Los surfactantes son moléculas anfifílicas, con una cabeza solvofílica y una cola solvofóbica. Cuando la concentración de surfactante en solución es suficientemente alta, las moléculas se agregan entre ellas para proteger las partes solvofóbicas del contacto con el medio. Tales agregados pueden tener forma y tamaño muy diferentes, dependiendo del surfactante y de las condiciones del sistema. La auto-organización de los surfactantes (self-assembly), debida a un compromiso energético y entrópico de su estructura molecular, es la clave que permite observar cristales líquidos muy ordenados. En presencia de un precursor inorgánico y dependiendo de las interacciones que este precursor establece con el surfactante, se puede observar la formación del material híbrido. Los materiales híbridos constituyen un paso intermedio fundamental para la síntesis de los materiales mesoporosos ordenados, los cuales se obtienen eliminando la matriz orgánica (surfactante) del substrato inorgánico. El presente estudio tiene como principal objetivo estudiar bajo cuales condiciones los sistemas formados por un surfactante, un precursor inorgánico y un solvente, se auto-organizan para dar lugar a estructuras híbridas muy ordenadas. En particular nos proponemos individuar cuales son las características más importantes que los precursores inorgánicos deberían tener para poder observar la formación de materiales mesoporosos ordenados.Simulaciones Monte Carlo en el colectivo canónico han sido utilizadas para analizar la agregación de los surfactantes en estructuras complejas, como micelas, cilindros organizados en forma hexagonal, o laminas, a partir de configuraciones totalmente desordenadas. Con particular interés hemos analizado el rango de condiciones que llevan a la formación de las estructuras cilíndricas, y estas mismas estructuras han sido comparadas en función de algunas importantes características morfológicas, como el tamaño de poro, el grosor de las paredes, la presencia y accesibilidad de los grupos funcionales en los poros. El modelo usado representa las moléculas de surfactante y de precursor inorgánico como cadenas de segmentos en una red tridimensional que discretiza el espacio en sitios de volumen unitario. Este modelo no entra en el detalle de las características físicas y químicas de las moléculas, pero permite reproducir su agregación en estructuras complejas en un tiempo de cálculo muy razonable. La separación de fase ha sido también evaluada recorriendo a una teoría de campo medio, la quasi-chemical theory, que, aunque no pueda predecir la formación de estructuras ordenadas, ha sido muy útil para confirmar los resultados de las simulaciones, sobretodo cuando no se observa formación de fases ordenadas. El estudio de surfactantes distintos, uno modelado por una cadena lineal y otro con una cabeza ramificada, nos ha permitido evaluar algunas diferencias estructurales de los materiales obtenidos. La ramificación de la cabeza, que merecería un estudio más profundo del que hemos descrito en este trabajo, ha evidenciado unas interesantes consecuencias en el tamaño de los poros. Este mismo surfactante con cabeza ramificada ha sido elegido para la síntesis de agregados cilíndricos utilizados como templates en la formación, agregación, y condensación de una capa de sílica modelada a través de un modelo atomístico. En particular, hemos aislado uno de los cilindros presentes en los cristales líquidos de estructura hexagonal, y a su alrededor hemos simulado la formación de una capa de sílica utilizando un modelo atomístico. De esta forma, hemos obtenido un poro típico de una estructura mesoporosa más realista, sin necesidad de asumir una forma mas o menos cilíndrica del template, por ser este generado de la auto-agregación del surfactante. / Surfactants are amphiphilic molecules with a solvophilic head and a solvophobic tail. When the surfactant concentration in a given solution is high enough, the molecules aggregate between them to shield the solvophobic part from the contact with the solvent. Such aggregates can show very different sizes and shapes, according to the surfactant and the conditions of the system. The surfactants self-assembly, being due to an energetic and entropic compromise of their molecular structure, is fundamental to observe the formation of very ordered liquid crystals. In the presence of an inorganic precursor and depending on the interactions established between such a precursor and the surfactant, it is possible to synthesize a hybrid