Multifunctional monomers on the basis of acryl- and methacryl derivatives were synthesized and different protective groups were used. After polymerization the protective groups were removed by different methods. Various initiators for the NMP of the monomers were synthesized and the reaction conditions were optimized. The results showed that NMP was not a suitable method for multifunctional acryl- and methacryl derivatives to achieve well-defined homopolymers, although it was successful for control of polymerization of styrene and block copolymerization of multifunctional acryl- and methacryl derivatives with alkoxyamine terminated polystyrene. The ATRP of multifunctional acrylates and methacrylates has been successfully performed, as well as the block copolymerization of multifunctional acrylates and methacrylates. Relatively low polydispersities of the corresponding polymers (PD=1.18-1.36) and reasonably high rates of polymerization could be achieved when Me6TREN and PMDETA were used as ligands. However, the ATRP of multifunctional acrylamides and methacrylamides failed. The RAFT-polymerization of styrene, acrylamide and acrylate using BDTB as a CTA and AIBN as an initiator afforded polymers with narrow molecular weight distribution (PD=1.13-1.26). A kinetic investigation and the further synthesis of block copolymers using dithioester-terminated homopolymers as macroCTAs showed that the RAFT polymerization of acrylamide M9b proceeded in a living manner. However, BDTB does not control the reaction of methacrylic monomers, such as methacrylates and methacrylamides. The bulk phase behavior of the block copolymers were examined by means of DSC and the surface behaviors of block copolymers as thin layers were examined with AFM. Two-phase transitions in the block copolymers were observed clearly by DSC, indicative of the appearance of phase separations, which were seen in an AFM image. In conclusion, multifunctional acryl- and methacryl derivatives failed to achieve well-defined homopolymers by NMP. However, this method was successful for block copolymerization of multifunctional acryl- and methacryl derivatives with alkoxyamine terminated polystyrene. Multifunctional acrylates and methacrylates were successfully homopolymerized and block copolymerized by ATRP. Multifunctional acrylates and acrylamides were suitable for homopolymerization and block copolymerization by the RAFT process. Thus far, it is difficult to homopolymerize multifunctional methacrylamides in controlled way.

Alzheimer’s disease (AD) is the most common cause of senile dementia worldwide. AD is a neurodegenerative disorder characterized by the loss of memory and language skill, collapse of the cognitive function, and distortion of social behavior. As of today, the onset mechanisms of AD and cure are unknown; however, three hallmarks are commonly encountered: extra and intracellular accumulation of amyloid beta (A!) peptide plaques, formation of intracellular neurofibrillary tangles, and inevitable neuronal death. Hypothetically, a possible scenario provoking or involved in the onset of AD is a cascade effect that starts with an imbalance in the production and clearance of Aß peptide that consequently leads to its accumulation, formation of tau protein tangles and neuronal death. This work studied and characterized the mechanisms governing A! peptide aggregation and the effects of using anti-Aß monoclonal antibodies to modify this process. These mechanisms play an important role in the formation of AD plaques and are critical in the search for therapies involving Aß peptide plaque clearance. Yet, antibody-based therapies for plaque clearance are not well understood, adding to the existing concerns about side effects in humans, hence there is a necessity of knowledge in this matter. In this work different Nterminus, C-terminus, and Mid-domain antibodies were used against Aß peptide species (monomers, oligomers, and fibrils) to probe peptide aggregates modification and disruption. Additionally, construction of a soft supported lipid bilayer membrane was proposed to study the adhesion mechanisms of Aß peptide and interactions with antibodies, mimicking the neuronal cell surface. The main characterization techniques used in this work were: atomic force microscopy (AFM) and transmission electron microscopy that allowed the physical exploration and visualization of the different processes of aggregation in terms of adhesion, size evolution, and distribution of the peptide; and attenuated total reflectance Fourier spectroscopy (ATR/FTIR) which allowed monitoring the change of secondary structures for the peptide during the processes studied. It is endeavored that this work will help to elucidate the effects attributed to the molecular interactions between A! peptide species and antibodies to target Aß plaque’s clearance in the brain of AD patients. Ultimately, this study provides novel information critical for the formulation of effective therapies to prevent and treat AD with less collateral effects. It also represents a contribution to the basic scientific knowledge regarding peptide-antibody interactions with application to other diseases related to protein misfolding.

