Cells execute mesmerizing functions using supramolecular polymers (SPs) formed through the self-assembly of biological precursors. Integration of the vast array of synthetic SPs with living cells would offer a powerful way to remold cellular functions and bridge the gap between synthetic materials and the biological realm, yet remains a challenge because of the lack of robust abiotic SP systems that can be triggered to self-assemble inside cells. Here, we report how fully abiotic SPs can be synthesized inside living cells via an organocatalysis-responsive self-assembly strategy, and how the in situ-generated SPs are capable of interfering and can interfere with cellular functions. The incorporation of a nucleophilic organocatalyst (CAT) into living cells accelerates the intracellular conversion of hydrazide (H) and aldehyde-derived precursors (A) to hydrazone-based monomers (HA3) that locally self-assemble into SPs. Interestingly, the in situ-generated SPs possess ignorable effects on cell viability and proliferation but remarkably hinder cell migration. Furthermore, the presence of SPs is found to retard intracellular diffusion and alter the organization of the actin cytoskeleton, both of which are suggested to be responsible for the hindered cellular migration. In considering the vastly wide range of synthetic SPs, tremendous non-natural cellular functionalities can be obtained by in situ-synthesizing SPs.

Living organisms are capable of dynamically changing their structures for adaptive functions through sophisticated reaction-diffusion processes. Here we show how active supramolecular hydrogels with programmable lifetimes and macroscopic structures can be created by relying on a simple reaction-diffusion strategy. Two hydrogel precursors (poly(acrylic acid) PAA/CaCl₂ and Na₂CO₃) diffuse from different locations and generate amorphous calcium carbonate (ACC) nanoparticles at the diffusional fronts, leading to the formation of hydrogel structures driven by electrostatic interactions between PAA and ACC nanoparticles. Interestingly, the formed hydrogels are capable of autonomously disintegrating over time because of a delayed influx of electrostatic-interaction inhibitors (NaCl). The hydrogel growth process is well explained by a reaction-diffusion model which offers a theoretical means to program the dynamic growth of structured hydrogels. Furthermore, we demonstrate a conceptual access to dynamic information storage in soft materials using the developed reaction-diffusion strategy. This work may serve as a starting point for the development of life-like materials with adaptive structures and functionalities.

Transient materials that function out-of-equilibrium have been of great interest due to their unique properties that are rarely observed in thermodynamically stable occasions. However, the current advances are still limited to supramolecular objects, and the applications using this transient nature remain largely unexplored. Herein we report on chemical fuel powered transient polymer hydrogels for controlled formation and free release of pharmaceutical crystals. The transient polymer hydrogels with highly tunable stiffness and lifetime were created by chemical fuel powered crosslinking, which can be well regenerated without obvious deteriorations by simply refueling. On the basis of these properties, especially the transient nature, these hydrogels can serve as novel reusable platforms to control the pharmaceutical crystallization, more importantly, freely release the obtained crystals, which is inaccessible by conventional static gels. This work is expected to serve as an example to accelerate the development of more advanced out-of-equilibrium materials and exploitations of their high-tech applications.

The present work shows how transient supramolecular hydrogels can be formed by catalytically controlled molecular self-assembly. Catalysis formation of molecular gelators leads the self-assembly along a kinetically favored pathway, resulting in transient hydrogels. This work demonstrates an effective approach towards pathway-dependent supramolecular materials.