material. Hybrid materials are the key step for the formation of periodic ordered mesoporous materials, which can be obtained by eliminating the organic soft matter (the surfactants) from the inorganic framework. Periodic ordered mesoporous materials represent an important family of porous materials as they find a large number of applications in several industrial fields, such as separations, catalysis, sensors, etc. In the last decade, the range of potential applications has increased with the possibility of functionalizing the pore walls by incorporating organic groups during the synthesis, or with post-synthesis treatments.In this work, we are interested in studying the formation of ordered materials when hybrid organic-inorganic precursors are used. Lattice Monte Carlo simulations in the NVT ensemble have been used to study the equilibrium phase behavior and the synthesis of self-assembling ordered mesoporous materials formed by an organic template with amphiphilic properties and an inorganic precursor in a model solvent. Three classes of inorganic precursors have been modeled: terminal (R-Si-(OEt)3) and bridging ((EtO)3-Si-R-Si-(OEt)3)) organosilica precursors (OSPs), along with pure silica precursors (Si-(OEt)4). Each class has been studied by analyzing its solubility in the solvent and the solvophobicity of the inorganic group. At high surfactant concentrations, periodic ordered structures, such as hexagonally-ordered cylinders or lamellas, can be obtained depending on the OSPs used. In particular, ordered structures were obtained in a wider range of conditions when bridging hydrophilic OSPs have been used, because a higher surfactant concentration was reached in the phase where the material was formed. Terminal and bridging OSPs produced ordered structures only when the organic group is solvophilic. In this case, a partial solubility between the precursor and the solvent or a lower temperature favored the formation of ordered phases.With particular interest, we have analyzed the range of conditions leaving to the formation of cylindrical structures, which have been evaluated according to the pore size distribution, the pore wall thickness, the distribution and the accessibility of the functional organic groups around the pores. The phase behavior has been also evaluated by applying the quasi-chemical theory, which cannot predict the formation of ordered structures, but was very useful to confirm the results of simulations, especially when no ordered structures were observed.The study of the phase and aggregation behavior of two different surfactants, one modeled by a linear chain of head segments and the other modeled by a branched-head, permitted us to evaluate some structural differences of the materials obtained.

This dissertation explores the potential applications of nanotechnology in the oilfield including poly(vinyl alcohol) stabilized carbon black nanoparticles for oil exploration and temperature-responsive carbon black nanoparticles for enhanced oil recovery. Also, it describes the rational design of graphene nanoribbons via intercalating reactive metals into multi-walled carbon nanotubes followed by addition of vinyl monomers or haloalkanes. Efficient production and modification of these aforementioned nanomaterials will make them more attractive for applications in the oilfield and electronics materials. A method is reported for detecting the hydrocarbon in the porous media with stabilized nanoparticles that are capable of efficiently transporting hydrophobic molecules through oil-containing rocks and selectively releasing them when a hydrocarbon is encountered. Nano-sized carbon black was oxidized and then functionalized with poly(vinyl alcohol) via a coupling reaction between the polymer's hydroxyl groups and the carboxylic groups on oxidized carbon black. Breakthrough curves show that poly(vinyl alcohol)-coated oxidized carbon black was stable in synthetic sea brine at room temperature and could carry the 14C-labeled radioactive tracer 2,2ˊ,5,5ˊ-tetrachlorobiphenyl through rocks and then released the tracer upon exposure to hydrocarbon. Due to the temperature-sensitivity of hydrogen bonds, higher molecular weight poly(vinyl alcohol) was used to improve the stability of carbon black nanoparticles in synthetic sea brine at higher temperatures. After sulfation, high molecular weight poly(vinyl alcohol) could stabilized carbon black nanoparticles in American Petroleum Institute standard brine at high temperatures. Those