Block copolymer self-assembly has demonstrated sub-optical lithographic resolution . High values of chi, the block copolymer interaction parameter, are required to achieve next-generation lithographic resolution . Unfortunately, high values of chi can lead to thin film orientation control difficulties , which are believed to be caused by large differences in the surface energy of each block relative to the substrate and the free surface. The substrate-block interface can be modified to achieve a surface energy intermediate to that of each individual block ; the air-polymer interface, however, presents additional complications. This thesis describes the synthesis of polymers for top coat surface treatments, which are designed to modify the surface energy of the air-block copolymer interface and enable block copolymer orientation control upon thermal annealing. Polymers with β-keto acid functionality were synthesized to allow polarity switching upon decarboxylation. Syntheses of anhydride containing polymers were established that provide another class of polarity switching materials. / text

Los polímeros de alto rendimiento (HPP) desempeñan un rol importante en la actualidad. El desarrollo de métodos más eco­nómicos para sintetizar estos polímeros minimizando el impacto tanto en la salud como en el medio ambiente es una prioridad. Las poliimidas (PI) pertenecen al grupo de los HPP y presentan características excepcionales como una gran estabilidad ante elevadas temperaturas, alta resistencia a los productos químicos agresivos y a la radiación, así como propiedades de aislamiento. Sin embargo, la síntesis de las PI presenta aún retos importantes. En este artículo presentamos un enfoque alternativo para sinte­tizar PI de forma y tamaño impresionante. / High-performance polymers (HPPs) play an important role in modern technology. Many efforts aim to develop cost-effective pathways to synthesize polymers without causing any harm to health and the environment. Polyimides (PIs) belong to the class of HPPs and they show outstanding features e.g. high-tempera­ture stability, resistance to aggressive chemicals and radiation, as well as insulating properties. PI synthesis, however, present yet major challenges. We herein present an alternative approach to PIs of intriguing shape and of impressive size.

O objetivo do trabalho foi investigar múltiplos aspectos relacionados ao pré-aquecimento da resina composta anterior à fotoativação: o grau de conversão e a cinética da polimerização em função da temperatura de polimerização, tempo de fotoativação e profundidade; o desempenho da fonte aquecedora (temperatura máxima, estabilidade térmica do aparelho e variações de temperatura ao pré-aquecer compules) e aspectos clínicos (o efeito de ciclos de pré-aquecimento repetidos e prolongados sobre o grau de conversão, a variação da temperatura intrapulpar in vitro e a variação da temperatura in vivo ao usar resina composta pré-aquecida ou a temperatura ambiente. A conversão de monômeros e os parâmetros de cinética foram determinados através de FTIR-ATR. Os espécimes foram fotoativados por 5, 10, 20 ou 40s entre 3 o e 60 o C. Foram calculados o grau de conversão em tempo real, a taxa máxima de conversão, o tempo em que ocorreu a taxa máxima, e a conversão na taxa máxima. Os dados foram tratados por análise de variância, teste-t e análise de regressão (p ≤0,05). O desempenho do dispositivo aquecedor foi medido monitorando-se a mudança de temperatura em tempo real com o auxílio de um termopar tipo-k conectado a um conversor analógico-digital. Os termopares foram colocados no aquecedor e dentro de compules de compósito. Os dados foram analisados com teste t (p ≤0,05). Compules (n=5) foram submetidos a um dos ciclos térmicos: Pré-aquecimento repetido (da temperatura ambiente a 60 o C, por 10 vezes) ou Prolongado (24h a 60 o C). O grau de conversão foi medido 24h após os ciclos, com o compósito à temperatura ambiente, seguindo o protocolo descrito acima. Os dados foram tratados por análise de variância e teste de Tukey (p≤0,05). O aumento da temperatura intrapulpar foi medido por um termopar colocado na câmara pulpar de um prémolar contendo uma cavidade de Classe V (com 1mm de espessura de dentina remanescente). O preparo foi preenchido com compósito à temperatura ambiente ou pré-aquecido enquanto a temperatura intrapulpar era continuamente monitorada (n=5). Os dados foram comparados por análise de variância e teste de Tukey (p ≤0,05). Para a medida da variação de temperatura in vivo, foram feitos preparos cavitários