Stretched or wrinkled? Looking into the polymer conformation within polymersome membranes

Self-assembly of amphiphilic block-copolymers into polymersomes is a well-established concept. In this membrane, the hydrophilic part is considered to be loosely assembled towards the solvent, and the hydrophobic part on the inside of the membrane is considered to be more densely packed. Within the membrane, this hydrophobic part could now have a stretched conformation or be a random coil, depending on the available space and also on the chemical nature of the polymer. We now analysed the literature for works on polymersomes that determined the membrane thickness via cryo-TEM and analysed the hydrophobic part of their polymers for their conformation. Over all available block-copolymers, a variety of trends became obvious: the longer a hydrophobic block, the more coiled the conformation and the bulkier the side chains, the more stretched the polymer became. Polymers with less conformational freedom like semi-crystalline ones were present in a more stretched conformation. Both trends could be exemplified on various occasions in this cross-literature meta-study. This overview hence provides additional insight into the physical chemistry of block-copolymer membranes.