced among the social actors involved in the ENE to dispute the production of an education project for Brazil was the case studied. As a result of this research, I observed that the social actors started from predominantly cooperative interactive strategies to articulate around the ENE in the Coordenação Nacional das Entidades em Defesa da Educação Pública e Gratuita (CONEDEP). The predominance of cooperation while interacting occurred because the actors identify related problems, start from common situations and pursue similar goals in relation to Brazilian educational policies. This articulation has built a unit of action of actors articulated nationally and that can be strengthened through the articulation of the regional bases of the actors. With this coordination of actions and the maintenance of permanent national and regional work practices, the actors will be able to produce the education project that they seek and constitute the sociopolitical subject. This subject acts as a unit of action of the actors oriented by the project produced, being able to accumulate power and thus have the force to dispute the production of an education project for Brazil.

Methylene-butyrolactones are readily accessed by two methodologies based on a particular ene reaction. Both methodologies have been applied to the synthesis of the northern fragment of Polycavernoside. A reverse Julia reaction was used as the key step of a new methodology towards triene frameworks ; a mechanistic study revealed the unexpected role of triflic acid in the field of metal triflates catalysed acylation of alcohols, and a new tandem Brook rearrangement-allylation sequence was developed in the viewpoint of an improved total synthesis of Polycavernoside A.

Methylene-butyrolactones are readily accessed by two methodologies based on a particular ene reaction. Both methodologies have been applied to the synthesis of the northern fragment of Polycavernoside. A reverse Julia reaction was used as the key step of a new methodology towards triene frameworks ; a mechanistic study revealed the unexpected role of triflic acid in the field of metal triflates catalysed acylation of alcohols, and a new tandem Brook rearrangement-allylation sequence was developed in the viewpoint of an improved total synthesis of Polycavernoside A.

Este trabalho teve como objetivo geral analisar de que modo a articulação entre os atores sociais envolvidos no Encontro Nacional de Educação (ENE) contribui para a constituição de um sujeito sociopolítico para disputar a produção de um projeto de educação para o Brasil. Para realizar este estudo, aproximei-me do grupo que construiu as etapas do RS e de POA frequentando, no período de março de 2016 a maio de 2017, reuniões e trabalhado na realização dessas duas etapas no mês de abril de 2016. Posteriormente, participei da etapa nacional do Encontro realizada entre os dias 16 e 18 de junho de 2016 na cidade Brasília - DF. Para realizar a análise proposta neste estudo, busquei na Teoria da Produção Social, elaborada pelo chileno Carlos Matus, e nas elaborações teóricas da argentina Isabel Rauber, a respeito da articulação entre atores e da constituição do sujeito sociopolítico, os elementos teóricos que pudessem contribuir no atingimento do objetivo deste trabalho. Assim, a articulação produzida entre os atores sociais envolvidos no ENE para disputar a produção de um projeto de educação para o Brasil foi o caso estudado. Como resultados desta pesquisa, observei que os atores sociais partiram de estratégias interativas predominantemente cooperativas para se articular em torno do ENE na Coordenação Nacional das Entidades em Defesa da Educação Pública e Gratuita (CONEDEP). A predominância da cooperação ao interagirem ocorreu porque os atores identificam problemas relacionados, partem de situações em comum e perseguem objetivos semelhantes em relação às políticas educacionais brasileiras. Essa articulação construiu uma unidade de ação de atores articulada nacionalmente e que pode ser fortalecida através da articulação das bases regionais dos atores. Com essa coordenação das ações e manutenção de práticas permanentes de trabalho nacionais e regionais, os atores poderão produzir o projeto de educação que almejam e constituir o sujeito sociopolítico. Esse sujeito atua como uma unidade de ação dos atores orientada pelo projeto produzido, podendo acumular poder e ter, assim, a força necessária para disputar a produção de um projeto de educação para o Brasil. / This study aimed to analyze how the articulation among social actors involved in the Encontro Nacional de Educação (ENE) contributes to the constitution of a sociopolitical subject to compete for the production of an education project for Brazil. In order to carry out this study, I approached to the group that built the RS and POA stages, attending meetings between March 2016 and May 2017 and worked on these two stages in April 2016. Later, I participated of the national stage of the Encontro held between June 16 and 18, 2016 in the city of Brasília - DF. In order to carry out the analysis proposed in this study, I sought in the Theory of Social Production, elaborated by the Chilean Carlos Matus, and in the theoretical elaborations of the Argentine Isabel Rauber, regarding the articulation between actors and the constitution of the sociopolitical subject, the theoretical elements that could contribute in the objective of this work. Thus, the articulation produced among the social actors involved in the ENE to dispute the production of an education project for Brazil was the case studied. As a result of this research, I observed that the social actors started from predominantly cooperative interactive strategies to articulate around the ENE in the Coordenação Nacional das Entidades em Defesa da Educação Pública e Gratuita (CONEDEP). The predominance of cooperation while interacting occurred because the actors identify related problems, start from common situations and pursue similar goals in relation to Brazilian educational policies. This articulation has built a unit of action of actors articulated nationally and that can be strengthened through the articulation of the regional bases of the actors. With this coordination of actions and the maintenance of permanent national and regional work practices, the actors will be able to produce the education project that they seek and constitute the sociopolitical subject. This subject acts as a unit of action of the actors oriented by the project produced, being able to accumulate power and thus have the force to dispute the production of an education project for Brazil.

