Submitted by Diego Venturini null (diego.venturini@lpnet.com.br) on 2017-04-26T03:06:48Z No. of bitstreams: 1 dissertação defesa FINAL.pdf: 3454973 bytes, checksum: 46340a211534e710264ebdb1e5d788ef (MD5) / Approved for entry into archive by Luiz Galeffi (luizgaleffi@gmail.com) on 2017-04-26T12:43:24Z (GMT) No. of bitstreams: 1 venturini_d_me_bauru.pdf: 3454973 bytes, checksum: 46340a211534e710264ebdb1e5d788ef (MD5) / Made available in DSpace on 2017-04-26T12:43:24Z (GMT). No. of bitstreams: 1 venturini_d_me_bauru.pdf: 3454973 bytes, checksum: 46340a211534e710264ebdb1e5d788ef (MD5) Previous issue date: 2017-03-23 / Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq) / A albumina é a proteína solúvel mais abundante no sangue e desempenha um papel crítico na manutenção da pressão osmótica e no transporte de substâncias. A divanilina apresenta propriedades antioxidantes e pode ser usada como intensificador de sabor e cremosidade nos alimentos. Em nosso trabalho realizamos um estudo abrangente sobre a interação da divanilina com a albumina do soro bovino (BSA) aplicando técnicas de fluorescência molecular e dicroísmo circular (CD) para determinar a constante de ligação, as características físico-químicas de suas interações e utilizar a divanilina como sonda suscetível a dicroísmo circular na discriminação de sítios de ligação na albumina a partir do monitoramento do sinal de Dicroísmo Circular Induzido (ICD). Os resultados obtidos indicaram que a divanilina pode se ligar aos sítios I e II, mas liga-se preferencialmente ao sítio de drogas I da BSA com constante de associação (Ka) de 3,33, 2,83, 2,03x105 M-1, em temperaturas de 298, 308 e 318 K, respectivamente. Esses valores foram cerca de 4 vezes mais elevados em comparação com a vanilina. Os valores obtidos de energia livre de Gibbs, variação de entalpia e entropia para a ligação a partir da equação de Van't Hoff foram de -31,5 kJ/mol, -19,42 kJ/mol e 40,8 J/mol.K-1, respectivamente, demonstrando que as forças principais que atuaram para a estabilização do complexo foram ligações de hidrogênio e interações hidrofóbicas. Em presença de BSA a divanilina tornou-se uma molécula quiral, fato evidenciado pelo seu espectro de dicroísmo circular induzido. A quiralidade axial foi teoricamente confirmada a partir do estudo das conformações mais estáveis adotadas pela divanilina usando a Teoria Funcional da Densidade (DFT). Os estudos de Docking molecular confirmaram a estrutura conformacional a qual a divanilina se ligou na BSA sendo a anti-aS com ângulo diedro entre 230º e 241º. A preferência pelo sítio I também pôde ser confirmada pelo docking devido a energia conformacional apresentada para a estrutura da divanilina quando inserida nesse sítio, sendo de -63,1 Kcal/mol enquanto que no sítio 2 a energia obtida foi de -59,7 Kcal/mol. / The albumin is the most abundant soluble protein in blood and plays a critical role in maintaining the osmotic pressure and transport of substances. The divanillin has antioxidant properties and can be used as flavor enhancer in food and creaminess. In this work, we carried out a comprehensive study on the interaction of divanillin with bovine serum albumin (BSA) applying molecular fluorescence techniques and circular dichroism (CD) to determine the binding constant and the physicochemical characteristics of their interactions and use divanillin as susceptible probe circular dichroism in discrimination of albumin binding sites from the ICD signal monitoring. The results indicated that divanillin can bind to sites I and II, but preferentially binds to site I of drugs in BSA with association constant (Ka) 3.33, 2.83, 2.03x105M-1, at temperatures (298, 308, 318K) respectively. These values were about 5 times higher compared to vanillin. The values of Gibbs free energy, enthalpy and entropy changes for the connection from the van't Hoff equation were -31,5 kJ/mol, -19,42 kJ/mol and 40,8 J/mol.K-1, respectively, showing that the main forces that have acted to stabilize the complex were hydrogen bonds and hydrophobic interactions. In the presence of BSA, divanillin became a chiral molecule as evidenced by its induced circular dichroism spectrum. The axial chirality was theoretically confirmed from the study of the most stable conformations adopted by divanillin using the Functional Theory Density (DFT). Axial chirality was theoretically confirmed from the study of the more stable conformations adopted by divanilin using the Functional Density Theory (DFT). Molecular docking studies confirmed the conformational structure to which divanilin bound in BSA with anti-aS having a dihedral angle between 230° and 241°. The preference for site I can also be confirmed by docking due to the conformational energy presented for the divanilin structure when inserted at that site, being -63.1 Kcal/mol while at site 2 the energy obtained was -59.7 Kcal/mol.

