Polymeric architecture as a tool for programming sequential enzyme-induced mesophase transitions

16 November 2022, Version 1
This content is a preprint and has not undergone peer review at the time of posting.


Di- and tri-block amphiphiles can form different mesophases ranging from micelles to hydrogels depending on their chemical structures, hydrophilic to hydrophobic ratios, and their ratio in the mixture. In addition, their different architectures dictate their exchange rate between the assembled and unimer states, and consequently affect their responsiveness towards enzymatic degradation. Here we report the utilization of the different reactivities of di- and tri-block amphiphiles towards enzymatic degradation as a tool for programming formulations to undergo three sequential enzymatically induced transitions from: (i) micelles to (ii) hydrogel and finally to (iii) dissolved polymers. We show that the rate of transition between the mesophases can be programmed by changing the ratio of the amphiphiles in the formulation, and that the hydrogels can maintain encapsulated cargo, which was loaded into the micelles. The reported results demonstrate the ability of molecular architecture to serve as a tool for programming smart formulations to adopt different structures and functions.


enzyme-responsive polymeric assemblies
macromolecular architecture
polymeric assemblies
stimuli-responsive polymers

Supplementary materials

Supporting information
Synthetic procedures, amphiphiles and micelles characterization data, detailed experimental protocols and control experiments.


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