Este trabalho teve como objetivo geral analisar de que modo a articulação entre os atores sociais envolvidos no Encontro Nacional de Educação (ENE) contribui para a constituição de um sujeito sociopolítico para disputar a produção de um projeto de educação para o Brasil. Para realizar este estudo, aproximei-me do grupo que construiu as etapas do RS e de POA frequentando, no período de março de 2016 a maio de 2017, reuniões e trabalhado na realização dessas duas etapas no mês de abril de 2016. Posteriormente, participei da etapa nacional do Encontro realizada entre os dias 16 e 18 de junho de 2016 na cidade Brasília - DF. Para realizar a análise proposta neste estudo, busquei na Teoria da Produção Social, elaborada pelo chileno Carlos Matus, e nas elaborações teóricas da argentina Isabel Rauber, a respeito da articulação entre atores e da constituição do sujeito sociopolítico, os elementos teóricos que pudessem contribuir no atingimento do objetivo deste trabalho. Assim, a articulação produzida entre os atores sociais envolvidos no ENE para disputar a produção de um projeto de educação para o Brasil foi o caso estudado. Como resultados desta pesquisa, observei que os atores sociais partiram de estratégias interativas predominantemente cooperativas para se articular em torno do ENE na Coordenação Nacional das Entidades em Defesa da Educação Pública e Gratuita (CONEDEP). A predominância da cooperação ao interagirem ocorreu porque os atores identificam problemas relacionados, partem de situações em comum e perseguem objetivos semelhantes em relação às políticas educacionais brasileiras. Essa articulação construiu uma unidade de ação de atores articulada nacionalmente e que pode ser fortalecida através da articulação das bases regionais dos atores. Com essa coordenação das ações e manutenção de práticas permanentes de trabalho nacionais e regionais, os atores poderão produzir o projeto de educação que almejam e constituir o sujeito sociopolítico. Esse sujeito atua como uma unidade de ação dos atores orientada pelo projeto produzido, podendo acumular poder e ter, assim, a força necessária para disputar a produção de um projeto de educação para o Brasil. / This study aimed to analyze how the articulation among social actors involved in the Encontro Nacional de Educação (ENE) contributes to the constitution of a sociopolitical subject to compete for the production of an education project for Brazil. In order to carry out this study, I approached to the group that built the RS and POA stages, attending meetings between March 2016 and May 2017 and worked on these two stages in April 2016. Later, I participated of the national stage of the Encontro held between June 16 and 18, 2016 in the city of Brasília - DF. In order to carry out the analysis proposed in this study, I sought in the Theory of Social Production, elaborated by the Chilean Carlos Matus, and in the theoretical elaborations of the Argentine Isabel Rauber, regarding the articulation between actors and the constitution of the sociopolitical subject, the theoretical elements that could contribute in the objective of this work. Thus, the articulation produced among the social actors involved in the ENE to dispute the production of an education project for Brazil was the case studied. As a result of this research, I observed that the social actors started from predominantly cooperative interactive strategies to articulate around the ENE in the Coordenação Nacional das Entidades em Defesa da Educação Pública e Gratuita (CONEDEP). The predominance of cooperation while interacting occurred because the actors identify related problems, start from common situations and pursue similar goals in relation to Brazilian educational policies. This articulation has built a unit of action of actors articulated nationally and that can be strengthened through the articulation of the regional bases of the actors. With this coordination of actions and the maintenance of permanent national and regional work practices, the actors will be able to produce the education project that they seek and constitute the sociopolitical subject. This subject acts as a unit of action of the actors oriented by the project produced, being able to accumulate power and thus have the force to dispute the production of an education project for Brazil.

