O polissacarídeo quitosana é usado em aplicações biológicas, tais como entrega de drogas e engenharia de tecidos como matriz para o crescimento celular, devido à sua biocompatibilidade e biodegradabilidade. Uma das suas utilizações mais frequentes é na forma de membranas obtidas por casting com poli (etileno glicol) (PEG). Neste trabalho, membranas de quitosana-PEG foram modificadas e otimizadas com filmes nanoestruturados de concanavalina A (Con A) e jacalina. O processo de purificação não afetou as propriedades da quitosana, tais como cristalinidade, tamanho de cristalitos, grupos funcionais e grau de acetilação. A única exceção foi a diminuição da massa molecular, provavelmente pela quebra de cadeias por adição de ácido acético à solução. As membranas fabricadas com mistura de quitosana e PEG exibiram superfície mais rugosa, porosa, com energia de superfície mais elevada do que aquelas com quitosana pura. Misturas com 20 e 30% de PEG foram testadas, sendo as que contêm 20% mais adequadas para a funcionalização, devido ao maior tamanho dos poros, de acordo com imagens de microscopia de força atômica. Na funcionalização das membranas de quitosana-PEG com proteínas, o objetivo é obter a cobertura mais uniforme com maior energia de superfície. No processo de otimização, a deposição do filme nanoestruturado de proteína foi confirmada com PM-IRRAS, espectroscopia de fluorescência e dicroísmo circular, e a energia de superfície foi calculada usando o modelo de Owens- Wendt-Rabel-Kaelble a partir dos ângulos de contato para diferentes líquidos. Para Con A e jacalina, propriedades otimizadas foram obtidas com a menor concentração de proteína testada, 0,1 mg/mL, para um tempo de adsorção de 90 minutos. Além disso, o filme de jacalina levou à maior energia de superfície, ou seja, 56,7 mJ/m², comparado com 55,9 mJ/m² para amostras modificadas com Con A. Além disso, sob essas condições de otimização, a atividade da proteína foi mantida por 4 semanas para membranas armazenadas a 4ºC. Portanto, as membranas funcionalizadas são promissoras para crescimento celular e aplicações de engenharia de tecidos / The polysaccharide chitosan is used in various biological applications such as drug delivery and especially in tissue engineering as a matrix for cell growth due to its biocompatibility and biodegradability. One of its most frequent uses is in the form of membranes made via casting blended with poly(ethylene glycol) (PEG). In this work, chitosan-PEG membranes were optimized and modified with nanostructured films of concanavalin A (Con A) and jacalin. The purification process did not affect the chitosan properties, such as crystallinity, crystallite size, functional groups and degree of acetylation. The only exception was a decrease in the molecular mass, probably owing to chain scission by addition of acetic acid to the solution. The membranes made with chitosan and PEG exhibited a rougher, porous surface, with higher surface energy than those with neat chitosan. Blends with 20 and 30% PEG were tested, and those with 20% were considered as more suitable for functionalization owing to the larger size of the pores, according to atomic force microscopy images. The functionalization of the chitosan-PEG membranes with the proteins is aimed at achieving the most uniform coverage with the highest surface energy. In the optimization procedure, the deposition of the protein nanostructured film was confirmed with PM-IRRAS, fluorescence spectroscopy and circular dichroism, while the surface energy was calculated using the Owens-Wendt-Rabel-Kaelble model and the measured contact angles for several liquids. For both Con A and jacalin, optimized properties were obtained with the lowest protein concentration tested, viz. 0.1 mg/mL, for an adsorption time of 90 min. Furthermore, the jacalin film led to the highest surface energy, namely 56.7 mJ/m², to be compared with 55.9 mJ/m² for samples modified with Con A. Under these optimized conditions, the protein activity was kept for ca. 4 weeks if the coated membranes were stored at 4ºC. Therefore, the functionalized membranes are promising for cell growth and tissue engineering applications

Orientador: Teresa Dib Zambon Atvars / Dissertação (mestrado) - Universidade Estadual de Campinas, Instituto de Quimica / Made available in DSpace on 2018-08-08T05:02:01Z (GMT). No. of bitstreams: 1 Barros_DavisonStoraide_M.pdf: 2037047 bytes, checksum: bfc81c7ccb14370261c20ba48859e0ec (MD5) Previous issue date: 2006 / Resumo: Neste trabalho são estudadas as propriedades fotoquímicas e morfológicas de filmes automontados compostos de um polieletrólito fraco e azocorantes em função das condições impostas nas soluções de origem, como o pH, a força iônica e tamponamento. Na automontagem, os filmes são fabricados pela deposição de camadas alternadas de dois materiais, de cargas elétricas opostas, a partir de suas soluções aquosas em um substrato de vidro. Os materiais usados foram o polieletrólito catiônico hidrocloreto de poli(alilamina) (PAH) e três azocorantes aniônicos: Vermelho do Congo (CR), Ponceau SS (PSS) e Alaranjado de Metila (MO). Foram fabricados filmes de PAH/CR, PAH/PSS e PAH/MO. Para avaliar somente o efeito do pH, foram usados três valores de pH (3, 