nanoparticles could efficiently transport mass-tagged probe molecules through a variety of oil-field rock types and selectively released the probe molecules into the hydrocarbon-containing rocks. Those proof-of-concept chemical nanoreporters can potentially be used under conditions commonly observed in the reservoir, and aid in the recovery of oil that remains in place. Amphiphilic carbon nanoparticles have been prepared that are capable of reversibly transferring across the water/oil interface in a temperature-controlled manner. Nano-sized carbon black was oxidized and then functionalized with amphiphilic diblock polyethylene-b-poly(ethylene glycol) copolymers that were water-soluble at low-to-moderate temperatures but oil-soluble at higher temperatures. The correlation between the phase transfer temperature and the melting temperature of the hydrophobic block of the copolymers and the weight percent of hydrophilic block were investigated. The amphiphilic nanoparticles were used to stabilize oil droplets for demonstrating potential applications in reducing the water/oil interfacial tension, a key parameter in optimizing crude oil extraction from downhole reservoirs. Graphene nanoribbons free of oxidized surfaces can be prepared in large batches and 100% yield by splitting multi-walled carbon nanotubes with potassium vapor. If desired, exfoliation is attainable in a subsequent step using chlorosulfonic acid. The low-defect density of these GNRs is indicated by their electrical conductivity, comparable to that of graphene derived from mechanically exfoliated graphite. Additionally, cost-effective and potentially industrially scalable, in situ functionalization procedures for preparation of soluble graphene nanoribbons from commercially carbon nanotubes are presented. To make alkane-functionalized graphene nanoribbons, multi-walled carbon nanotubes were intercalated by sodium/potassium alloy under liquid-phase conditions, followed by addition of haloalkanes, while polymer-functionalized graphene nanoribbons were prepared via polymerizing vinyl monomers using potassium-intercalated graphene nanoribbons. The correlation between the splitting of MWCNTs, the intrinsic properties of the intercalants and the degree of graphitization of the starting MWCNTs has also been demonstrated. Those functionalized graphene nanoribbons could have applications in conductive composites, transparent electrodes, transparent heat circuits, and supercapcitors.

In our laboratory, we using simple synthetic methods to synthesize one series of amphiphilic discotic liquid crystal which has the dipole-dipole forces. We not only research the effect about the length of hydrophilic chain, but also explore the arrangement of this series through some cross-comparison.

Living anionic polymerization techniques were applied to the synthesis of arborescent (dendritic) well-defined graft polymers having core-shell morphologies, with a hydrophobic core and a hydrophilic shell. Cycles of polystyrene substrate acetylation and anionic grafting yielded successive generations of arborescent polystyrenes. The anionic polymerization of styrene with sec-butyllithium provided polystyryllithium serving as side chains. These were coupled with a linear acetylated polystyrene substrate to obtain a generation zero (G0) arborescent polymer. An analogous G0 hydroxyl-functionalized polystyrene substrate with hydroxyl end groups was also obtained by a variation of the same technique, using a bifunctional organolithium initiator containing a hydroxyl functionality protected by a silyl ether group to generate the polystyrene side chains. These were coupled with the linear acetylated polystyrene substrate and subjected to a deprotection reaction to give the G0 polymer functionalized with hydroxyl groups at the chain ends. A similar procedure was used to generate a hydroxyl-functionalized arborescent G1 polymer from the corresponding G0 acetylated polystyrene substrate. The growth of polyglycidol chain segments was attempted from the hydroxyl-functionalized cores, to form a hydrophilic shell around the hydrophobic cores, but led to extensive degradation. A click reaction was also developed to synthesize the amphiphilic copolymers and was much more successful. In this case alkyne-functionalized arborescent polystyrene substrates, obtained by a modification of the hydroxyl-functionalized arborescent polystyrenes, were coupled with azide-functionalized polyglycidol side chains.

No description available.

