Hierarchically structuralized hydrogels with ligament-like mechanical performance

Abstract Mechanical properties of synthetic hydrogels remain inferior to those of load-bearing tissues such as ligaments, one of the strongest and stiffest natural hydrogels in the human body. Inspired by biological structures and their mechanisms conferring high mechanical properties, we report strong, stiff, and tough hydrogels composed of fiber-shaped elements that can be assembled into parallel bundles, closely resembling natural ligaments. These hydrogel fibers, readily fabricated with diameters of a few hundred micrometers, comprise polymer–particle hybrid agglomerates embedded in a continuous, interconnected polymer matrix. Strong polymer–particle interactions combined with spatial confinement within the agglomerates enable efficient load transfer, resulting in significant load-transfer lengths and substantial energy dissipation across the network. This design overcomes the conventional trade-offs between strength/stiffness and toughness/stretchability in polymer composites, thereby achieving tensile strength of 61 ± 8 MPa, elastic modulus of 131 ± 15 MPa, toughness 135 ± 11 MJ m −3 , and stretchability exceeding 400%. When assembled into millimeter-scale hierarchical bundles, the hydrogels mimic the structural organization of ligaments, sustain loads of tens of kilograms, and function as strain sensors.