7 e 10). Para verificar o efeito da força iônica, foram usadas soluções aquosas de cloreto de potássio em diferentes concentrações e, para verificar a influência de tampão, foram usados três sistemas tampão, um para cada valor de pH. Foram usadas as técnicas de espectroscopia UV-vis e turbidimetria para investigar as propriedades espectroscópicas das soluções, dos filmes e a solubilidade do PAH. Foi utilizada a técnica de microscopia de força atômica para verificar a morfologia do filme. Observa-se que a deposição dos corantes e do PAH no filme depende de suas densidades de carga, bem como da presença de outras espécies iônicas em solução. Tanto um aumento do pH como a presença de contra-íons, leva a uma redução da carga do PAH e causa um aumento de sua adsorção no filme, acompanhado de um aumento de rugosidade superficial. Porém, a primeira condição pode ou não diminuir as cargas dos corantes e a segunda enfraquece a atração eletrostática, reduzindo as suas deposições. As interações do par corante-PAH induzem a agregação dos corantes em solução e nos filmes. As diferenças estruturais dos corantes são igualmente importantes, pois o CR e o PSS são os que mais se depositam e apresentam diferentes comportamentos de deposição em função do pH. Verifica-se também que o PAH interage distintamente com diferentes contra-íons, o que pode ser explicado considerando-se a especificidade iônica e não o simples conceito de força iônica / Abstract: In this work, the photochemical and morphological properties of layer-by-layer self¿assembly films made of a weak polyelectrolyte and azodyes are studied in dependence of the solution¿s pH, ionic strength and buffering. In self-assembly technique, films are made from deposition of alternate layers of two compounds, which have opposite electrical charges, from their solutions onto a glass substrate. We employed the polyelectrolyte poly(allylamine) hydrochloride (PAH) which is positively ionized when in aqueous solution and the three different anionic azodyes: Congo Red (CR), Ponceau SS (PSS) and Methyl Orange (MO). Films of PAH/CR, PAH/PSS and PAH/MO were prepared. To investigate only the pH effect, three pH values were used (3, 7 and 10). To investigate the ionic strength, potassium chloride aqueous solution at different concentrations were used and to verify the buffer effect, three buffer systems were used, one for each pH. The UV-Vis Spectroscopy and Turbidimetry were employed to study the spectroscopic properties of the solutions, films and PAH solubility. The Atomic Force Microscopy was used to verify the film morphology. One observes that the dyes and PAH deposition depend on their charge densities as well the presence of other ionic species. An increase in solution¿s pH and/or the presence of counter-ions reduces PAH¿s charge increasing its adsorption on film, accompanied by a higher surface roughness. Differently, the first condition can or cannot reduce the dye¿s charge and the second weakens the electrostatic interaction, reducing dye adsorption. The pair dye-PAH interactions induces the dye aggregation both in solution and film. The structural differences between dyes are equally important, as CR and PSS are the ones that adsorb most and show different deposition behavior in function of solution¿s pH. Also, one verifies that PAH interacts distinctly with different counter-ions, a fact that can be explained considering ionic specificity and not by the simple concept of ionic strength / Mestrado / Físico-Química / Mestre em Química

The present thesis entitled “Design, Synthesis and Characterization of Novel Nanomaterials” is divided into five chapters, staring with a general introduction. The remaining chapters focus on four different areas/projects that I have worked on. Chapter 1: Introduction to nanomaterials This chapter reviews the basic concepts of nanomaterials and their fabrication methods. Nanomaterials are defined as materials whose dimensions (at least one) are below 100 nm. One of the most exciting aspects of nanomaterials is that their properties may differ significantly from those of the corresponding bulk materials. Nanomaterials fabrication methods can be broadly classified according to whether the assembly follows either i) the bottom-up approach or ii) the top-down approach. These methods have been discussed with various examples including the self-assembly of proteins, peptides and small molecules. In the top-down approach synthetic procedures for Graphene Oxide and its application are discussed. All characterization techniques that are used for characterizing the nanomaterials are also described briefly. Chapter 2 Section A: Self-assembly of 1-Hydroxy benzotriazole (HOBT) in water The studies presented in Chapter 2 identifies HOBT as the smallest non-peptide building block that spontaneously self-assembles into hollow micro tubular structures upon evaporation of water. The tubes form under ambient conditions by rolling over of crystalline sheets of HOBT. The packing of HOBT in the tubes seem to be predominantly driven by intermolecular π-stacking interactions between the aromatic rings of HOBT. These structural and packing patterns are similar to those found in nanotubes formed by the self-assembly of peptides