Depuis une quinzaine d’années, les polymères chiraux sont utilisés dans de nombreuses applications, comme phases stationnaires pour la séparation d’énantiomères ou encore en tant que catalyseurs en synthèse asymétrique. Aux vues de ces intérêts grandissants, de nombreuses méthodes ont émergé afin de les synthétiser. Nous nous sommes concentrés sur des méthodes organocatalytiques originales de synthèse de polymères chiraux par réaction de polyaldolisation et par désymétrisation de bis-anhydrides. Nous avons ainsi développé des processus de désymétrisation itératifs et ainsi généré une chiralité C-centrée sur la chaine polymérique. Des polyesters chiraux ont ainsi été obtenus avec de très bonnes séléctivités. / Chiral polymers are used in many applications such as stationary phases for chiral HPLC and catalysts in asymetric synthesis. The synthesis of chiral polymers traditionally deals with metal catalysts-based methodologies and often involved sensitive substrates. On the other hand, only a limited number of publications has been reported through environmentally-friendly organocatalytic pathways.The goal of this Ph.D. studies was devoted to the design of new routes toward chiral polymers under organocatalysis. We chose polyaldolisations and anhydride desymmetrizations with alcohols as key reactions to obtain original polymers with a C-centered chirality in the main polymer chain.

Polipropileno (PP) é um termoplástico com ótimo balanço de propriedades, baixo custo e largo espectro de aplicações. Seu uso como material de engenharia é limitado pelos seus valores relativamente baixos de propriedades mecânicas. A adição de reforço ao PP melhora suas propriedades termomecânicas, tornando-o adequado para fabricação de peças de engenharia como composto termoplástico. Fibra de vidro (FV) é o reforço mais empregado em compostos de PP devido a maior resistência mecânica específica gerada no PP e por atuar como agente nucleante. Devido à diferença entre as naturezas das ligações secundárias, há pouca afinidade química entre PP-FV, sendo necessária a modificação interfacial através de agentes de acoplamento poliméricos (AA) para melhorar o desempenho termomecânico deste composto. Averiguou-se neste trabalho a influência de dois AA, um à base de PP e outro à base de EPDM, ambos graftizados com anidrido maleico (PAM e EAM, respectivamente), no comportamento térmico do composto PP∕FV. Os compostos PP30FV-AA foram preparados em extrusora dupla rosca ZSK 26, e posteriormente injetados em uma injetora Airburg para obtenção de corpos de prova utilizando teor fixo de 30% FV e teores de 0,5∕1,0∕2,0% AA. O PP e seus compostos foram caracterizados via microscopia óptica acoplada à placa Hot Stage, cristalização isotérmica e não isotérmica por calorimetria (DSC), resistência à deflexão térmica (HDT), morfologia da fratura (MEV) e comportamento viscoelástico (DMA) para analisar a influência do AA e da FV. Os resultados obtidos foram avaliados estatisticamente via metodologia ANOVA (Analysis of Variance). O efeito sinérgico FV-AA na cristalização isotérmica do PP foi dependente da combinação temperatura-natureza-teor de AA, sendo a temperatura o fator preponderante. A interação interfacial entre a matriz- reforço foi substancialmente favorecida pelo PAM. O uso de EAM retardou a cristalização do PP, enquanto que o PAM favoreceu este processo. Constatou-se que o AA teve pouca influência no tempo de meia-vida de cristalização nas menores isotermas e, para isotermas mais próximas à fusão do PP, o PAM apresentou menores valores deste parâmetro. Os valores de deflexão térmica foram semelhantes para todas as formulações contendo PAM, enquanto que a adição de EAM decresceu esta propriedade. Em temperaturas inferiores à transição vítrea (Tg) do PP, todos os compostos com AA apresentaram menor módulo elástico em relação ao composto puro; em temperaturas superiores à Tg, o PAM favoreceu aumentou esta propriedade na faixa de temperatura em que o composto usualmente é utilizado. / Polypropylene (PP) features by its properties balance, price and large array of applications. However, its use as engineering component is limited by relative low mechanical properties. PP reinforcement improves its thermomechanical properties, turning it into suitable to produce engineering components as a reinforced thermoplastic composite. Glass fiber (GF) is the most usual reinforce utilized in PP due to its great specific mechanical strength elastic modulus and nucleation capability. In reason of different secondary bonds between PP and GF, it is mandatory to modify the interface between these domains through polymeric coupling agents (CA) to improve thermomechanical performance. It was evaluated the influence of two CA based on PP and EPDM grafted with maleic anhydride (PAM and EAM) on thermal behavior of PP∕GF composite. PP30GF-CA composites were prepared in a twin screw extrusor ZSK 26 and injected in an injector Airburg with fixed GF content (30%) and different CA contents (0.5∕1.0∕2.0%). PP and PP composites were analyzed by optical microscopy with Hot Stage, isothermal and non-isothermal crystallization (DSC), as well as viscoelastic behavior. The results were statistically evaluated by ANOVA (Analysis of Variance) methodology. The synergic role between GF∕CA in PP crystallization was dependent on temperature-nature-CA content, mainly influenced by temperature. Interfacial adhesion was mainly favored by PAM. The results pointed a possible PP isotherm crystallization retardant by EAM, whereas PAM significantly favored this same process. CA presence in PP30GF composite did not influence crystallization half-life time values in lower isotherms, while in isotherms near PP melting temperature, PAM considerably decreased this parameter. Deflection thermal values were not affected by PAM, while EAM decreased this property in whole formulations. CA did not improved PP∕GF elastic modulus below PP glass transition (Tg), while in temperatures above Tg, PAM improved PP-GF this same parameter.

