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Polymersomes have gained a lot of attention in recent years. Their compartmentalized, hollow nature, stability and ability to transport both hydrophilic and hydrophobic cargo has made them attractive for increasingly complex applications in various fields of biomedicine, catalysis and diagnostics. Progress in these fields would therefore benefit from improvements in polymersome functionality. Recently, morphological control of polymersomes, namely the fabrication of various non‐spherical morphologies, has emerged as a means to enhance the usefulness of the polymersomes. In the present review, we highlight the most topical trends in this field and how these developments and the newly acquired knowledge about their nature can be leveraged towards applications. © 2021 Society of Chemical Industry

 

Recent developments in the field of polymer vesicles, i.e. polymersomes, have demonstrated that disrupting the equilibrium conditions of the milieu could lead to shape transformation into stable non-spherical morphologies, bringing on-demand shape control to reality and bearing great promise for cell mimicry and a variety of biomedical applications. Here, we studied the self-assembly behavior of glassy amphiphilic triblock copolymers, poly(ethylene glycol)- block -polystyrene- stat -poly(coumarin methacrylate)- block -poly(ethylene glycol) (PEG- b -P(S- stat -CMA)- b -PEG), and their response to various stimuli. By changing the respective molecular weights of both the hydrophobic P(S- stat -CMA) and the hydrophilic PEG blocks, we varied the hydrophobic volume fraction thereby accessing a range of morphologies from spherical and worm-like micelles, as well as polymersomes. For the latter, we observed that slow osmotic pressure changes induced by dialysis led to a decrease in size while rapid osmotic pressure changes by addition of a PEG fusogen led to morphological transformations into rod-like and tubular polymersomes. We also found out that chemically crosslinking the vesicles before inducing osmotic pressure changes led to the vesicles exhibiting hypotonic shock, atypical for glassy polymersomes. We believe that this approach combining the robustness of triblock copolymers and light-based transformations will help expand the toolbox to design ever more complex biomimetic constructs.