Bioinspired baroplastic glycosaminoglycan sealants for soft tissues

We describe biomimetic adhesives inspired by the marine glues fabricated by the sandcastle worm. The formation of stable polyelectrolyte complexes between poly-L-lysine (PLL) and glycosaminoglycans (GAGs) with different sulfation degree - heparin (HEP), chondroitin sulfate (CS) and hyaluronic acid (HA) - is optimized by zeta-potential titrations. These PLL/GAG complexes are transformed into compact polyelectrolyte complexes (coPECs) with controlled water contents and densities via baroplastic processing. Rotational shear tests demonstrate that coPECs containing sulfated GAGs (HEP or CS) have solid-like properties, whereas HA-based complexes form highly hydrated viscous-like networks. The adhesiveness of the generated coPECs (normalized lap shear strength) is tested in dry and wet states using polystyrene and rabbit skin, respectively. In dry state, the adhesives exhibit lap shear strengths in the order of hundreds of kPa, with coPLL/HEP and coPLL/CS being about 1.5 times stronger than coPLL/HA. In wet state, all coPECs seal rabbit skin and recover over 60% of the elongation capacity of intact skin with coPLL/HA providing the sturdiest adhesion (∼85% elongation recovery). We demonstrate that this is due to the higher water fraction that improves the bonding between the wet specimens, showcasing the potential superior mechanical recovery on injured tissues. STATEMENT OF SIGNIFICANCE: The development of medical sealants with sufficient adhesive strength in the presence of water and moist remains a huge challenge. We present glycosaminoglycans (GAGs) as biomaterials for the assembly of baroplastics with strong adhesive strength to soft tissues at physiological conditions. Baroplastics with tacky properties were generated by a mild assembly process based on polyelectrolyte complexation and compaction. These materials behave as versatile sealants: their adhesiveness can be adjusted to either dry or wet specimens because of the different sulfation degree of GAGs. These sealants were noncytotoxic towards L929 cells and allowed the damaged skin to recover a great deal of its native elasticity: they preserved the J-shaped stress/strain mechanical response that is typical of biological soft tissues.