Resumo: O presente trabalho teve como objetivo analisar a viabilidade de uso do anidrido naftálico (NA) no tratamento de sementes de espécies gramíneas, assim como no tratamento de toletes de Saccharum spp, contra os efeitos causados por herbicidas inibidores da síntese de carotenóides. O trabalho foi constituído de quatro etapas, sendo as etapas 1 e 3 conduzidas a campo e em casa de vegetação no NUPAM/FCA/UNESP, Botucatu-SP, e as etapas 2 e 4, em estufa plástica e a campo na ESAPP e Empresa Guacho S/A, Paraguaçu Paulista-SP. Nas etapas 1, 2 e 3, de forma geral, foi estudado para as espécies Sorghum bicolor; Penisetum americanum, Panicum maximum, Brachiaria brizantha e Zea mays o efeito da combinação ou não do tratamento de sementes com NA submetidas ao uso dos herbicidas isoxaflutole (IFT) e clomazone, utilizando-se diferentes dosagens, tipos de solos e formas de aplicação. Na etapa 4 foi estudada a combinação de NA no tratamento de toletes da variedade SP 813250 (testemunhas sem NA; aplicação por imersão em solução de 3,0 g L-1 por duas horas; pulverização de 25 g ha-1 de NA sobre os colmos) e herbicida (testemunha; 112 g ha-1 de isoxaflutole; 1440 g ha-1 de metribuzin), e mais um tratamento adicional, onde os toletes foram imersos apenas em água sem adição de NA. O uso de NA (0,50% de p/p) no tratamento de sementes reduziu a intoxicação do híbrido Colorado 32 contra a ação do isoxaflutole, em pré-emergência da cultura, assim como favoreceu o aumento da produtividade dos híbridos Cargill 435 e Colorado 32, na ausência ou presença do efeito herbicida. O tratamento de sementes com NA (0,50% de p/p) protegeu a espécie S. bicolor BR 304 contra os sintomas visuais de intoxicação do isoxaflutole (112 g ha-1) e clomazone (1000 g ha-1)... (Resumo completo, clicar acesso eletrônico abaixo) / Abstract: The present work had as objective to analyze the viability of naphthalic anhydride (NA) use in grass crops, through seed treatment, as well as in stalks treatment of Saccharum spp, against the effects caused by carotenoid synthesis inhibitor herbicides. The work was constituted by four step, being the 1st and 3rd ones carried out in field conditions and glasshouse at the NUPAM/FCA/UNESP, Botucatu - São Paulo State; 2nd and 4th step were conducted in plastic greenhouse and field at the ESAPP and Guacho S/A, Paraguaçu Paulista - São Paulo State. In a general way, 1st, 2nd and 3rd step was studied Sorghum bicolor; Penisetum americanum, Panicum maximum; Brachiaria brizantha and Zea mays L. species in the combination with the effect or not of seed treatment with NA submitted to the isoxaflutole and clomazone, being used different doses, kinds of soils and application forms. In 4th step, treatments included the combination of three conditions of NA stalk treatment, SP 813250 variety (check without NA; application by immersion in solution of 3,0 g L-1 of NA for two hours; spraying of 25 g ha-1 of NA over the stalks) and three herbicide conditions (check without herbicide; 112 g ha-1 at isoxaflutole; 1440 g ha-1 at metribuzin), and an additional treatment, where the stalks were just put inside water without NA. Seed treatment with NA (0,50% of w/w) reduced Colorado 32 hybrid intoxication by isoxaflutole action in preemergence of the crop, as well as favored the increase of Cargill 435 and Colorado 32 hybrids yield, in the absence or presence of herbicide effect. Seed treatment with NA (0,50% of p/p) protected S. bicolor BR 307 against the visual isoxaflutole (112 g ha-1) and clomazone (1000 g ha-1... (Complete abstract, click electronic address below) / Orientador: Edivaldo Domingues Velini / Coorientador: Sílvio José Bicudo / Banca: Dagoberto Martins / Banca: Julio Cesar Durigan / Banca: Rubem S. de Oliveira Junior / Banca: Reginaldo Teodoro de Souza / Doutor

