Hierarchical compartmentalization through the bottom-up approach is ubiquitous in living cells but remains a formidable task in synthetic systems. Here we report on hierarchically compartmentalized supramolecular gels that are spontaneously formed by multilevel self-sorting. Two types of molecular gelators are formed in situ from nonassembling building blocks and self-assemble into distinct gel fibers through a kinetic self-sorting process; interestingly, these distinct fibers further self-sort into separated microdomains, leading to microscale compartmentalized gel networks. Such spontaneously multilevel self-sorting systems provide a “bottom-up” approach toward hierarchically structured functional materials and may play a role in intracellular organization.

Here we report on howm etastable supramolecular gels can be formed through seeded self-assembly of multicomponent gelators.Hydrazone-based gelators decorated with non-ionic and anionic groups are formed in situ from hydrazide and aldehyde building blocks,a nd lead through multiple self-sorting processes to the formation of heterogeneous gels approaching thermodynamic equilibrium. Interestingly,the addition of seeds composing of oligomers of gelators bypasses the self-sorting processes and accelerates the selfassembly along ak inetically favored pathway,r esulting in homogeneous gels of whichthe network morphologies and gel stiffness are markedly different from the thermodynamically more stable gel products.I mportantly,o ver time,t hese metastable homogeneous gel networks are capable of converting into the thermodynamically more stable state.This seedingdriven formation of out-of-equilibrium supramolecular structures is expected to serve as as imple approach towards functional materials with pathway-dependent properties.

Extremely low-volatility functional deep eutectic solvents (DESs), based on ethylene glycol (EG) and diethylene glycol (DG) as hydrogen-bond donor and the ammonium salts obtained from triethylenetetramine (TETA) and HCl at different mole ratios as hydrogen-bond acceptor, were designed and used to capture CO2. All of the designed DESs can efficiently capture CO2 even at low partial pressures. CO2 absorption capacity of [TETA]­Cl-EG DES with n [TETA]Cl/n EG 1:3 is high up to 17.5 wt % (1.456 mol CO2/mol [TETA]­Cl) at 40 °C and 1 atm. CO2 absorption capacity decreases with increasing temperature and decreasing CO2 partial pressure. Regeneration experiments show that CO2 absorption capacities in [TETA]­Cl-EG DES and [TETA]­Cl-DG DES do not vary after five absorption/desorption cycles. It is found that EG or DG can increase the absorption capacity via activating −NH– or −NH2 on [TETA]­Cl and enhance the basicity of DESs. In addition, CO2 absorption mechanism in [TETA]­Cl-EG DES based on the change of its viscosity during absorption and FTIR analysis indicates that there is a chemical interaction between CO2 and [TETA]­Cl, and the stoichiometry for the reversible absorption is 1.5 molecules of CO2 per [TETA]­Cl-EG DES molecule.

Hydrogel microparticles are important in materials engineering, but their applications remain limited owing to the difficulties associated with their manipulation. Herein, we report the self‐orientation of crescent‐shaped hydrogel microparticles and elucidate its mechanism. Additionally, the microparticles were used, for the first time, as micro‐buckets to carry living cells. In aqueous solution, the microparticles spontaneously rotated to a preferred orientation with the cavity facing up. We developed a geometric model that explains the self‐orienting behavior of crescent‐shaped particles by minimizing the potential energy of this specific morphology. Finally, we selectively modified the particles’ cavities with RGD peptide and exploited their preferred orientation to load them with living cells. Cells could adhere, proliferate, and be transported and released in vitro. These micro‐buckets hold a great potential for applications in smart materials, cell therapy, and biological engineering.

Supramolecular structures with strain‐stiffening properties are ubiquitous in nature but remain rare in the lab. Herein, we report on strain‐stiffening supramolecular hydrogels that are entirely produced through the self‐assembly of synthetic molecular gelators. The involved gelators self‐assemble into semi‐flexible fibers, which thereby crosslink into hydrogels. Interestingly, these hydrogels are capable of stiffening in response to applied stress, resembling biological intermediate filaments system. Furthermore, strain‐stiffening hydrogel networks embedded with liposomes are constructed through orthogonal self‐assembly of gelators and phospholipids, mimicking biological tissues in both architecture and mechanical properties. This work furthers the development of biomimetic soft materials with mechanical responsiveness and presents potentially enticing applications in diverse fields, such as tissue engineering, artificial life, and strain sensors.