A thermo-responsive and photo-polymerizable chondroitin sulfate-based hydrogel for 3D printing applications

• Published in: Carbohydrate polymers Vol. 149; pp. 163 - 174
• Main Authors: Abbadessa, A., Blokzijl, M.M., Mouser, V.H.M., Marica, P., Malda, J., Hennink, W.E., Vermonden, T.
• Format: Journal Article
• Language: English
• Published: England Elsevier Ltd 20-09-2016
• Subjects: Cartilage 3D printing; Cell Line; Cell Proliferation - drug effects; Cell Survival - drug effects; Chondroitin Sulfates - chemistry; Drug Design; Hydrogels - chemistry; Hydrogels - pharmacology; Methacrylated chondroitin sulfate; Methacrylates - chemistry; Photo-polymerization; Photochemical Processes; Polymerization; Printing, Three-Dimensional; Shear thinning; Temperature; Thermo-sensitive hydrogel; Mn; Mp; DMSO; DM; ratio TBA; CS-TBA; TBA; MA; PDI; pen/strep; DMAP; GMA; CSMA; Photo-polymerization; Tgel; PBS; Methacrylated chondroitin sulfate; pHPMAlac; Thermo-sensitive hydrogel; DAPI; 1H NMR; Cartilage 3D printing; CP; bFGF; M15P10; Shear thinning; CS; PEG; DMEM/F-12; EdU; HA
• ISSN: 0144-8617; 1879-1344
• DOI: 10.1016/j.carbpol.2016.04.080

•Efficient, reproducible, tunable methacrylation of chondroitin sulfate.•Rheology of thermo-sensitive hydrogels based on methacrylated chondroitin sulfate.•3D printing of hydrogels based on methacrylated chondroitin sulfate.
The aim of this study was to design a hydrogel system based on methacrylated chondroitin sulfate (CSMA) and a thermo-sensitive poly(N-(2-hydroxypropyl) methacrylamide-mono/dilactate)-polyethylene glycol triblock copolymer (M15P10) as a suitable material for additive manufacturing of scaffolds. CSMA was synthesized by reaction of chondroitin sulfate with glycidyl methacrylate (GMA) in dimethylsulfoxide at 50°C and its degree of methacrylation was tunable up to 48.5%, by changing reaction time and GMA feed. Unlike polymer solutions composed of CSMA alone (20% w/w), mixtures based on 2% w/w of CSMA and 18% of M15P10 showed strain-softening, thermo-sensitive and shear-thinning properties more pronounced than those found for polymer solutions based on M15P10 alone. Additionally, they displayed a yield stress of 19.2±7.0Pa. The 3D printing of this hydrogel resulted in the generation of constructs with tailorable porosity and good handling properties. Finally, embedded chondrogenic cells remained viable and proliferating over a culture period of 6days. The hydrogel described herein represents a promising biomaterial for cartilage 3D printing applications.