and other larger molecules. The cavities of these thermolabile microtubes act as molds for casting gold nanoparticles for the synthesis of gold microrods with monodisperse dimensions. The non-reacting inner surfaces of the cavities have been used to uniquely synthesize R6G-functionalized gold microrods. With these features, HOBT is an important novel non-peptide building block for accessing micro and nanometric materials for their applications in medicine, biology and molecular biotechnology. Section B: Controlling the orientation of self-assembly of HOBT microtubes The studies presented in this chapter address the self-assembly of HOBT into microtubular structures in different solvents of varying polarities (H2O and DCM:MeOH) to understand the role of solvent volatility and its direction on the orientation of the HOBT microtubes. HOBT self-assembles from DCM:MeOH mixtures in its bipolar canonical form and is coordinated with its water of hydration, similar to its crystals obtained from water. FTIR and TGA data shows that MeOH is also integrated with the microtubes. We observe for the first time that the orientation of microtubular self-assembly is controlled in the direction of evaporation of the solvent. We demonstrate further this feature by controlling the orientation of HOBT self-assembly in exclusively vertical direction through controlled vertical evaporation of the solvent mixture DCM:MeOH (9:1). Additionally, the unique transition between vertical and horizontal orientations for self-assembled HOBT microtubes is achieved by simple change of solvation between aqueous and organic solvents. These results reveal a dynamic relationship between the rate of evaporation of solvent and the rates of formation of different self-assembled morphologies. The rate of evaporation of the solvent primarily governs the rate of formation of the tubes, rather than their orientations in three dimensions. Chapter 3: Chemical origins of debris in Graphene Oxide (GO) This chapter is focused on the investigation of the carbonyl rich fragments arising from GO and provides an understanding of its formation. The fragments are expelled from GO due to an uncontrolled nucleophile driven reaction in aqueous medium leaving the holes on the sheet. These fragments are carbonyl rich small (5 ± 2 nm) nonaromatic molecules that form as by-products of oxidative chemical reactions that occur at the sp3 clusters on the basal surface of GO sheets when they are treated with nucleophilic bases under aqueous conditions. The structure and size of the debris, and hence that of the hole, depend on the size of the sp3 cluster on the sheet. These debris fall out of the GO sheet surface, leading to formation of nanometer sized holes. Formation of debris and hence the holes can be avoided by using anhydrous polar solvents. This work sheds new light on the fundamental structure of GO and the prevention of debris from it during redox reactions enabling better control over functionalization of the GO surface. Chapter 4: Measurement of mechanical properties of polypeptide fragment from Insulin like growth factor binding protein nanotubes by the Peak Force QNM method This chapter describes the discovery of Polypeptide fragment from an IGFBP-2. This fragment self-assembles spontaneously and reversibly into nanotubular structures under oxidizing conditions. These nanotubes were characterized by using Transmission electron microscopy. Notably as compared to the monomer, an increase in intrinsic fluorescence upon self-assembly. The thermal stability of these nanotubes is realized form the fluorescence studies. Peak Force Quantitative Nanomechanical Mapping method of AFM was used to measure the Young’s modulus of the nanotubes. These nanotubes were found to have Young’s modulus value of ~10 Gpa, which is comparable to those of bones presumably due to intermolecular disulphide bonds. These nanotubes will have potential applications in tissue engineering. Chapter 5: Probing the pathways of n→π* interaction in peptides This chapter deals with the theoretical study of n→π* interaction in designed peptidomimetics. The n→π* interaction involves the delocalization of the lone pair of the donor group into the antibonding orbital (π*) of a carbonyl group. However despite beeing extensively studied there exists a debate over the validation of these n→π* interaction which is reminiscent to Bürgi and Dunitz trajectory. This chapter present our findings that peptidomimetics containing the 5,6-dihydro-4H-1,3-oxazine (Oxa) and 5,6-dihydro-4H-1,3-thiazine (Thi) functional groups at the C-terminus of Pro selectively stabilizes the cis conformer by reverse n→πi-1* interaction. These systems have been used to study the n→πi1* interaction using Natural Bond Orbital (NBO) method. Our study reveals that the energetically most favorable trajectory of a nucleophile for a favorable n→π* interaction presumably to facilitate the overlap between the lonepair of the nucleophile and the antibonding orbital of the carbonyl group. The geometrical requirements for the optimum n→π* interaction depends on the relative orientations of the orbitals that are involved. This study has implications for more accurately identifying long distant n→π* interaction.

