Vinylogous Urea-Urethane Vitrimers: Accelerating and Inhibiting Network Dynamics through Hydrogen Bonding.

Vinylogous urethane (VUO ) based polymer networks are widely used as catalyst-free vitrimers that show rapid covalent bond exchange at elevated temperatures. In solution, vinylogous ureas (VUN ) undergo much faster bond exchange than VUO and are highly dynamic at room temperature. However, this difference in reactivity is not observed in their respective dynamic polymer networks, as VUO and VUN vitrimers prepared herein with very similar macromolecular architectures show comparable stress relaxation and creep behavior. However, by using mixtures of VUO and VUN linkages within the same network, the dynamic reactions can be accelerated by an order of magnitude. The results can be rationalized by the effect of intermolecular hydrogen bonding, which is absent in VUO vitrimers, but is very pronounced for vinylogous urea moieties. At low concentrations of VUN , these hydrogen bonds act as catalysts for covalent bond exchange, while at high concentration, they provide a pervasive vinylogous urea - urethane (VU) network of strong non-covalent interactions, giving rise to phase separation and inhibiting polymer chain dynamics. This offers a straightforward design principle for dynamic polymer materials, showing at the same time the possible additive and synergistic effects of supramolecular and dynamic covalent polymer networks.

Shape-transformation of polymersomes from glassy and crosslinkable ABA triblock copolymers.

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.

Polymersomes: Breaking the Glass Ceiling?

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.