Construction from Destruction: Hydrogel Formation from Triggered Depolymerization-Based Release of an Enzymatic Catalyst

Biomimetic systems that undergo macroscopic phase transformations by transducing and amplifying external cues are highly desirable for applications such as self-healing. Here, we report self-assembly of polyelectrolyte complexes into a vesicular structure that can accommodate hydrophilic guest molecules, including enzymes. Triggered depolymerization of one of the polyelectrolyte molecules in the complex causes the vesicle to disassemble and release its contents. Such a triggered release of enzymes causes molecular-scale events to be amplified due to the enzyme’s catalytic properties. This feature has been utilized to demonstrate construction of hydrogels from the destruction of nanoscopic polymeric vesicles. The design principles developed here are broadly adaptable to other triggerable depolymerization motifs reported in the literature.