Poly (co iso-butyl vinyl ether-alt-maleic anhydride), an alternating copolymer, was synthesised. For this class of copolymers the formation of an electron-donor complex is invoked to explain their microstructure in which the two comonomers strictly alternate. Due to its polarity, this copolymer constitutes a potential additive for imparting hydrophilic properties to a hydrophobic matrix. In order to obtain narrow molecular weight polymers and study the relation between the molecular weight of this additive and its ability to migrate to the host polymer surface, chain transfer agents were introduced in the system and also the Reversible Addition-Fragmentation chain Transfer (RAFT) process was employed. Free radical polymerisation was first carried out to allow for a comparison with the RAFT process and kinetics of copolymerisation was studied by NIR-FTIR and 1H NMR spectroscopy in order to analyse the rate of reaction of each comonomer. Dibenzyl trithiobenzoate, 3-benzyl sulfanyl thiocarbonyl sulfanyl-propionic acid and dibenzyl trithiobenzoate were used as RAFT agents. Results demonstrate that only benzyl dithiobenzoate is able to control the molecular weight of this copolymer and decrease its polydispersity index; possible reasons laying behind this result are discussed. It was also found that, in particular in the presence of benzyl dithiobenzoate, poly(iso-butyl vinyl ether) forms. This is an unusual phenomenon considering that the free radical polymerisation affords alternating copolymers and that iso-butyl vinyl ether is a monomer that polymerises through the cationic process. Experiments were carried out in various solvents in an attempt to counteract this side reaction, but no appreciable correlation between the properties of the solvents and the formation of homopolymer were found. Various hypothesis are considered, however it is likely that, in the conditions adopted, the presence of the RAFT agents alters the equilibrium constant of complex formation favouring the synthesis of the homopolymer. In addition to this side???reaction also inhibition of the copolymerisation reaction was at times encountered and an investigation into this phenomenon was also conducted.

In the recent years, development of various organic and inorganic nano-sized systems has gained great interests especially for cancer diagnosis and treatment and intense researches are carried out in this area. Regarding to the recent trends for drug delivery system design, the novel approaches for drug carriers are mainly based on development of smart and nano-size drug carriers which are targeted to cancer cells. Hence, for an effective tumor-targeted delivery device, besides its chemical structure further criteria such as detection of tumor site and sensitivity to the higher temperature and lower pH of the tumor compare to rest of the body gains importance. The aim of this study is to design and prepare polysebacic anhydride (PSA) based nanocapsules (NCs) loaded with Doxorubicin (DOX) which is an anti cancer drug. In order to obtain an intelligent delivery system, drug-loaded nanocapsules were coated with pH sensitive poly (L-histidine). PSA nano-carriers were firstly loaded with DOX and then in order to introduce pH sensitivity, they were coated with poly (L-histidine). PLH-coated NCs were modified with polyethylene glycol (PEG) to prevent their macrophage uptake. Drug release profile from this system was examined in two different buffer solutions prepared as acidic (pH 4) and physiological (pH 7.4) media. The physical and chemical properties of the nano particles were characterized by Fourier transform infrared spectroscopy (FTIR), dynamic light scattering (DLS), ultraviolet and visible absorption spectroscopy (UV-VIS), and scanning electron microscopy (SEM). In vitro studies of the prepared nanocapsules were performed on MDA-MB-231 breast cancer cells by using WST Kit 8 cell viability test. In order to obtained results, pH sensitive nanocapsules with size 230 nm exhibited cellular uptake and promising intracellular release of drug.

No description available.

Due to brittleness of polystyrene, PS, its usage area is restricted. To solve this problem and expand the usage area of PS, it can be blended and impact modified with an elastomeric material. In this study, the decrease in the modulus and tensile strength imparted by impact modification was overcome by reinforcing this mixture by incorporating organoclays and producing nanocomposites. This study consists of two parts. In the first part of this study three different types of aliphatic elastomeric materials and three different types of organoclays were used and their effects on the morphology, mechanical, thermal, and rheological properties of PS were investigated. Lotader AX8900, Lotader AX8840 and Lotader 2210 were chosen as the aliphatic elastomeric compatibilizers / and Cloisite