Cette thèse a eu pour objectif la préparation d’aimants nanostructurés sains terres rares à base d’un assemblage dense de nanobâtonnets de cobalt (Co NBs). Nous avons démontré la faisabilité d’un changement d’échelle du procédé polyol, avec des conditions d’agitation contrôlées, pour obtenir 5 g de NBs monodisperse. La modification de l’agent nucléant nous a permis de contrôler la taille et la forme des NBs conduisant à des valeurs élevées de champ coercitif. La réalisation d’aimants macroscopiques denses et robustes a été possible via la dispersion des bâtonnets dans du chloroforme et son évaporation sous champ magnétique à température ambiante. La valeur de (BH)max résultante a atteint dans le meilleur des cas une valeur de 165 kJ·m-3. Des résultats préliminaires sur la compaction d’assemblées de NBs montre que la fraction volumique magnétique peut être augmenté significativement (jusqu’à 30%). Cette étude prouve que l’approche « bottom-up» est très prometteuse pour obtenir des nouveaux matériaux magnétiques durs qui peuvent compléter le panorama des aimants permanents et combler le fossé entre les ferrites et les aimants NdFeB. / The objective of this thesis is the preparation of nanostructured rare earth free permanent magnets based on dense assemblies of Co nanorods. We demonstrate the up-scaling of the polyol process for the synthesis of 5 g of monodispersed cylindrical Co NR with controlled cylindrical-like shape. Modification of the nucleating agent allows optimizing further the nanorods’ shape, leading to the highest coercivity values measured. Dense and robust macroscopic magnets were obtained via the rods’ alignment under a magnetic field presenting an ideal hysteresis loop. Additional structural and magnetic characterization was accomplished via small angle neutron scattering. A quantitative assessment of the (BH)max values showed a maximum of 165 kJ·m-3. Preliminary compaction experiments resulted in the fabrication of bulk magnets with increased magnetic volume fraction (up to 30%). We prove that the bottom-up approach is very promising to get new hard magnetic materials that can compete in the permanent magnet panorama and fill the gap between the ferrites and the NdFeB magnets.