de 2mm de profundidade em dentes posteriores de um indivíduo (n=3). Uma sonda que mensurava a temperatura foi introduzida no dente preparado em cada procedimento restaurador e durante a inserção da resina composta à temperatura ambiente ou pré-aquecida a 60°C. Os dados foram comparados com análise de variância e teste de Tukey (p ≤0,05). Os resultados indicaram que: 1) o pré-aquecimento da resina composta anterior à fotoativação aumenta o grau de conversão, reduz o tempo de fotoativação e resulta em maior taxa de conversão, sem alterar o tempo em que a taxa máxima ocorre; 2) tanto o dispositivo aquecedor quanto os compules atingiram temperaturas inferiores das determinadas pelo fabricante; ao remover o compósito do aquecedor a perda de calor é acentuada ; 3) o grau de conversão não foi afetado por ciclos repetidos e prolongados de pré-aquecimento da resina composta; 4) não houve aumento da temperatura intrapulpar ao serem comparadas as resinas composta à temperatura ambiente e pré-aquecida; 5) a medida da temperatura in vivo revelou que o compósito pré-aquecido a 60 o C fica somente 8 o C acima da temperatura intrabucal; a técnica de pré-aquecimento deve ser usada com cautela. / This work examined multiple aspects of pre-heating dental resin composite prior to light-curing: the monomer conversion and polymerization kinetics as a function of cure temperature, light-exposure duration and depth; the performance of the heating device (maximum temperature, thermal stability of device and temperature change when pre-heating compules); and clinically relevant issues (the effect of repeated and extended pre-heating cycles on conversion; in vitro intrapulpal temperature change and in vivo temperature change when using either room-temperature or pre-heated composite). Monomer conversion and kinetic parameters were determined using FTIR-ATR. Specimens were cured for 5, 10, 20 or 40s between 3 o and 60 o C. Real-time monomer conversion, maximum conversion rate, time into exposure when maximum rate occurred, and conversion at maximum rate were calculated. Data were analyzed using regression analysis, Student's t-tests, and ANOVA with appropriate post-hoc tests (alpha = 0.05). Performance of the heating device was measured by monitoring the real-time temperature change with a K-type thermocouple connected to an analog-to-digital converter. Thermocouples were placed both in the heater and inside composite compules. Data were analyzed using Student t-test (alpha = 0.05). Compules (n=5) were submitted to one of the temperatures cycles: Repeated (from room temperature to 60 o C, 10 times) or Extended pre-heating (24h at 60 o C). Monomer conversion was measured 24h after cycling, with composite at room temperature, following the protocol described above. Data were analyzed using ANOVA and the Tukey-Kramer post-hoc test (alpha = 0.05). Intrapulpal temperature rise was measured by placing a K-type thermocouple in the pulp chamber of a extracted, human premolar, which had a Class V preparation (1mm remaining dentin thickness). The preparation was filled using composite either at room-temperature, or pre-heated while continuously monitoring intrapulpal temperature (n=5). Data were compared using ANOVA and the Tukey-Kramer post-hoc test (α =0.05). For measurement of temperature change in vivo, 2mm deep preparations were made on posterior teeth of a live human subject (n=3). Temperature values were recorded by placing a custom-made probe on the tooth preparation after each restorative procedure and during insertion of resin-composite at room temperature or pre-heated to 60°C. Data were compared using a 2-way ANOVA, and Tukey-Kramer post-hoc test (α =0.05). Results indicated that: 1) pre-warming composite prior to polymerization results in greater conversion, requires shorter exposure duration, and enhances maximal rate of conversion without changing the time into the exposure when the maximum rate occurs; 2) either the heating device or the compules achieved lower temperatures than those stated by the manufacturer; composite temperature loss upon removal from the heater was dramatic; 3) neither repeated nor extended pre-heating of composites significantly affected monomer conversion values; 4) no increase in intrapulpal temperature values was observed when comparing room temperature and pre-heated composite; 5) temperature measurement in vivo revealed that composite pre-heated to 60°C attains only 8 o C above intraoral temperature upon delivery; thus, the composite pre-heating technique should be used with caution.

