Supramolecular Biocomposite Hydrogels Formed by Cellulose and Host–Guest Polymers Assisted by Calcium Ion Complexes

Hydrogels are biocompatible polymer networks; however, they have the disadvantage of having poor mechanical properties. Herein, the mechanical properties of host-guest hydrogels were increased by adding a filler and incorporating other noncovalent interactions. Cellulose was added as a filler to the hydrogels to afford a composite. Citric acid-modified cellulose (CAC) with many carboxyl groups was used instead of conventional cellulose. The preparation began with mixing an acrylamide-based αCD host polymer (p-αCD) and a dodecanoic acid guest polymer (p-AADA) to form supramolecular hydrogels (p-αCD/p-AADA). However, when CAC was directly added to p-αCD/p-AADA to form biocomposite hydrogels (p-αCD/p-AADA/CAC), it showed weaker mechanical properties than p-αCD/p-AADA itself. This was caused by the strong intramolecular hydrogen bonding (H-bonding) within the CAC, which prevented the CAC reinforcing p-αCD/p-AADA in p-αCD/p-AADA/CAC. Then, calcium chloride solution (CaCl₂) was used to form calcium ion (Ca²⁺) complexes between the CAC and p-αCD/p-AADA. This approach successfully created supramolecular biocomposite hydrogels assisted by Ca²⁺ complexes (p-αCD/p-AADA/CAC/Ca²⁺) with improved mechanical properties relative to p-αCD/p-AADA hydrogels; the toughness was increased 6-fold, from 1 to 6 MJ/m³. The mechanical properties were improved because of the disruption of the intramolecular H-bonding within the CAC by Ca²⁺ and subsequent complex formation between the carboxyl groups of CAC and p-AADA. This mechanism is a new approach for improving the mechanical properties of hydrogels that can be broadly applied as biomaterials.