L’objectif premier de ce travail a été de trouver une méthode de synthèse permettant depréparer des terpolymères ABC linéaires et en étoile en gardant la masse molaire des blocs A et B(PS et P2VP) constantes, tout en faisant varier la masse molaire du bloc C (PI) de sorte à avoiraccès à différentes morphologies. Le deuxième objectif consistait en l’auto-assemblage desterpolymères synthétisés sous forme de films minces.Afin de répondre au premier objectif de cette thèse, une voie de synthèse, combinant lapolymérisation anionique avec une méthode de couplage, a été mise au point. La polymérisationanionique séquentielle des blocs PS et P2VP a donné lieu à des chaînes PS-b-P2VPfonctionnalisées qui ont été ensuite couplées à différents blocs PI via une estérification de Steglich.Cette méthode de synthèse s’est révélée pertinente car des terpolymères ABC linéaires et en étoiletrès bien définis (c-à-d ayant une dispersité inférieure à 1.1) ont pu être synthétisés. De plus, laméthode de couplage, ayant un rendement proche de 100%, ne met pas en jeu l’utilisation de métalen tant que catalyseur.Dans un deuxième temps, l’auto-organisation des terpolymères a permis d’obtenir denouvelles morphologies sous forme de films minces. Un recuit par vapeur de solvant a été utilisépour apporter de la mobilité aux chaînes terpolymères. Ainsi, nous avons montré que l’autoorganisationde chaînes terpolymères linéaires (PS-b-P2VP-b-PI) permettait la formation d’unephase double gyroid coeur-écorce en film mince. De plus, l’auto-organisation des terpolymères enétoile (3 μ-ISP) a permis d’obtenir un pavage d’Archimède de type (4.6.12) pour la première foisen film mince. Dans ce cas, nous avons aussi montré que varier la masse molaire du bloc PI ainsique la nature du solvant de recuit permettait une rotation des domaines au sein la structure.Typiquement le coeur de la structure peut être occupé soit par le PI ou bien le PS. / The first objective of this work was to develop a synthesis method enabling the preparationof linear and star ABC terpolymers. The molecular weights of the A and B (PS and P2VP) blockswere kept constant while the size of the C (PI) block was varied to achieve different morphologies.The second objective of this work was devoted to the study of the self-assembly of linear and starABC terpolymer thin films. A synthesis route combining the anionic polymerization with acoupling method was developed. The PS and P2VP blocks were synthesized by a sequential anionicpolymerization. The PI block separately synthesized by anionic polymerization was then coupledto the PS-b-P2VP diblock via a Steglich esterification. This method revealed to be efficient sinceit is a catalyst metal-free reaction enabling to achieve well-defined terpolymers with a dispersitybelow 1.1The study of star and linear ABC terpolymer self-assembly led to new morphologies in thinfilm. A solvent vapor annealing treatment was used to promote the mobility of the polymericchains. A core-shell double gyroid structure was produced from the self-assembly of linear PS-b-P2VP-b-PI thin films. Four different crystallographic planes were observed depending on the filmthickness. Moreover, the self-assembly of star ABC terpolymer chains into a thin film (4.6.12)Archimedean tilling pattern was demonstrated for the first time. Here, the PS and PI blocksoccupied different places within the (4.6.12) tiling pattern depending on the PI volume ratio andthe solvent selected to swell the film.

Des propriétés optiques inédites sont prédites si des nanorésonateurs optiques sont organisés dans un matériau, ce qui peut être réalisé par l’auto-assemblage de nanoparticules plasmoniques synthétisées chimiquement. Dans ce travail de doctorat, nous utilisons des structures ordonnées de copolymères à blocs pour organiser des nanoparticules plasmoniques. Nous étudions le lien entre la structure des nanocomposites en films minces, et en particulier la nature, la densité et l’organisation des nanoparticules, et leurs propriétés optiques. Pour cela, nous avons tout d’abord produit des phases lamellaires de copolymères diblocs poly(styrène)-block-poly(2-vinylpyridine) (PS-b-P2VP) en films minces d’épaisseur (100nm-700nm) et de période lamellaire (17nm-70nm) contrôlées, et dont l’alignement et l’homogénéité sont optimisés. Nous avons développé une synthèse in situ, au sein de ces films lamellaires, qui permet de produire de façon contrôlée et reproductible, des nanoparticules plasmoniques de diamètre 7-10nm sélectivement dans les domaines P2VP. Nous avons montré que la taille et la forme des particules d’or formées in situ peuvent être modifiées en jouant sur le solvant et le réducteur chimique mis en jeu. Nous avons étudié en détail la structure des nanocomposites formulés, ce qui est en particulier nécessaire à la bonne exploitation des données d’ellipsométrie spectroscopique afin de déterminer les réponses optiques. La structure des échantillons a été étudiée par différentes méthodes de microscopie (électronique en transmission ou à balayage, à force atomique), ainsi que de la diffusion des rayons X. Nous avons utilisé une microbalance à Quartz pour étudier la quantité d’or introduite dans les matrices lamellaires de manière « cinétique » au fil de son augmentation progressive. La quantité d’or atteint des