Biomimetic Structural Hydrogels Reinforced by Gradient Twisted Plywood Architectures

Naturally structural hydrogels such as crustacean exoskeletons possess a remarkable combination of seemingly contradictory properties: high strength, modulus, and toughness coupled with exceptional fatigue resistance, owing to their hierarchical structures across multiple length scales. However, replicating these unique mechanical properties in synthetic hydrogels remains a significant challenge. This work presents a synergistic approach for constructing hierarchical structural hydrogels by employing cholesteric liquid crystal self‐assembly followed by nanocrystalline engineering. The resulting hydrogels exhibit a long‐range ordered gradient twisted plywood structure with high crystallinity to mimic the design of crustacean exoskeletons. Consequently, the structural hydrogels achieve an unprecedented combination of ultrahigh strength (46 ± 3 MPa), modulus (496 ± 25 MPa), and toughness (170 ± 14 MJ m−3), together with recorded high fatigue threshold (32.5 kJ m−2) and superior impact resistance (48 ± 2 kJ m−1). Additionally, through controlling geometry and compositional gradients of the hierarchical structures, a programmable shape morphing process allows for the fabrication of complex 3D hydrogels. This study not only offers valuable insights into advanced design strategies applicable to a broad range of promising hierarchical materials, but also pave the ways for load‐bearing applications in tissue engineering, wearable devices, and soft robotics.