This thesis focuses on the self-assembly of the boron cluster compounds and the coassembly of metallacaborane cobalt bis(dicarbollide), COSAN, with hydrophilic polymers. The research was motivated by the discovery of HIV inhibition by COSAN and its conjugates. Therefore, we decided to study in detail the behavior of boron cluster compounds in water. We demonstrated the amphiphilic character of several boranes and carboranes by the study of surface tension and self-assembly despite the absence of classical amphiphilic topology. The behavior of COSAN showed similarities with classical surfactants, such as SDS, whereas the behavior of smaller clusters with high charge density reminded of hydrotropes or chaotropes. Furthermore, we searched for the most suitable carriers of COSAN for drug delivery. Based on the earlier findings that COSAN interacts with both poly(ethylene oxide), PEO, and poly(2-oxazoline), POX, we prepared nanoparticles by mixing COSAN with block copolymers of various types of POX. Comparing linear and star-like block copolymers, we showed that the polymer architecture has a crucial role in the morphology of nanoparticles. In addition, we proved different selectivity of alkaline cations towards PEO and POX, resulting in the different structures of nanoparticles depending on the present...

This thesis is focused on synthesis and polymerization of caprolactone and its derivatives by living ring opening polymerization (LROP), Self-assembly in aqueous solutions produced nanoaggregates comprised of amphiphilic block copolymers or telechelic polymers with incorporated boron compounds (phenyl boronic acids and boron clusters). Incorporation of boron compounds was facilitated either by covalent or non-covalent bonding. Obtained complex nanoparticle structures manifested stimuli-responsive behaviour and were investigated under varying conditions by combination of light scattering, fluorescence spectroscopy and electron microscopy. The obtained results on solution behaviour of polymers in combination with added value of boron compounds, yield general aspects of nano aggregate morphology, responsive character tuning and practical aspects of synthesis and self-assembly overcame in the preparation process. The publications wrote during this thesis are therefore adding valuable information to researchers engaged in biomedical utilization of such nano assemblies.

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Cette thèse présente une étude de la structure de solutions de polyélectrolytes (PEs) dans les liquides ioniques (LIs) et de la structure locale des LIs en présence de PEs. Les techniques de diffusion de rayons X et de neutrons ont été principalement utilisées pour cette étude. Dans une première partie, la capacité des LIs à former des « clusters » à l’échelle nanoscopique est démontrée. Dans une seconde partie, l’influence de la nature des contreions et du solvant sur le comportement du polystyrène sulfonate (PSS) en solution est abordée. La conformation moyenne du PSS et son état de dispersion dans les milieux aqueux et organiques sont alors explorés dans une troisième partie. Une étude similaire pour le cas spécifique des milieux LIs est présentée dans une quatrième partie. Finalement, d’autres polymères, chargés ou neutres, en solution dans les LIs, sont considérés dans une cinquième et dernière partie. / In this thesis the structure of polyelectrolyte (PE) solutions in ionic liquids (ILs) and mutual influence of bothcomponentsthe local structure of the latter in the presence of PEs are studied. X-ray and neutron scatteringtechniques have been mainly used for the present investigation. In a first part, the ability of considered ILs toform clusters at nanoscale is demonstrated. In a second part, the influence of the nature of counterions andthe solvent on the polystyrene sulfonate (PSS) behavior in solution is tackled. PSS average conformation anddispersion state in aqueous and organic media are then explored in a third part. A similar investigation, carriedout on the specific case of PSS in IL media, is described in a fourth part. Finally, other polymers, both chargedand neutral, in IL solutions are considered in a fifth and last part.