Methacrylated cellulose nanocrystals as fillers for the development of photo-crosslinkable cytocompatible biosourced formulations targeting 3D printing
Résumé
Cellulose nanocrystals (CNCs) from cotton were functionalized in aqueous medium using methacrylic anhydride (MA) to produce methacrylated cellulose nanocrystals (mCNCs) with a degree of methacrylation (DM) up to 12.6 ± 0.50 %. Dispersible as-prepared CNCs and mCNCs were then considered as reinforcing fillers for aqueous 3D-printable formulations based on methacrylated carboxymethylcellulose (mCMC). The rheological properties of such photo-crosslinkable aqueous formulations containing non-modified CNCs or mCNCs at 0.2 or 0.5 wt% in 2 wt% mCMC were fully investigated. The influence of the presence of nanoparticles on the UV-curing kinetics and dimensions of the photo-crosslinked hydrogels was probed and 13 C CP-MAS NMR spectroscopy was used to determine the maximum conversion ratio of methacrylates as well as the optimized time required for UV post-curing. The viscoelasticity of crosslinked hydrogels and swollen hydrogels was also studied. The addition of 0.5 wt% mCNC with a DM of 0.83 ± 0.040 % to the formulation yielded faster crosslinking kinetics, better resolution, more robust crosslinked hydrogels and more stable swollen hydrogels than pure mCMC materials. Additionally, the produced cryogels showed no cytotoxicity toward L929 fibroblasts. This biobased formulation could thus be considered for the 3D printing of hydrogels dedicated to biomedical purposes using vat polymerization techniques such as stereolithography or digital light processing.