Frequently, the classical self-assembly techniques applied to amphiphilic glycopolymers lead to primitive morphologies, i.e. spherical micelles/nanoparticles. Herein, we report a facile and rapid one-pot synthesis and self-assembly of grafted amphiphilic glycopolymers using photo-initiated Polymerization-Induced Self-Assembly (Photo-PISA) under UV-irradiation at room temperature. Such glycopolymers were based on dextran as a hydrophilic steric stabilizer backbone and poly(hydroxypropyl methacrylate) PHPMA as a hydrophobic graft. Transmission electron microscopy and light scattering analysis reveal the formation of a broad set of advanced glyco-nanostructures ranging from spherical micelles to worm-like micelles and vesicles depending on both the PHPMA graft length and the solids content.

Self-assembly of polysaccharide-containing amphiphilic copolymers: polymerization induced self-assembly versus traditional techniques.

Phase separation in giant polymer/lipid hybrid unilamellar vesicles (GHUVs) has been described over the last few years. However there is still a lack of understanding on the physical and molecular factors governing the phase separation in such systems. Among these parameters it has been suggested that in analogy to multicomponent lipid vesicles hydrophobic mismatches as well as lipid fluidity play a role. In this work, we aim to map a global picture of phase separation and domain formation in the membrane of GHUVs by using various copolymers based on poly(dimethylsiloxane) (PDMS) and poly(ethylene glycol) (PEO) with different architectures (grafted, triblock) and molar masses, combined with phospholipids in the fluid (POPC) or gel state (DPPC) at room temperature. From confocal imaging and fluorescence lifetime imaging microscopy (FLIM) techniques, the phase separation into either micro- or nano-domains within GHUVs was studied. In particular, our systematic studies demonstrate that in addition to the lipid/polymer fraction or the lipid physical state, important factors such as line tension at lipid polymer/lipid boundaries can be finely modulated by the molar mass and the architecture of the copolymer and lead to the formation of stable lipid domains with different sizes and morphologies in such GHUVs.