La grande majorité des résines époxy utilisées aujourd’hui sont issues ou dérivées du bisphénol-A (BPA). Cependant, le BPA est soumis à de très fortes régulations, notamment vis-à-vis de sa récente classification comme substance chimique extrêmement préoccupante par l’agence européenne des produits chimiques (ECHA). Dans un but d’anticiper les évolutions de régulation, ArianeGroup a décidé de remplacer cette substance chimique de ces formulations. Ces travaux de thèse portent donc sur l’élaboration de nouvelles résines époxy biosourcées ayant des propriétés similaires voire supérieures aux références dérivées du bisphénol-A. Pour cela, une bioplatforme de monomères polyépoxydés issus de la vanilline, du méthyl vanillate, du 2,6-diméthoxyphénol et de l’eugénol a été développée. Ces précurseurs biosourcés ont ensuite été utilisés comme précurseurs de réseaux époxyde par réticulation avec des amines. Les réseaux réticulés biosourcés ainsi obtenus ont démontré des propriétés thermomécaniques remarquables bien supérieures à la référence de type DGEBA, notamment en termes de température de transition vitreuse (>300 °C) et taux de coke (>50%). En parallèle de ces travaux, la synthèse de diamines biosourcées, dérivées de la divanilline, et pouvant être utilisées comme agents de réticulation de résines époxy, a été réalisée. Des réseaux époxyde entièrement biosourcés ont ainsi été synthétisés et présentent des propriétés thermomécaniques prometteuses. / Today, most of the epoxy resins produced are derived from bisphenol-A (BPA). However, BPA is subject to strong regulations, particularly because of its recent classification as chemical of very high concern by the European Chemicals Agency (ECHA). In order to anticipate new regulations, ArianeGroup has decided to replace this substance in its applications. The aim of this thesis is to develop new bio-based epoxy thermosets with comparable thermomechanical properties as the ones issued from bisphenol-A-based materials. For this purpose, a bio-platform of epoxy monomers from vanillin, methyl vanillate, 2,6-dimethoxyphenol and eugenol was developed. These precursors were cross-linked with amines used as curing agent to obtain bio-based epoxy networks. The latter demonstrated thermomechanical properties well above the DGEBA-type reference, especially in terms of glass transition temperature (> 300 °C) and char content (> 50%). Finally, the synthesis of bio-based diamines derived from divanillin was developed and enabled the synthesis of fully bio-based epoxy networks with promising thermomechanical properties.

Dans cette thèse sont développées les synthèses et caractérisations de nouveaux polymères conjugués pour des applications dans l’électronique organique. Ces polymères ont été synthétisés via des réactions de polymérisation sans utilisation de métaux de transition. Des polyazomethines à base de carbazole ont ainsi été synthétisés par polycondensation entre des carbazole portant des fonctions amine et aldéhyde en positions 2,7 et 3,6. Leurs propriétés optiques et électroniques ont été étudiées en fonction de la position des fonctions imines ainsi formées. Un comonomère de type EDOT a ensuite été intégré dans le polymère et l’impact de ce comonomère sur les propriétés du copolymère ainsi formé a été étudié.Des polymères à base d’acide squarique et croconique ont ensuite été synthétisés. En faisant varierles conditions de synthèse, les propriétés optoélectroniques ont pu être contrôlées, permettant d’obtenir des composés présentant une émission blanche, qui ont ensuite été intégrés en tant que couche active dans des dispositifs de type OLED.Enfin, des polymères plus originaux ont été étudiés, utilisant des réactions de polymérisation originale, permettant par exemple la formation de benzobisthiazole in situ. D’autres polymères ont été synthétisés en intégrant dans leur chaine des monomères originaux, comme la tetrazine ou la divanilline. Les propriétés optoélectroniques de ces composés ont ensuite été étudiées en vue deleur éventuelle intégration dans des dispositifs. / In this work, synthesis and characterizations of new conjugated polymers are described.These polymers, developed for their integration into devices, have been synthesized via transitionmetalfree polymerizations. Carbazole based polyazomethines have been synthesized via polycondensation reactions between di-substituted carbazoles, bearing amino and formyl functionsin positions 3,6 or 2,7. Optical and electronical properties of such polymers have been studieddepending of the linkage position. A comonomer EDOT has then been integrated into the polymer chain, and impact of such insertion has been studied. Squaric and croconic acid base polymers have also been synthesized. By varying polymerization conditions, optoelectronic properties have been tuned, leading to the formation of polymers exhibiting a white emission. These polymers have then been integrated into OLED, as the active layer. Finally, more original polymers have been synthesized, using more original reactions or monomers such as by forming in situ benzobisthiazole. Other polymers integrating more originals monomers, such a tetrazine or divanillin, have been synthesized. Optoelectronic properties of such materials have been studied for the purpose of their integration into devices.