Di- and triblock
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 toward enzymatic degradation. Here we report
the utilization of the different reactivities of di- and triblock
amphiphiles, having exactly the same hydrophilic to lipophilic balance,
toward enzymatic degradation as a tool for programming formulations
to undergo 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.