valeurs de 40 % en volume. Les propriétés optiques des films nanocomposites sont déterminées par ellipsométrie spectroscopique à angle variable et analysées à l’aide de modèles de milieux effectifs. Les films sont homogènes et anisotropes uniaxes, et on peut définir leur tenseur de permittivité diélectrique avec une composante ordinaire εo (parallèle au substrat) et une composante extraordinaire εe (perpendiculaire au substrat). L’analyse permet de montrer que les deux composantes εo and εe présentent une résonance proche de la longueur d’onde =540nm, avec une amplitude très supérieure pour εo. Lorsque la quantité d’or dans la structure lamellaire est suffisante, εo devient négatif au voisinage de la résonance et le matériau atteint le régime appelé hyperbolique, ce qui constitue un jalon essentiel pour le développement de matériaux pour des applications en imagerie hyper-résolue. / Novel optical properties in the visible range are foreseen when organizing nanoresonators, which can be performed by the self-assembly of plasmonic nanoparticles prepared by wet chemistry. In this project, we use templating block copolymers structures to organize plasmonic particles. Our goal is to relate the structure of the prepared nanocomposites thin films, and in particular the nature, density and spatial organization of the nanoparticles, with their optical index.For this purpose, we first fabricate lamellar superlattices of diblock copolymers (poly(styrene)-block-poly(2-vinylpyridine) of controlled thickness (100nm-700nm), controlled lamellar period size(17 nm-70 nm) and optimized alignment and homogeneity. Following the fabrication of the multilayer templates, an in situ and reproducible synthesis of metallic nanoparticles was developed in order to generate nanocomposites selectively inside the P2VP layers. The size of Au nanoparticles can be well controlled around 7-10 nm. We also found that the reduction process could influence the shape (sphere, triangle or cylinder) and size by using different solvents or reducing agents. Because the extraction of accurate optical responses from the spectroscopic ellipsometry data, which will come in the last part, critically relies on the precise knowledge of the sample structure. We have used several experimental techniques to access a precise description of the produced materials. In particular, we used a Quartz Crystal Microbalance as a measurement tool to ‘kinetically’ study the volume fraction of Au loading. We find that the amount of gold in the composite layers can be varied up to typically 40 volume%. The optical properties of the nanocomposite films are determined by variable angle spectroscopic ellipsometry and analyzed by appropriately developed effective medium models. The films are structurally uniaxial and homogeneous, and we can define their dielectric permittivity tensor with the ordinary (parallel to the substrate) and extraordinary (normal to the substrate) components. The analysis of the lamellar structures allows the extraction of the components εo and εe, both presenting a resonance close to =540nm, with a significantly stronger amplitude for εo. When the gold load is high enough and the couplings between particles are strong enough, the values of εo become negative close to the resonance, and the material reaches the so-called hyperbolic regime, which constitutes a step towards applications in hyper-resolution imaging.

Dans ce travail, la chimie supramoléculaire est utilisé pour créer des polymères triarylamine auto-assemblées affichant l’auto-assemblage, la conduction, et les propriétés plasmoniques. Deux classes de polymères triarylamine auto‐assemblées sont décrits en détail, y compris leurs propriétés d'auto-assemblage, structure à empiler, ainsi que le comportement électrochimique. En outre, l'application de ces matériaux à l'égard des cellules solaires organiques et spintronique moléculaire est examinée. Enfin, la capacité de ces fibres pour être utilisé dans des applications plasmoniques est détaillé, dans lequel les assemblages supramoléculaires sont présentés à quelques résonances plasmoniques de nanoparticules, agissent comme guides plasmoniques, et induisent l'ordre des nanoparticules plasmoniques à une interface liquide-liquide. Ces propriétés émergentes sont intimement liés aux interactions supramoléculaires démontrant ainsi de nouvelles applications de polymères supramoléculaires. / In this work, supramolecular chemistry is used to create self-assembled triarylamine polymers displaying novel self-assembly, conduction, and plasmonic properties. Two classes of self-assembled triarylamine polymers are described in detail, including their self-assembly properties, stacking structure, as well as electrochemical behavior. Additionally, the application of these materials towards organic solar cells and molecular spintronics is examined. Finally, the ability of these fibers to be used in plasmonic applications is detailed, wherein the supramolecular assemblies are shown to couple plasmonic nanoparticle resonances, act as plasmonic waveguides, and induce the ordering of plasmonic nanoparticles at a liquid-liquid interface. These emergent properties are intimately linked to the supramolecular interactions thereby demonstrating novel applications of supramolecular polymers.