Submitted by TULLIO HENRIQUE CANO DE HARO BARROS null (tullioharo@hotmail.com) on 2018-07-12T13:22:39Z No. of bitstreams: 1 Barros_Tullio_me_sjrp_int.pdf.pdf: 1544265 bytes, checksum: a6f5f0bd88b4957b4f0ca22899ec9aae (MD5) / Approved for entry into archive by Paula Torres Monteiro da Torres (paulatms@sjrp.unesp.br) on 2018-07-13T17:48:42Z (GMT) No. of bitstreams: 1 barros_thch_me_sjrp.pdf.pdf: 1544265 bytes, checksum: a6f5f0bd88b4957b4f0ca22899ec9aae (MD5) / Made available in DSpace on 2018-07-13T17:48:42Z (GMT). No. of bitstreams: 1 barros_thch_me_sjrp.pdf.pdf: 1544265 bytes, checksum: a6f5f0bd88b4957b4f0ca22899ec9aae (MD5) Previous issue date: 2018-06-28 / Este estudo teve como objetivo a síntese e caracterização de dietilaminoetilquitosana (QHdDEAE) e dodecil-dietilaminoetil-quitosana (QHdDEAEDOD) de baixa massa molar (Mw), para avaliar suas atividades antifúngicas contra os fungos Alternaria solani, Alternaria alternata e Penicilliun expansum, que provoca um grande impacto na produção e preservação de alimentos processados e minimamente processados. Os derivados de baixa massa molar (Mw) foram obtidos por reação de degradação de quitosana desacetilada com nitrito de sódio, seguido pela inserção de grupos DEAE e Dodecil na estrutura do polímero. O grau de desacetilação (DD) e de substituição (DS) por grupos dietilaminoetil (DEAE) e dodecil foram determinados usando ressonância magnética nuclear de hidrogênio (RMN-H) e caracterizados por infravermelho (IR). O grau de desacetilação e o grau de substituição por grupos DEAE foram de 94,8% 39,8%, respectivamente. Os derivados hidrofóbicos obtidos foram substituídos com 15% e 39,8% de grupos dodecil, conforme determinado por RMN-H. As massas molares foram determinadas usando Cromatografia de Permeação em Gel (GPC) e um Mw de 9,2 kDa foi obtido para quitosana desacetilada degradada. Ensaios in vitro contra os fungos Alternaria alternata, Peninicillium expansum e Alternaria solani foram realizados. Na concentração de 0,5g.L-1, QHdDEAEDOD e QHdDEAE foram mais eficazes que as quitosanas comercial e desacetilada e apresentaram inibições de 80% contra Alternaria alternata e Alternaria solani. A quitosana deacetilada degradada foi mais eficiente na inibição do crescimento fúngico de Penicillium expansum e para 0,5 g.L-1 atingiu cerca de 80% de inibição. Todos os derivados apresentaram viabilidade celular superior a 70% em células 3T3, demonstrando uma boa citocompatibilidade e potencial para aplicações na conservação de alimentos / This study aimed at the synthesis and characterization of Diethylaminoethyl-Chitosan (QHdDEAE) and Dodecyl-Diethylaminoethyl-Chitosan (QHdDEAEDOD) of low molar mass(Mw), to evaluate their antifungal activities against the fungi Alternaria solani, Alternaria alternata and Penicilliun expansum, which causes a great impact on the production and preservation of processed and minimally processed foods. The low Mw derivatives were obtained by degradation reaction with sodium nitrite, followed by the insertion of DEAE and Dodecyl groups on the polymer backbone. The degrees of deacetylation (DD) and substitution (DS) for DEAE and Dodecyl groups were determined using nuclear magnetic resonance of hydrogen (¹H-NMR) and characterized by FTIR. The degree of deacetylation and degree of substitution by DEAE gropus were 94,8% 39,8%, respectively. The obtained hydrophobicized derivatives were substituted with 15% and 39,8% of dodecyl groups as evaluated by ¹H-NMR. The molar masses were determined by using Gel Permeation Chromatography (GPC) and a Mw of 9,2kDa was obtained for deacetylated chitosan. In vitro assays against the fungi Alternaria alternata, Peninicillium expansum and Alternaria solani. At the concentration of 0.5 g.L-1 both, QHdDEAEDOD and QHdDEAE were more effective than commercial and deacetylated chitosans and exhibited inhibitions of 80% against Alternaria alternata and Alternaria solani. Degraded deacetylated chitosan was more efficient in inhibiting the fungal growth of Penicillium expansum and for 0.5 g.L-1 reached around 80% of inhibition. All the derivatives presented cell viabilities higher 70% on 3T3 demonstrated a good cytocompatibility and potential for applications in food preservation.