Neste trabalho, estudos da copolimerização em emulsão de estireno e butadieno foram realizados em duas etapas. A primeira etapa consistiu na obtenção de um modelo matemático que representasse os processos em batelada e em semicontínuo através das principais variáveis do processo. Na segunda etapa, o efeito de diversas variáveis importantes ao processo foi avaliado, dentre elas: o tempo de adição dos reagentes, o tipo de alimentação empregado e a temperatura da reação. O modelo matemático se baseia em um trabalho previamente publicado que foi adaptado para simular o processo de copolimerização de estireno e butadieno em emulsão. Foram simulados processos em batelada e em semicontínuo. Em conjunto com os resultados experimentais, foi realizada a estimação de parâmetros não obtidos na literatura utilizando o método de Marquardt. As características do processo e as propriedades do polímero, tais como, conversão, diâmetro de partícula, taxa de polimerização e pressão interna do reator também foram obtidas, fornecendo condições para otimização e avaliação do processo de polimerização em batelada e em semicontínuo. Adicionalmente, também foi proposto um modelo de equilíbrio líquido-vapor dos monômeros. Os ensaios experimentais foram realizados em reator encamisado semicontínuo de mistura com 3 litros, nos quais foram utilizados persulfato de sódio como iniciador, lauril sulfato de sódio como emulsificante e tercdodecil mercaptana como agente de transferência de cadeia. Foram estudados os efeitos da temperatura, do tipo e do tempo de alimentação utilizada. A velocidade de polimerização, os diâmetros médios de partículas, o teor de monômero residual, o teor de insolúveis e o teor de resíduos foram avaliados. A cromatografia gasosa foi aplicada com sucesso em análises de látex e monômeros com finalidades diversas, destacando-se a obtenção de coeficientes de atividade necessários ao modelo de equilíbrio líquido-vapor, análise da concentração de monômeros ao longo da reação e análise da concentração de monômero residual. / In this work, studies of the styrene butadiene emulsion copolymerization had been performed in two stages. The first stage composed of a mathematical model that represented the batch and semi continuous process. In the second stage, the effects of diverse process variables were evaluated, among them: the time of addition of the reagents, feeding type and temperature reaction. The mathematical model was based on previously published work that it was adapted to simulate the styrene butadiene emulsion copolymerization process. Batch and semi continuous processes were simulated. In assembly with the experimental results, Marquardt method was applied to estimate some parameters that wasn’t found in literature. The variable process and the properties of polymer, such as, conversion, particle diameter, rate of polymerization and pressure of the reactor had been also simulated to batch and semicontinous process. A liquid-vapor balance of monomers model was proposed. The experimental stage had been carried through in a semi continuous stirring jacket tank reactor with 3 liters. Sodium persulfate as initiating, sodium lauryl sulfate as surfactant and Tert dodecyl mercaptan as chain transference agent had been used. The effect of temperature, type and time feeding had been studied. Polymerization rate, particles diameter, residual monomer had been evaluated. The gaseous chromatography was successfully applied in analyses of latex with diverse purposes: activity coefficient estimation, adjustment of liquid-vapor model, analysis of residual monomer of the reaction and volatiles organic components concentration in final latex.