La structure unique et les propriétés des fullerènes ont suscité l’intérêt des chercheurs, en particulier dans les domaines de l’électronique et de l’optoélectronique. Dans ce contexte, plusieurs mono- et de poly-adduits du fullerène ont été décrits pour leurs développements comme nouveaux matériaux originaux et comme polymères supramoléculaires. Nous présentons ici les synthèses et les études de nouveaux polymères supramoléculaires donneur-accepteur à base de penta(organo)[60]fullerènes. La parfaite régiosélectivité de la réaction de pentafonctionnalisation sur le [60]fullerène permet de former une cavité conique formée de cinq fragments éthynylaryles. A cette structure, différentes unités électro et/ou photoactives (tétrathiafulvalène et porphyrine de zinc) ont été liés par des liaisons covalentes via cinq réactions de cycloaddition 1,3- dipolaire. Le composé hôte-invité avec ses propriétés donneur-accepteur permet la formation d’assemblages par des interactions supramoléculaires. Nous avons réalisé les synthèses des penta(organo)[60]fullerènes comme nouveaux matériaux donneur-accepteur et nous avons étudié les propriétés des assemblages supramoléculaires en solution et à l’état solide. / The unique structure and properties of fullerenes have attracted wide interest especially in electronic and optoelectronic fields. In this context, a variety of mono-and poly-fullerene adducts have been described for theirs interest in the development of new complex materials and supramolecular polymers. Here, we present the synthesis and studies of new donor-acceptor supramolecular polymers based on penta(organo)[60]fullerenes. The perfect regioselectivity of the [60]fullerene pentafunctionalization reaction has provided us a singular conical structure formed by five ethynylaryl fragments. To this structure different electro and/or photoactive fragments (tetrathiafulvalene or zinc-porphyrin) were covalently linked using five simultaneous 1,3-dipolar cycloaddition reactions. The formed host-cavity together with the donor-acceptor properties of these system allow their assembly by supramolecular interactions. We have realized the synthesis of these penta(organo)[60]fullerenes as new donor-acceptor materials and the studies of their remarkable supramolecular arrangement in solution and solid state.

Trois architectures de copolymères (dibloc, tribloc et hétérogreffé) amphiphiles photo-stimulables à base de polyoxazoline et de groupements photo-sensibles de type coumarine sont étudiées dans ce travail. Ces copolymères s’auto-assemblent en milieu aqueux sous forme de nanoparticules de morphologies sphériques, ovales mais également de nanofibres hélicoïdales de plusieurs micromètres de longueur. Selon les cas, les morphologies sont induites par de la cristallisation des motifs coumarine entre eux ou bien des interactions polyoxazoline-coumarine. Par ailleurs, la photo-réponse des nanoparticules a été examinée après irradiation UV des groupements coumarine, capables de dimériser de manière réversible selon la longueur d’onde utilisée. Elle diffère selon l’architecture du copolymère qui constitue les nanoparticules et donne lieu à des phénomènes de (pré-)photo-dimérisation ou photo-réticulation du cœur de celles-ci avec des réversibilités sous UV variables et un maximum d'efficacité dans le cas des copolymères triblocs. La stabilité de ces auto-assemblages a également été examinée avant et après exposition UV. Dans tous les cas, l’irradiation des nanoparticules améliore leur stabilité en température et dans le temps avec un effet maximal dans le cas de la pré-photodimérisation (tribloc). Enfin, la réticulation et la cristallisation se sont révélées être des freins au piégeage de molécules hydrophobes, illustrées ici avec le Nile Red, alors que les copolymères diblocs se sont révélés être les systèmes les plus efficaces. En somme, les nanoparticules de copolymères triblocs présentent le meilleur compromis entre stabilité, efficacité UV et piégeage. / Three photo-responsive amphiphilic copolymer architectures (diblock, triblock and heterografted) based on polyoxazoline and coumarin photo-sensitive units are studied in this work. These copolymers self-assemble in water into spherical or ovalic nanoparticles and also supramicrometer helicoidal nanofibers. Depending on the macromolecular architectures, these morphologies are induced by crystallization of coumarin units or polyoxazoline-coumarin interactions. Moreover, the nanoparticle photo-response is examinated after the UV-exposure of coumarin units, that are able to reversibly dimerize according to the wavelength used. This photo-response varies with the copolymer structure and leads to (previous) photo-dimerization or photo-crosslinking phenomena. These latters present various photo-reversibility behaviors under UV and a maximal efficiency for triblock copolymers. The nanoparticle stability was additionally studied before and after UV-irradiation. In both cases, the nanoparticle stability is improved towards time and temperature with a maximal impact for the previous photo-dimerization (triblock). Finally, the crosslinking and the crystallization appear as brakes for the hydrophobic molecule entrapment, illustrated here by Nile Red, whereas diblock copolymers seem to be the most efficient systems. To conclude, previously photo-dimerized nanoparticles (triblock) are the best way combining stability, UV-efficiency and entrapment.