Orientador: Maria Isabel Felisberti / Dissertação (mestrado) - Universidade Estadual de Campinas, Instituto de Química / Made available in DSpace on 2018-08-17T19:45:22Z (GMT). No. of bitstreams: 1 Oliveira_HeitorFernandoNunesde_M.pdf: 3345603 bytes, checksum: 2f9d75a948fbe215b8da7ff775997c04 (MD5) Previous issue date: 2011 / Resumo: Neste trabalho foram sintetizados copolímeros anfifílicos constituídos de 1¿-O-metacrilato de sacarose (SMA) com os monômeros comerciais metacrilato de metila (MMA) ou N-isopropilacrilamida (NIPAAm), em diferentes composições molares. Catálise enzimática foi empregada para obtenção do monômero regioseletivamente monofuncional 1¿-O-metacrilato de sacarose, com rendimento reacional superior a 70 % de SMA. Esta etapa foi baseada em trabalho estabelecido na literatura e adequada às condições deste projeto. O SMA foi copolimerizado com os monômeros NIPAAm e MMA via polimerização radicalar. Estes materiais foram caracterizados por ressonância magnética nuclear de C (RMN C), cromatografia de permeação em gel (GPC), calorimetria diferencial de varredura (DSC) e análise termogravimétrica (TGA). Os resultados revelam o êxito da síntese de copolímeros aleatórios com elevada massa molar (ordem de 10 g mol), com propriedades físico-químicas dependentes da composição. Estes copolímeros foram submetidos a ensaios de solubilidade, intumescimento e de avaliação do comportamento de fases de soluções aquosas com a temperatura. Todos os polímeros sintetizados se apresentaram solúveis em algum solvente, evidenciando que tratam-se de macromoléculas de cadeias lineares. Para ambas as séries de copolímeros constatou-se que o caráter anfifílico é fortemente dependente da composição, tal como era esperado. Apenas o homopolímero de SMA e o copolímero de SMA e MMA mais rico no primeiro monômero são solúveis em água, enquanto que os demais copolímeros desta série intumescem neste solvente e a quantidade de água sorvida aumenta com o aumento da fração de SMA. A temperatura para separação de fases de soluções aquosas dos copolímeros constituídos de SMA e NIPAAm é superior em relação à temperatura observada para o poli(N-isopropilacrilamida), o que se atribui a maior hidrofilicidade dos copolímeros / Abstract: In this work, amphiphilic copolymers consisting of conjugated sucrose 1'-O-methacrylate (SMA) with methyl methacrylate (MMA) or N-isopropylacrylamide (NIPAAm) in different molar ratio were synthesized. Enzymatic catalysis was employed for obtaining regioselective monofunctional sucrose 1'-O-methacrylate with reaction yield above 70 % of SMA. This step was based on established work in literature and adequate conditions of this project. The SMA has been copolymerized with NIPAAm and MMA monomers by free radical polymerization. These materials were characterized by C nuclear magnetic resonance (C NMR), gel permeation chromatography (GPC), differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA). The results show the successful synthesis of random copolymers with high molar mass (order of 10 g mol), with physical and chemical properties dependent on composition. Solubility, swelling tests and the phase behavior studies of aqueous solutions were also performed for these copolimers. All polymers are soluble in some solvent, showing that these are linear macromolecules. For both series of copolymers was found that the amphiphilic character depends strongly on composition, as expected. Only the homopolymer of SMA and the copolymer of SMA and MMA richer in the first monomer are soluble in water, while the rest of this series copolymers swell in this solvent and the amount of sorbed water increases with increasing SMA fraction. The temperature for phase separation of aqueous solutions of copolymers composed of NIPAAm and SMA is higher than in the observed temperature for poly(N-isopropylacrylamide), which is attributed to higher hydrophilicity of the copolymers / Mestrado / Físico-Química / Mestre em Química