Made available in DSpace on 2014-08-20T14:30:12Z (GMT). No. of bitstreams: 1 Tese _Luciano_de_Vargas_ Habekost.pdf: 2287600 bytes, checksum: 421084441401a2957e40573944b6a691 (MD5) Previous issue date: 2011-01-14 / The objective of this study was to investigate the influence of nanoparticle loading and the use of silane (TSPM), phosphate (PAM) or carboxylic (CAM) methacrylates as coupling agents on key properties of experimental resin luting agents. An experimental photocurable resin blend composed with 50 wt% of Bis-GMA and 50 wt% of TEGDMA was obtained. To study the influence nanoparticle loading, five different experimental resin luting agents were prepared with a total mass fraction of 60% of inorganic fillers. Silanated 2-μm barium borosilicate glass microparticles and 7-nm silica nanoparticles were used; the mass fraction of nanoparticles was set at 0 (control), 1 (G1), 2.5 (G2.5), 5 (G5) and 10% (G10). To study the influence of coupling agents, the resin blend was loaded with a 60% mass fraction of inorganic fillers (59/1 mass ratio of micro/nanoparticles) of Ba-B-Al-Si glass and colloidal silica coated with 5 wt% of TSPM, PAM or CAM; no filler treatment was performed in the control group. The properties evaluated were flexural strength () and modulus (Ef), Knoop hardness number (KHN), and film thickness (FT). Dispersion/interaction of particles with the resin phase was assessed by scanning electron microscopy (SEM).The degree of conversion (DC) was evaluated only to study the influence of coupling agents. Data were submitted to statistical analysis (5%). Results for nanoparticle loading: for , G1 > G2.5 = G5 = G10, and control > G10. For Ef, G2.5 > control = G1 > G5 > G10. For KHN, G5 = G10 > control = G1 = G2.5. For FT, control = G1 < G5 = G10, and G2.5 < G10. Incorporation of nanoparticles was associated with observation of clusters in the SEM analysis. Results for different coupling agents: for  and Ef, TSPM > CAM > control > PAM. For KHN, TSPM > CAM > PAM = control. For FT, TSPM < control < CAM < PAM. The SEM analysis revealed clustering of nanoparticles for all groups and better interaction between the organic-inorganic phases for TSPM and CAM. No significant differences in DC were observed. The results demonstrated that moderate incorporation of silanated silica nanoparticles may improve the properties of hybrid resin cements. However, mass fraction above 2.5% had a detrimental effect on the luting agent properties and the increase of clusters is associated with the increase of nanoparticles. The use of TSPM generated agents with improved properties as compared with the acidic methacrylates, with CAM showing better performance than PAM. The use of PAM generated agents with properties usually poorer compared with the material with no coupling agent. / O objetivo deste estudo foi investigar a influência da incorporação de nanopartículas e o uso de silano (TSPM), monômero ácido fosfatado (PAM) ou monômero ácido carboxilado (CAM) como agentes de união nas propriedades de cimentos resinosos experimentais. Uma matriz resinosa fotopolimerizável modelo foi desenvolvida com 50% de Bis-GMA e 50% de TEGDMA. Para observar o comportamento da incorporação de nanopartículas, cinco cimentos resinosos experimentais foram preparados pela adição de 60% (em massa) de micropartículas de bário borosilicato de vidro (2μm) e nanopartículas de sílica coloidal (7nm). As nanopartículas foram utilizadas nas seguintes proporções (em massa): 0 (controle), 1 (G1), 2.5 (G2.5), 5 (G5) e 10% (G10). Para estudar a influência dos agentes de união, 60% (em massa) de partículas inorgânicas (59/1 de micro/nanopartículas) de vidro de Ba-B-Al-Si e sílica coloidal, cobertas com 5% de TSPM, PAM ou CAM, foram acrescidas à matriz resinosa; o grupo controle foi composto por partículas não tratadas. As propriedades avaliadas foram resistência flexural (), módulo de elasticidade (Ef), número de dureza Knoop (KHN) e espessura de película (FT).A dispersão/interação das partículas com a fase resinosa foi avaliada com microscópio eletrônico de varredura (MEV). O grau de conversão (DC) foi avaliado somente para estudar a influência dos diferentes agentes de união. Os dados foram submetidos à análise estatística (5%). Resultados para incorporação de nanopartículas: para , G1 > G2.5 = G5 = G10 e controle > G10. Para Ef, G2.5 > controle = G1 > G5 > G10. Para KHN, G5 = G10 > controle = G1 = G2.5. Para FT, controle = G1 < G5 = G10 e G2.5 < G10. Nas análises em MEV, a presença de aglomerados foi associada à incorporação de nanopartículas. Resultados para a utilização de diferentes agentes de união: para e Ef, TSPM > CAM > controle > PAM. Para KHN, TSPM > CAM > PAM = controle. Para FT, TSPM < controle < CAM < PAM. As análises em MEV revelaram aglomerados de nanopartículas em todos os grupos e melhor interação entre as fases orgânica/inorgânica para TSPM e CAM. Não foram observadas diferenças para o DC. Os resultados demonstraram que a incorporação moderada de nanopartículas de sílica silanizada pode beneficiar as propriedades dos cimentos resinosos híbridos. Entretanto, proporções de nanopartículas acima de 2,5% possuem um efeito prejudicial nas propriedades destes cimentos, e seu aumento está associado com o aumento da presença de aglomerados. O uso de TSPM gerou cimentos com melhores propriedades quando comparado ao uso de monômeros ácidos, o CAM demonstrou melhor desempenho que o PAM. O uso do PAM gerou cimentos com propriedades inferiores a cimentos sem a utilização de agentes de união.

