Polymersomes: Breaking the Glass Ceiling?

Abstract Polymer vesicles, also known as polymersomes, have garnered a lot of interest even before the first report of their fabrication in the mid‐1990s. These capsules have found applications in areas such as drug delivery, diagnostics and cellular models, and are made via the self‐assembly of amphiphilic block copolymers, predominantly with soft, rubbery hydrophobic segments. Comparatively, and despite their remarkable impermeability, glassy polymersomes (GPs) have been less pervasive due to their rigidity, lack of biodegradability and more restricted fabrication strategies. GPs are now becoming more prominent, thanks to their ability to undergo stable shape‐change (e.g., into non‐spherical morphologies) as a response to a predetermined trigger (e.g., light, solvent). The basics of block copolymer self‐assembly with an emphasis on polymersomes and GPs in particular are reviewed here. The principles and advantages of shape transformation of GPs as well as their general usefulness are also discussed, together with some of the challenges and opportunities currently facing this area.