Visando o crescente interesse em pesquisa de novos materiais que utilizam polímeros biodegradáveis, este presente trabalho teve como objetivo a síntese de novos copolímeros através da reação de transesterificação no estado fundido entre poli(3-hidroxibutirato) (PHB), um polímero biodegradável, com poli(etileno glicol) (PEG). Sabe-se que um dos grandes problemas no uso do PHB é a sua elevada cristalinidade e instabilidade térmica, pois possui temperatura de fusão entre 170 e 180°C e apresenta degradação térmica a 190°C. A reação de transesterificação é uma alternativa para fazer a modificação química deste polímero, o que também viabiliza a formação de copolímeros anfifílicos triblocos. O objetivo final foi utilizar este novo material para o preparo de nanopartículas poliméricas a partir do método de difusão do solvente. Tais partículas são utilizadas para microencapsulamento de fármacos. Os copolímeros foram sintetizados e caracterizados por ensaio de solubilidade, espectrometria de ressonância magnética nuclear de hidrogênio (RMN), calorimetria diferencial exploratória (DSC), espectroscopia no infravermelho com transformada de Fourier (FTIR), cromatografia de permeação em gel (GPC), análise por difração de Raios-X (WAXS), microscopia ótica de luz polarizada (MOLP) e microscopia eletrônica de varredura (MEV). A indicação de formação de copolímero anfifílico pode ser observada nos ensaios de solubilidade, pois o copolímero mostrou-se parcialmente solúvel em uma série de solventes em que o PHB original é insolúvel. A modificação química pode ser observada com as técnicas de RMN e FTIR, cujos espectros apresentaram absorções referentes ao grupo carbonila da ligação éster. As técnicas de DSC, WAXS e MOLP mostraram uma ligeira redução na cristalinidade do material, além da temperatura de fusão reduzir-se de 171ºC para 154°C. Com o GPC observou-se uma redução da massa molar, o que facilita a formação das nanopartículas poliméricas. As nanopartículas apresentaram tamanhos com diâmetros ao redor de 250nm, quando observadas por MEV. / Aimed at the growing interest in research on new materials using biodegradable polymers, the present work was aimed at the synthesis of new copolymers through transesterification reaction in the molten state of poly (3-hydroxybutyrate) (PHB), a biodegradable polymer, poly (ethylene glycol) (PEG). It is well known that a major problem in the use of PHB is its high crystallinity and thermal instability, as it has melting temperature between 170 and 180° C and shows thermal degradation at 190°C. The transesterification reaction is an alternative to the chemical modification of this polymer, which also enables the formation of amphiphilic triblock copolymers. The mainly goal of this studies was to use this new material for the preparation of polymeric nanoparticles from the solvent diffusion method. Such particles are used for microencapsulation of drugs. The copolymers were synthesized and characterized by solubility test, Nuclear Magnetic Resonance Spectroscopy of Hydrogen (NMR), Differential Scanning Calorimetry (DSC), Infrared Spectroscopy with Fourier transform (FTIR), Gel permeation chromatography (GPC) analysis by X-ray diffraction (WAXS), polarized light optical microscopy (MOLP) and scanning electron microscopy (SEM). The signs of the formation of amphiphilic copolymer can be observed in the trials of solubility, since the copolymer was found to be partially soluble in a variety of solvents in the original PHB is insoluble. The chemical modification can be observed with the techniques of NMR and FTIR spectra which showed absorptions for the carbonyl group of the ester linkage. The techniques of DSC, WAXS and MOLP showed a decrease in crystallinity of the material in 15%, and reduce the melting temperature is 171ºC to 154°C. With the GPC showed a reduction in molar mass, which facilitates the formation of polymeric nanoparticles. The nanoparticles showed sizes with diameters around 250nm observed by SEM.