La morphologie de l’endommagement par cavitation est analysée dans un EPDM non chargé sous différentes conditions de décompression d’hydrogène. Les expériences permettent devisualiser l’évolution de l’endommagement au cours du temps. Les images obtenues sont traitées pour obtenir l’instant d’apparition, le nombre et la distribution de taille des cavités au cours du temps. Elles permettent également de suivre les cinétiques de croissance / décroissance des plus grosses cavités. Le tracé de covariogrammes permet de quantifier la distribution spatiale de ces cavités. L’analyse de cet ensemble de données porte donc sur deux échelles :celle de cavités indépendantes et celle de champs de cavités. A l’échelle de la cavité, les cinétiques expérimentales sont corrélées à des calculs numériques par Eléments Finis en conditions diffuso-mécaniques couplées sur une cellule élémentaire contenant une ou deuxcavité(s). Ces calculs permettent par ailleurs d’éclairer les évolutions locales des champs mécaniques et de concentration de gaz, ainsi que les mécanismes d’interaction entre cavités voisines. Les covariogrammes fournissent des éléments pour estimer les caractéristiques d’un Volume Elémentaire Représentatif (VER) (taille, isotropie) et discuter la représentativité d’untel modèle numérique selon les conditions de décompression. A l’échelle des champs de cavités,les conditions de décompression influencent la répartition spatiale. Le nombre et la taille des cavités augmentent avec la pression de saturation et/ou la vitesse de décompression, et une seconde population de petites cavités apparaît autour des premières sous conditions sévères.L’homogénéité et l’isotropie de la distribution à l’échelle macroscopique sont étudiées. Il est finalement montré que la morphologie des champs de cavités évolue au cours de cycles successifs. Cette analyse fournit des informations pour discuter et renseigner le cadre et les ingrédients de modèles d’endommagement. / The morphology of cavitation is analyzed in an unfilled EPDM under different hydrogen decompression conditions. The experimental device allows a time-resolved tracking of the evolution of damage. Images are processed to obtain the onset time, the number and sizedistribution of cavities over time, and the inflation / deflation kinetics of the biggest cavities.Covariograms quantifies the spatial distribution of cavity fields. The analysis is thus led at two scales: that of independent cavities and that of the full cavity fields. At the cavity scale, kineticsis shown to be identical for independent cavities but different between inflation and deflation.Experimental kinetics is compared to that issued from Finite Element calculations in a cell containing one or two cavities, in coupled diffuso-mechanical conditions. Calculationshighlight the evolution of local mechanical and gas content fields, as well as interaction effects between close cavities. At the scale of cavity fields, the spatial distribution is influenced by the decompression conditions. The number and size of cavities increase with saturation pressure and/or decompression rate and a second population of small cavities is nucleated around the first one under severe decompression conditions. The homogeneity and isotropy of the distribution at macroscopic scale are studied. The influence of cycling on the evolution of cavitation morphology is addressed in the final part. It was finally found that the morphology of cavity fields evolves during successive cycles. The analysis provides information to discuss and to inquire the framework and ingredients of damage models.

