Injectable Dopamine–Polysaccharide In Situ Composite Hydrogels with Enhanced Adhesiveness

Polysaccharide bio-adhesives used for non-invasive repair often show weak mechanical strength and tissue adhesion, even when covalently modified with dopamine (DA) from mussel proteins and its derivatives. Low cohesion of the polysaccharide adhesives and easy oxidation of DA may result in the low adhesion properties of the polysaccharide-DA adhesives. In this work, we aimed to prepare a series of injectable hydrogel adhesives to improve their cohesion and adhesion by in situ mixing DA with the polysaccharide without covalent modification. The injectable and rapid curing adhesives were prepared by mixing oxidized dextran (ODE) and chitosan (CS) through a Schiff base reaction in the presence (or absence) of DA. The gelation time of the adhesive was customized to be less than 20 s by controlling the amount of ODE, regardless of the amount of DA. Multi-cross-linked (MC) hydrogels were further prepared by adding cross-linking agents such as sodium periodate (NaIO₄) and ferric trichloride (FeCl₃), and their sol-gel transitions were easily adjusted by changing the amounts of the cross-linking agents. The MC-FeCl₃ hydrogel adhesive displayed good tissue adhesion with a lap shear adhesion strength of 345 kPa, which was 43 times that of fibrin glue. Results from Raman spectra, texture profile analyses, and atomic force microscopy images confirmed the enhanced adhesion induced by a higher cohesion of MC-FeCl₃, owing to the coordination of Fe³⁺ and DA and non-covalent and covalent bonds of DA. Moreover, the adhesives showed good biodegradability and biocompatibility. These results demonstrate that the injectable and sticky hydrogels with good adhesion are promising materials for tissue repair.