Fluoropolymers are a versatile and attractive group of compounds having an interesting mix of properties that make them highly useful for various applications. Because of strong bonding between the carbon and fluorine atom, they exhibit unique physical and chemical properties such as high thermal stability, increased chemical resistance, low refractive index, enhanced inertness towards many solvents and hydro-compounds. These characteristics have led them to be widely used in aerospace, aeronautics, optics, microelectronics, paints and coatings, and engineering structures and as biomaterials. Amphiphilic copolymers possess unique solution and solid-state properties due to their well-defined molecular architecture. These properties arise as the result of covalently combining two thermodynamically different polymer blocks that phase separate on the nanoscale. Amphiphilic copolymers based on a fluoro-monomer will combine the favourable physiochemical properties of the desired fluorine segment in combination with complementary hydrophilic segments. Such fluorinated amphiphilic copolymers are potentially useful for drug delivery vehicles and membrane applications. This project is aimed at making fluorinated amphiphilic block copolymers of hydrophobic 2, 3, 4, 5, 6 –pentafluorostyrene (PFS) and hydrophilic methacrylic acid (MAA). A controlled radical polymerization mechanism, nitroxide mediated polymerization (NMP) using NHS-BlocBuilder as the initiator was employed. The advantage of using NMP is that it facilitates the synthesis of copolymers with well-controlled narrow molecular weight distribution. However, methacrylate homopolymerization by NMP is challenging due to the high dissociation equilibrium constant therefore, the use of PFS as a controlling comonomer was explored. We established that to obtain a controlled copolymerization, a minimum of 70 mol% PFS was required, which is significantly greater than other copolymerization systems such as using as little as 4.5-8 mol% styrene to control the copolymerization of MAA. We surmise that this lack of control is due to the unfavourable reactivity ratios (Appendix I) which favour the addition of MAA rather than PFS (rPFS = 0.012, rMAA = 8.12). However, these unique reactivity ratios suggest that a semi-batch approach can be utilized to synthesize almost pure block copolymers in one pot. Therefore, poly(PFS)–b-(PFS-ran-MAA) block copolymers were synthesized and characterized by a semi batch addition of MAA. While successful, the concentration of irreversibly terminated chains was evident and greater care in reducing these unwanted reactions needs to be addressed.

Les « siRNA » sont des molécules double brin d’acide ribonucléique capables d’inhiber l’expression d’un gène spécifique, présentant ainsi un fort potentiel thérapeutique pour les maladies génétiques, les cancers et les infections virales. Cependant, son utilisation in vivo est restreinte par sa sensibilité à la dégradation enzymatique. Le projet de thèse consiste à créer un système de vectorisation des siRNA pour des applications in vivo. Nous avons synthétisé des copolymères à blocs amphiphiles biocompatibles et biodégradables capable de s’auto-assembler en diverses structures et d’encapsuler les siRNA. Les propriétés physico-chimiques des assemblages formées et l’évaluation cellulaire préliminaire est réalisée / Amphiphilic block copolymers are molecules composed of hydrophilic and hydrophobic segments having the capacity to spontaneously self-assemble into a variety of supramolecular structures like micelles and vesicles. Here, we propose an original way to self-assemble amphiphilic block copolymers into a supported bilayer membrane for defined coating of nanoparticles. The heart of the method rests on a change of the amphiphilicity of the copolymer that can be turned off and on by varying the polarity of the solvent. In this condition, the assembly process can take advantage of specific molecular interactions in both organic solvent and water. The higher gene silencing activity of the copolymer-modified complexes over the complexes alone shows the potential of this new type of nanoconstructs for biological applications, especially for the delivery of therapeutic biomolecules.