Ce travail concerne l'étude de la polymérisation de l'éthylène allant de l'homopolymérisation purement radicalaire jusqu'à la copolymérisation utilisant un mécanisme hybride radicalaire/catalytique. Ce travail montre que le polyéthylène peut être synthétisé par voie radicalaire dans des conditions expérimentales beaucoup plus douces que celles utilisées industriellement (P>1000 bar et T>100°C). L'éthylène a été polymérisé à partir de 10°C et 5 bar de pression d'éthylène. Un important effet activateur du solvant a été mis en évidence. De plus la polymérisation en milieu dispersé aqueux de l'éthylène a aussi été étudiée. Des latex stables de PE avec des taux de solide de 40% ont pu être obtenus. Deux morphologies de nanoparticules, cylindre ou sphère, ont été observées. La copolymérisation radicalaire avec des monomères vinyliques polaires a été également étudiée en solution ou en émulsion. Des insertions d'éthylène jusqu'à 50% ont été obtenues. De plus l'influence du comonomère et du solvant organique utilisé sur la polymérisation radicalaire de l'éthylène a été quantifiée. Une nouvelle technique de polymérisation hybride radicalaire/catalytique a été développée pour pouvoir obtenir toute la gamme de compositions possibles de copolymères éthylène/monomère polaire à partir d'un complexe de nickel qui amorce la polymérisation radicalaire et catalyse également la polymérisation de l'éthylène. Ce complexe subit une rupture homolytique réversible de la liaison nickel carbone et permet la synthèse de copolymères multiblocs. Des insertions d'éthylène de 1% à 99% ont été obtenues en faisant varier la pression d'éthylène et la concentration en comonomères polaires / This work aims to study ethylene polymerization from the free radical polymerization process to the copolymerization by a hybrid radical/catalytic mechanism. PE is synthesized by free radical polymerization under milder experimental conditions than industrial ones (P>1000 bar and T>100°C). Indeed free radical polymerization of ethylene is efficient even down to pressure of 5 bar and temperature of 10°C. Several unexpected behaviors are observed such as a high solvent activation effect. Beside the slurry process in organic solvent, polymerization in aqueous dispersed media is also performed. Stable PE latexes are obtained with solid contents up to 40%. Two different PE particles morphologies are observed cylinder-like and sphere-like. Then free radical copolymerization is studied using a broad range of polar vinyl monomers in organic solvent and emulsion. Insertions up to 50% of ethylene are obtained under mild conditions. The ambivalent role of comonomer as monomer and activator of the polymerization is highlighted. In order to obtain a wide range of composition of polar/non-polar copolymers a new technique of polymerization has been developed. A nickel complex is used to initiate the free radical polymerization and to catalyse the coordination/insertion ethylene polymerization. This nickel complex is capable of a reversible homolytic cleavage of its nickel-carbon bond. Finally, this hybrid process is used to copolymerize efficiently ethylene with various polar vinyl monomers. Multiblock copolymers with ethylene content from 1% to 99% are obtained by simply varying the monomer feeds

Dans cette thèse, nous avons démontré la faisabilité de la préparation de polymères à empreinte moléculaires (MIP) hautement sélectifs pour la reconnaissance dans des matrices aqueuses complexes avec des applications dans les cosmétiques et en technologie alimentaire. Les MIP (de l'anglais molecularly imprinted polymers) sont des récepteurs synthétiques comparables aux anticorps, qui sont synthétisés par co-polymérisation de monomères fonctionnels et réticulants en présence d'un gabarit moléculaire. Leurs propriétés de reconnaissance moléculaire, associées à leur grande stabilité, robustesse mécanique, faible coût et leur synthèse facile les rendent extrêmement intéressants comme matériaux de capture sélective, avec des applications dans les séparations analytiques, la détection et la vectorisation des médicaments. Cependant, leur reconnaissance sélective dans des milieux aqueux reste toujours problématique et c'est l'une des raisons de leur expansion commerciale restreinte. Dans une première partie, nous avons développé un MIP fonctionnant en milieu aqueux pour son application comme ingrédient actif dans un déodorant. Les odeurs corporelles sont principalement dues à des acides gras volatils générés à partir de leurs précurseurs, des conjugués de glutamine par des enzymes hydrolytiques produites à partir de bactéries présentes sur la peau. La plupart des anti-transpirants et des déodorants actuellement commercialisés contiennent des sels d'aluminium et des agents antibactériens non spécifiques, respectivement. Cependant, l'utilisation extrêmement étendue de ces produits nécessite des solutions alternatives en ce qui concerne divers problèmes (environnement, respect de l'écosystème de la peau, toxicité, etc.). Pour cette raison, un MIP a été synthétisé pour capturer les précurseurs conjugués de glutamine afin qu'ils ne soient plus disponibles aux bactéries, empêchant