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<dc:title xml:lang="en">Photo-responsive systems in aqueous solution : from model polyelectrolytes to polyelectrolyte-surfactant complexes</dc:title>
<dcterms:alternative xml:lang="fr">Systèmes photo-stimulables en solution : polyélectrolytes modèles et complexes polyélectrolytes-tensioactifs</dcterms:alternative>
<dc:subject xml:lang="fr">Polyélectrolytes (PEs) photosensibles</dc:subject>
<dc:subject xml:lang="fr">Azo-tensioactif/PE complexes</dc:subject>
<dc:subject xml:lang="fr">Auto-assemblage</dc:subject>
<dc:subject xml:lang="fr">Azo-tensioactif/co-tensioactif</dc:subject>
<dc:subject xml:lang="fr">Diffusion des rayons X et des neutrons aux petits angles</dc:subject>
<dc:subject xml:lang="en">Photoresponsitive polyelectrolytes (PEs</dc:subject>
<dc:subject xml:lang="en">Azo-surfactant/PE complexes</dc:subject>
<dc:subject xml:lang="en">Self-assembly</dc:subject>
<dc:subject xml:lang="en">Azo-surfactant/co-surfactant</dc:subject>
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<dcterms:abstract xml:lang="fr">Cette thèse vise à concevoir, synthétiser et étudier des systèmes photo-stimulables modèles en solution aqueuse formés à partir de polyélectrolytes (PEs) et de tensioactifs. La photosensibilité est liée à la présence de chromophores azobenzène (Azo) qui subissent une isomérisation trans → cis sous irradiation UV. Nous avons considéré dans un premier temps un PE hydrophile sur lequel nous avons greffé des groupements Azo. Ce système forme de agrégats globulaires en solution en raison du collapse des chaînes et des associations intermoléculaires. La taille des agrégats varie sous irradiation UV. Elle dépend également de la masse molaire des PEs et du taux de greffage des groupements Azo. Nous avons considéré dans un second temps des tensioactifs dans lesquels des groupements Azo ont été introduits (Azo-tensioactifs). Nous avons étudié leur complexation avec des PEs de charge opposée. Ces systèmes s’organisent en colliers de perles. Les polyions décorent les micelles et pénètrent à l’intérieur de celles-ci (co-micellisation). Sous irradiation UV, la taille des perles diminue sans vraiment modifier l’organisation des complexes. Nous nous sommes enfin intéressés à l’auto-assemblage d’Azo-tensioactifs et de co-tensioactifs. Ce mélange conduit à la formation des micelles allongées et à la création d’un gel. Sous irradiation UV, on observe une transition gel - fluide. L’origine ce phénomène est lié à un changement morphologique des agrégats micellaires (micelles allongées - micelles globulaires).</dcterms:abstract>
<dcterms:abstract xml:lang="en">This thesis aims at designing, synthesizing and characterizing model photo-responsive systems in aqueous solution. These systems are based on polyelectrolytes (PEs) and surfactants. The photo-sensitivity arises from the presence of azobenzene (Azo) groups that undergo a transition from a trans to a cis isomer. We first considered a hydrophilic PE on which we grafted Azo groups. This system forms globular aggregates in solution due to chains collapse and intermolecular associations. The size of the aggregates varies under UV irradiation. It also depends on the molar mass of the PEs and the Azo content. We then considered surfactants in which Azo groups have been introduced (Azo-surfactants). We studied their complexation with oppositely charged PEs. These systems show a pearl necklace organization. The PEs decorate the micelles and penetrate inside (co-micellisation). Under UV irradiation, the size of the pearls decreases without really modifying the general organization of the complexes. Finally, we were interested in the self-assembly of Azo-surfactants and co-surfactants. This mixture leads to the formation of wormlike micelles and the creation of a gel. Under UV irradiation, a gel - fluid transition is observed. The origin of this phenomenon is linked to a morphological transition of the micellar aggregates (wormlike micelles - globular micelles).</dcterms:abstract>
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