This technology is a hydrogel composition and manufacturing method containing oxidized diol-modified hyaluronic acid (odHA) with diol groups introduced into the side chains and then oxidized, hydrazide-modified hyaluronic acid (hHA), and alginate. A gel is formed simply by mixing the odHA/alginate solution with the hHA solution, making it suitable for use as an ink for 3D bioprinting.
Hyaluronic acid is an extracellular matrix component that aids in cartilage and bone regeneration, making it widely used as a bioink. However, oxidizing the backbone with sodium periodate reduces its hydrolytic stability, leading to a significant decrease in molecular weight. Furthermore, most polysaccharide hydrogels have weak mechanical properties, preventing them from maintaining their shape after 3D printing without a separate frame, and they often require additional post-processing such as UV crosslinking or coagulation baths.
This technology oxidizes only the diol groups on the side chains rather than the backbone to create aldehyde groups, resulting in almost no loss of molecular weight. A dual network is formed through electrostatic interactions between the carboxyl groups of odHA and the hydrazide groups of hHA, as well as acylhydrazone bonds between the aldehyde and hydrazide groups. Alginate, which is crosslinked by divalent cations such as calcium or barium, is added at 0.5 to 2 parts by weight relative to odHA to enhance tensile strength and toughness. The oxidation degree is 10–50%, the hydrazide substitution degree is 20–80%, and the weight ratio of the two HAs is 3:1 to 1:3. Applicable to 3D printed scaffolds for cartilage regeneration, self-healing extrusion bioinks, and injectable cell delivery scaffolds, it enables the creation of robust hyaluronic acid structures that are self-supporting immediately after printing without the need for separate frames or post-crosslinking.
This invention was developed with support from the Ministry of Science and ICT for complex tissue regeneration using 3D bioprinting methods.
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