ainsi leur transformation en composés malodorants. Afin de générer des liaisons sélectifs dans des environnements aqueux, un monomère à base d'amidinium qui peut former une interaction électrostatique stoechiométrique forte avec les groupes carboxyle sur le gabarit moléculaire a été synthétisé. Le MIP, mélangé dans une formulation dermo-cosmétique, pourrait capter sélectivement les précurseurs conjugués de glutamine, au milieu d'une multitude d'autres molécules présentes dans la sueur humaine. En outre, le MIP n’affecte pas les bactéries de la peau, ouvrant la voie à des déodorants innovateurs de nouvelle génération, moins problématiques pour la santé. Dans une deuxième partie, nous avons développé une procédure rapide et efficace basée sur l'extraction en phase solide à empreinte moléculaire (MISPE) pour la purification sélective de la bétanine et de son stéréoisomère l’isobétanine à partir d'extraits de betterave. La bétanine est un pigment naturel ayant un fort pouvoir antioxydant et dont les propriétés pharmacologiques sont de plus en plus étudiées. Ce pigment est actuellement utilisé comme simple colorant alimentaire. Dans notre étude, l'acide dipicolinique a été utilisé comme gabarit moléculaire pour la synthèse de MIP, en raison de sa similarité structurelle avec le groupe chromophore de la bétanine. Les procédures MISPE ont été optimisées permettant l'élimination presque complète des glucides issus de la matrice végétale ainsi que la majorité des protéines, ce qui permet d'obtenir un rendement élevé d'extraction de la bétanine / isobétanine en une seule étape. De plus, toute la procédure d'extraction a été réalisée dans des solvants respectueux de l'environnement, tels que l'éthanol ou l'eau. Pour conclure, nous sommes convaincus que ce travail pave le chemin au développement d'une nouvelle génération des MIP fonctionnant en milieu aqueux avec des propriétés de reconnaissance améliorées dans des environnements complexes, qui pourra s'appliquer également à d'autres domaines biotechnologiques et biomédicaux. / In this thesis, we have demonstrated the feasibility of preparing highly selective molecularly imprinted polymers (MIPs) for recognition in complex aqueous matrices with applications in cosmetics and food technology. MIPs are synthetic tailor-made receptors, with binding affinities and specificities comparable to those of natural antibodies. Their molecular recognition properties, combined with their high stability, mechanical robustness, low cost and easy synthesis make them extremely attractive as selective capture materials with applications in analytical and preparative separations, sensing and drug delivery, among others. However, their selective recognition in aqueous samples still remains problematic and is one of the reasons for their so far lilited commercial expansion. In the first part, we developed a water compatible MIP for its application as an active ingredient in a deodorant. Body odors are mainly due to volatile fatty acids generated from their glutamine conjugate precursors by hydrolytic enzymes from bacteria present on the skin. Most currently marketed anti-perspirants and deodorants contain, respectively aluminum salts and unspecific antibacterials. However, the extremely wide use of these products requires alternative solutions with regard to various problems (environmental, respect of skin ecosystem, toxicity, etc.). For this reason, a MIP was developed to capture the glutamine conjugate precursors so that they are no longer available to the bacteria, thus preventing their transformation to malodorous compounds. In order to generate binding selectivity in aqueous environments, an amidinium-based monomer which can form a strong stoichiometric electrostatic interaction with the carboxyl groups on the template, was synthesized. The MIP, blended in a dermo-cosmetic formulation, could capture selectively the glutamine precursors, amidst a multitude of other molecules present in human sweat. Furthermore, the MIP did not affect the skin bacteria, paving the way to an innovative and 'safer ' future-generation deodorant. In the second part, we developed a fast and efficient procedure based on molecularly imprinted solid­ phase extraction (MISPE) for the selective clean-up of betanin and its stereoisomer isobetanin from red beetroot extracts. Betanin is a natural pigment with significant antioxidant and biological activities currently used as food colorant. Dipicolinic acid was used as template for the MIP synthesis, because of its structural similarity to the chromophore group of betanin The MISPE procedures were optimized allowing the almost complete removal of carbohydrates and the majority of proteins, resulting in high extraction recovery of betanin / isobetanin in a single step. Moreover, the whole extraction procedure was performed in environmentally friendly solvents with either ethanol or water. To conclude, we believe that this study paves the way towards the development of a new generation of water compatible MIPs with improved recognition properties in highly complex aqueous environments, and should be applicable to other biotechnological and biomedical areas as well.