Le présent travail vise la synthèse d’organosilices nano-structurées à partir de briques élémentaires de silsesquioxanes polyédriques fonctionnalisées (T8-POSS) de structure cube (RSiO1,5)8. L’assemblage de briques fonctionnelles T8-POSS a été étudié selon deux voies : par des interactions fortes en formant des liaisons covalentes et par des interactions faibles en formant des liaisons hydrogène.La première partie décrit la formation de réseaux hybrides covalents à partir de structure T8 POSS portant huit fonctions aldéhydes. La synthèse et la structure cristalline de ces « cubes » fonctionnalisés sont décrites et la réactivité des fonctions aldéhydes est examinée. La formation de liaisons C=N par réaction d’amines conduit à des réseaux tridimensionnels grâce à la formation de ponts organiques bis-imines joignant les unités silsesquioxanes. Bien que la formation d’imine soit réversible, les solides obtenus ne présentent pas d’ordre à longue distance. La formation de liaisons C=C, dans des conditions de synthèse non réversibles, par réaction de bis-ylures de phosphonium avec les aldéhydes a également été étudiée. Ces réactions de type Wittig engendrent la formation de réseaux hybrides amorphes contenant des sous-structures phenylène-vinylènes dotées de propriétés de fluorescence. La deuxième partie décrit la synthèse de nouvelles molécules de T8-POSS, possédant des fonctions organiques amines ou acides carboxyliques capables d’interactions intermoléculaires grâce à des liaisons hydrogène. Ces interactions permettent l’assemblage des dérivés du T8-POSS fonctionnalisés par huit fonctions acides carboxyliques en un réseau 3D ordonné. Les briques élémentaires T8- POSS s’auto-assemblent par dimérisation des fonctions acides pour engendrer des silices hybrides cristallines. Les structures ont été déterminées par diffraction de rayons X. Les fonctions acides carboxyliques sont intéressantes non seulement par leur capacité à former des liaisons hydrogènes mais également par leur aptitude à former des carboxylates métalliques. Ces derniers ouvrent des perspectives pour la formation de réseaux d’oragnosilices incorporant des métaux. / The present work aimed at synthesising nano-structured organosilicas using polyhedral silsesquioxane building blocks (T8-POSS) having a cube structure. The assembly of T8-POSS building blocks to form a 3D network was studied in two ways: first by formation of strong covalent bonds and secondly by formation of weak hydrogen bonds.The first part described the formation of covalent hybrid networks from T8-POSS structures with eight aldehyde functional groups. The synthesis and crystal structure of these functionalised silsesquioxane cubes is described and the reactivity of the aldehyde groups is studied. The formation of C=N bonds upon reaction with amines lead to tree-dimensional networks upon formation of bis-imine bridges linking the silsesquioxane units. Despite the imine formation was reversible, the resulting solids were amorphous materials and exhibited no long distance order. The formation of C=C bonds, under non-reversible reaction conditions, was achieved by reaction of phosphonium bis-ylides. The Wittig type reactions generated amorphous hybrid networks containing bridging phenylene-vinylene substructures with fluorescence properties.The second part described the synthesis of new functionalised T8-POSS cubes with eight amine or carboxylic acid functions capable of intermolecular interactions by hydrogen bonding. It allowed the assembly of the octa-carboxylique acid cubes to form an ordered 3D hybrid network. The T8-POSS building blocks self-assembled upon dimerization of the acid groups and generated crystalline hybrid silicas. The crystal structures were determined by X-ray diffraction. The use carboxylic acid groups is interesting because of its ability to form hydrogen bonds and also because of its ability to form metal carboxylate derivatives. It could lead to hybrid metal organic silica frameworks.