Cette thèse présente la réactivité de diènes polyfonctionnalisés incorporant un atome de bore (diènes borylés) en présence de composés de type nitroso. La première partie est une étude de la réactivité des diènes borylés en présence de dérivés arylnitroso. Le produit formé ainsi que l'efficacité de la réaction est dépendant de la substitution sur l'atome de bore ainsi que du solvant utilisé pour la réaction. Suivant les conditions employées, la formation de composés avec différentes structures; pyrroles, oxazines substitués par un atome de bore, ou nitrones a été obtenue. Une stratégie one-pot a ensuite été développée pour la synthèse d'oxazolines utilisant la formation des nitrones en tant qu'intermédiaire. Des investigations théoriques et pratiques concernant le mécanisme de la formation du pyrrole ont été réalisées. La séquence expliquant la synthèse de cette structure est basée sur la cascade suivante; cycloaddition régiosélective (Nitroso Diels-Alder)/réarrangement/élimination du borate. La formation des composés de type nitrone n'a pas été totalement explicité. Des recherches sont actuellement en cours dans le but d'obtenir plus de détails sur le mécanisme mis en jeu. La deuxième partie de l'étude est orientée sur la réactivité des diènes borylés en présence de dérivés carbonylnitroso. Au contraire des dérivés arylnitroso, la nature du composé carbonylnitroso joue un rôle majeur sur la réactivité. Si le même type de réactivité engendrant la formation de pyrroles et d'oxazines substitués par un atome de bore a été observé dans certains cas, l'utilisation d'un composé carbonylnitroso étant assez pauvre en électrons génère la formation du produit issu d'une réaction nitroso-ène. Ce produit, issu de la réaction nitrosoène, a été utilisé comme intermédiaire clé pour la synthèse de différents produits polycycliques. Une séquence one-pot, multicomposants, Diels-Alder/allylboration a été optimisée donnant différentes structures suivant le dienophile et l'aldehyde employé. Dans le but de diversifier la chimie du produit résultant de la réaction nitroso-ène, une autre séquence a été mise au point utilisant la synthèse des pyrroles. Une voie multi-étape a permis la synthèse de nouvelles structures bicycliques incorporant une oxazine et un pyrrole. / This thesis presents the reactivity of dienylboronated compounds towards arylnitroso and carbonylnitroso derivatives and its use in the synthesis of heterocyclic and polycyclics compounds. The first study focused on the reactivity of dienylboronate compounds with arylnitroso derivatives resulting in pyrrole or furan products. The outcome and efficiency of the reaction is related to the boron on the dienyl moiety and the solvent used. Using the certain conditions, pyrroles, boronated MIDA ester oxazines or nitrones could be obtained. A one-pot strategy was then applied to synthesise oxazoline derivatives using nitrones as an intermediate. Theoretical, as well as experimental, work has supported that the formation of the pyrrole was obtained by a regioselective nitroso Diels-Alder reaction/rearrangement/borate elimination cascade process. Details on the nitrone formation have not been clarified, but further investigations are on-going. Secondly, attention was focused on the reactivity of dienylboronate compounds with carbonylnitroso derivatives. Contrary to the arylnitroso species, the nature of the carbonylnitroso had a dramatic impact on reactivity. On the one hand, similar reactivity towards the formation of pyrroles and boronated MIDA ester oxazines was observed, however, by employing a higher electron-deficient carbonylnitroso species, the product resulting from a nitroso-ene reaction was obtained. Ene-product was used as the key intermediate for the synthesis of different polycyclic compounds. A multicomponent, one-pot, Diels-Alder/allylboration procedure was optimised to yield various structures depending on the nature of the dienophile and the aldehyde. To diversify the chemistry of the ene-product another sequence was designed using the pyrrole synthesis. A multi-step pathway was optimised to afford novel fused bicylic oxazine-pyrrole products.