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, Various techniques like nanoprecipitation, film hydration and double emulsion are used to perform the self-assemblies with the objective to obtain polypeptoid vesicles. The self-assemblies are investigated in detail by DLS, cryo-EM, confocal laser scanning microscope (CLSM) and 1 H-NMR. In the first family of copolymers, ROP of sarcosine NTA (Sar-NTA) is initiated by oxyamino-ended poly(?-caprolactone) (PCL), to obtain diblock copolymer PCL-b-PSar and triblock copolymer PSar-b-PCL-b-PSar. Unilamellar sheets and nanofibers are obtained by nanoprecipitation of PSarb-PCL-b-PSar copolymers at room temperature. These lamellae and fibrous structures are tra nsformed into worm-like cylinders and spheres after heating to 65 °C. Heating at 90 °C leads eventually to multilamellar polymersomes. The second family of copolymers is based on a thioetherbearing polypeptoid, poly(N-3-(methylthio)propyl glycine) (PMeSPG). The new monomer, MeSPG-NTA is obtained from a "decarboxylation?Ncarboxymethylation" procedure from methionine, followed by cyclization. The amphiphilic block copolymers PEG -b-PMeSPG and PMeSPG-b-PSar are synthesized with different molecular weights and hydrophilic/hydrophobic ratios. Vesicles have been achieved with different methods, and the mechanism of vesicle formation through diverse nonergodic morphologies are discussed in detail. The thioether-bearing polypeptoid is designed because of its oxidation-responsive features. Effectively, oxidation-responsive disruption is achieved for the PMeSPG-b-PSar polypeptoid vesicles, ABSTRACT As a robust nanocontainer with polymeric bilayer structure, polymer vesicle, also called polymersome, has been considered as potential drug carrier in biomedical field, because of its cell-mimicking structure, high stability and capability to be functionalized. For practical use of polymersomes in biomedical applications, the biocompatibility of the copolymers that compose the vesicles become an important issue

, En évitant la formation de liaisons hydrogène inter -et intramoléculaires, les polypeptoids ont des solubilités bien meilleures que les polypeptides dans des solvants organiques usuels, tandis que la biocompatibilité est bien maintenue. Des travaux sur l'auto-assemblage de copolymères à blocs contenant polypeptoids émergent dans la littérature. Cependant, les travaux sur les vésicul es polypeptoids sont encore rares. Dans cette thèse, deux familles de copolymères à blocs amphiphiles contenant les polypeptoids ont été synthétisées par la polymérisation par ouverture de cycle (ROP) de N-thiocarboxyanhydrides d'acides aminés N-substitués (NNTA). Différentes techniques telles que la nanoprécipitation, l'hydratation de film mince et la double émulsion ont été utilisées pour réaliser les auto -assemblages dans le but d'obtenir des vésicules polypeptoids, MOTS CLÉS Auto-assemblage, polypeptoids, polymersome, oxydation-stimulable, photo-stimulable RÉSUMÉ Comme un nanoconteneur robuste formé d'une bicouche de polymères amphiphiles, vésicule polymère, aussi appelée polymersome, a été considérée comme un vecteur de médicament potentiel dans le domaine biomédical, grâce à sa structure imitant les cellules, sa grande stabilité et sa capacité à être fonctionnalisée

. Dans-la-première-famille-de-copolymères, Sar-NTA) a été initiée par le poly(?-caprolactone) (PCL) à terminaison -oxyamine, pour obtenir le copolymère dibloc PCL-b-PSar, et le copolymère tribloc PSar-b-PCL-b-PSar. Des feuilles et nanofibres unilamellaires ont été obtenues par nanoprécipitation des copolymères PSar-b-PCL-b-PSar à température ambiante. Ces lamelles et structures fibreuses peuvent être transformées en particules cylindriques et sphèriques après chauffage à 65 °C. Le chauffage à 90 °C conduit finalement à des polymeromes multilamellaires. La seconde famille de copolymères est basée sur un polypeptoid portant thioéthers

M. Le-nouveau, MeSPG-NTA, a été préparé par une procédure de « décarboxylation? N-carboxyméthylation » à partir de la méthionine, suivie d'une cyclisation. Les copolymères à blocs amphiphiles PEG -b-PMeSPG et PMeSPG-b-PSar ont été synthétisés avec de différentes masses moléculaires et de différents rapports de blocs hydrophile/hydrophobe. Les études d'auto -assemblage ont été menées sur ces copolymères pour la formation de vésicules polypeptoids, Des vésicules ont été obtenues avec de différentes méthodes, et le m écanisme de la formation des vésicules à travers diverses morphologies non-ergodiques a été discuté en détail

, En effet, le des assemblage des vésicules polypeptoids de PMeSPG-b-PSar sensible à l'oxydation a été obtenu en raison de la transition « thioéther?sulfoxyde » stimulée respectivement par le peroxyde d'hydrogène (H2O2) et par l'oxygène singulet ( 1 O2) produit en presence de la lumière, Les vésicules polypeptoids oxydation-stimulable et photo-stimulable ainsi réalisés peuvent être des systèmes prometteurs dans des applications de relargages contrôlés des médicaments. KEYWORDS Self-assembly, polypeptoids, polymersome, oxidation-responsive