The synthesis of ion-exchange resin which can be used in various separation and chemical purposes, such as diffusion dialysis, electro dialysis, electrolysis and fuel cells has of considerable interest. For all these applications, the interactions of the ionic groups and the resulted morphologies are critical for establishing the unique properties. Considerable researches have been continued to understand the microstructure of these materials. The aim of this study is to synthesize polypropylene (PP) based ion exchange resins and to investigate their ion-exchange properties. In the first part of this study polypropylene was functionalized by grafting maleic anhydride onto the polypropylene and the product was characterized by ATR. The effect of maleic anhydride introduced to the grafting medium and the effect of the radical initiator on the maleic anhydride content of the MA-g-PP samples were investigated. In the second part, neutralization of the MA-g-PP samples with Na+, K+, Mg2+ and Ca2+ ions and peroxide cross-linking of neutralized MA-g-PP samples were performed. Characterization of the neutralized MA-g-PP samples were performed by ATR and SEM-EDX. In the last part of the study, ion exchange properties of MA-g-PP resins towards Cu2+, Co2+, Cd2+, Pb2+ and Fe3+ ions at different pHs were investigated by batch equilibrium method. Rate of metal uptake, concentration effect on the metal uptake and regeneration of the MA-g-PP samples were also examined.

Les polyélectrolytes sont une classe importante de polymères qui ont été étudiés durant plus de 3 décennies. Le domaine des polyélectrolytes subit actuellement une étonnante explosion d'activité dans plusieurs champs scientifique: chimie, biologie, médecine, physique, nanomatériaux, nanotechnologies L'intérêt particulier montré aux polyélectrolytes est dû non seulement au besoin d'une meilleure compréhension de leur comportement, mais aussi à leurs applications commerciales potentielles.<br />La solubilité dans l'eau est la propriété la plus importante des polyélectrolytes, ce qui nous permet d'obtenir des dérivés multifonctionnels avec une toxicité réduite, respectueux de l'environnement et à bas prix. Une des applications nouvelles et prometteuses des polyélectrolytes est l'auto-assemblage électrostatique pour la formation de films minces multicouches avec une vaste gamme de propriétés électriques, magnétiques et optiques. En réponse à la demande en croissance de dispositifs électroniques respectueux de l'environnement, nous avons conçu, synthétisé et caractérisé de nouveaux copolymères hydrosolubles à chromophore pendant a base d'anhydride maléique. Ces dérivées solubles dans l'eau peuvent s'auto-organiser à partir d'une solution en films multicouches. L'utilisation des copolymères d'anhydride maléique est attirante par la variabilité de leurs propriétés réalisées par l'introduction de comonomères différents.<br />D'autre part, ces copolymères contiennent l'unité réactive anhydride, qui offre des possibilités pour la modification chimique ultérieure du polymère, dans des conditions douces (températures basses, sans catalyseur). Les réactifs nucléophilies utilisés pour la fonctionnalisation étaient: Disperse Red 1, 3-amino-ethyl-carbazole, 9-ethanol-9 carbazole, 1-aminopyrene, 2-(4-aminophenyl)-5-(4-biphenylyl)-1,3,4-oxadiazole, 1-aminohexane, 4-aminoazobenzene, 4-nitroaniline and [6,6]-C61-bismethanoic acid ethyl ester 6-hydroxyhexyl ester.<br />Ces réactions ont un grand intérêt parce que l'ouverture de l'anneau d'anhydride fait apparaître un groupe carboxylique permettant l'hydrosolubilité ou l'hydrophilicité des produits finaux. Ainsi, les copolymères d'acide maléique peuvent être utilisé comme partenaires anioniques dans l'interaction électrostatique, connu comme technique de Couche-Par-Couche (LbL).

Ce travail porte sur le greffage radicalaire de l'anhydride maléique sur un polyéthylène basse densité, en voie fondu, et en présence d'un abstracteur d'atome d'hydrogène. L'utilisation des radicaux nitroxyle, comme agent de terminaison, en présence d'un peroxyde a permis de bloquer la réaction de réticulation du polyéthylène, réaction secondaire fréquemment rencontré lors de l'utilisation de radicaux peroxyle, tout en permettant le greffage d'une faible quantité d'anhydride maléique. L'élimination d'une partie de l'anhydride maléique et des radicaux nitroxyle via des réactions secondaires à haute température semble toutefois inévitable. La substitution du peroxyde par une alcoxyamine dans le rôle d'abstracteur d'atome d'hydrogène a alors permis d'atteindre des taux de greffage en anhydride maléique supérieurs pour une modification des propriétés rhéologiques du polyéthylène équivalente. Néanmoins, des incertitudes demeurent encore sur le mécanisme de décomposition thermique de cette alcoxyamine permettant la réaction de greffage.