Non-swelling polyelectrolyte complex hydrogels with tissue-matchable mechanical properties for versatile wet wound closure

The stable adhesion of hydrogel-based bioadhesives with tissue-matchable mechanical properties in biological environments remains a significant challenge. In this work, we propose a polyethyleneimine-polyacrylic acid (PEI-PAA, PEA) double-network polyelectrolyte hydrogel with swelling resistant capacity and tunable mechanical properties via one-step UV-initiated polymerization. Driven by electrostatic interactions and polymer-chain entanglement, this PEA hydrogel displays a distinctive microphase separation behavior, which facilitates a wide tunability in mechanical properties. Specifically, the modulus varies from 0.4 MPa to 106 MPa, and the toughness ranges from 1479 kJ/m3 to 7641 kJ/m3, respectively. Besides, the microphase separation endows PEA hydrogel with notable anti-swelling properties in saline, TBS buffer, and blood, leading to consistent adhesion to diverse moist tissues. We further demonstrate that our PEA hydrogels provide matchable mechanical properties and long-lasting adhesion to rat skin and arteries, which promote skin injury healing and effectively halt artery rupture bleeding in vivo. This work presents a straightforward method to generate non-swelling hydrogels and offers novel insight into the development of bioadhesives to meet diverse mechanical requirements.