In-Bath 3D Printing of Anisotropic Shape-Memory Cryogels Functionalized with Bone-Bioactive Nanoparticles


Cryogels exhibit unique shape memory with full recovery and structural stability features after multiple injections. These constructs also possess enhanced cell permeability and nutrient diffusion when compared to typical bulk hydrogels. Volumetric processing of cryogels functionalized with nanosized units has potential to widen their biomedical applications, however this has remained challenging and relatively underexplored. In this study, we report a novel methodology that combines suspension 3D printing with directional freezing for the fabrication of nanocomposite cryogels with configurable anisotropy. When compared to conventional bulk or freeze-dried hydrogels, nanocomposite cryogel formulations exhibit excellent shape recovery (>95%) and higher pore connectivity. Suspension printing, assisted with a prechilled metal grid, was optimized to induce anisotropy. The addition of calcium- and phosphate-doped mesoporous silica nanoparticles into the cryogel matrix enhanced bioactivity toward orthopedic applications without hindering the printing process. Notably, the nanocomposite 3D printed cryogels exhibit injectable shape memory while also featuring a lamellar topography. The fabrication of these constructs was highly reproducible and exhibited potential for a cell-delivery injectable cryogel with no cytotoxicity to human-derived adipose stem cells. Hence, in this work, it was possible to combine a gravity defying 3D printed methodology with injectable and controlled anisotropic macroporous structures containing bioactive nanoparticles. This methodology ameliorates highly tunable injectable 3D printed anisotropic nanocomposite cryogels with a user-programmable degree of structural complexity.


Edgar J. Castanheira, Luís P. G. Monteiro, Vítor M. Gaspar, Tiago R. Correia, João M. M. Rodrigues, João F. Mano

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Work developed under the project CICECO-Aveiro Institute of Materials, UIDB/50011/2020 (DOI 10.54499/UIDB/50011/2020), UIDP/50011/2020 (DOI 10.54499/UIDP/50011/2020) & LA/P/0006/2020 (DOI 10.54499/LA/P/0006/2020), financed by national funds through the FCT/MEC (PIDDAC). This work was also funded by the Programa Operacional Competitividade e Internacionalização (POCI) and Programa Operacional Regional do Centro – Centro 2020, in the component FEDER, through FCT/MCTES in the scope of the project COP2P (PTDC/QUIQOR/30771/2017 – POCI-01-0145-FEDER-30771) and also funded by European Union’s Horizon 2020 research and innovation programme under the scope of InterLynk project with grant agreement No 953169. E.J.C, L.P.G.M., V.M.G. and J.M.M.R. gratefully acknowledge FCT for the individual PhD grants: SFRH/BD/144880/2019 – E.J.C.; 2020.06767.BD – L.P.G.M., and individual researcher contracts: 2022.02106.CEECIND – V.M.G. (DOI 10.54499/2022.02106.CEECIND/CP1720/CT0028); CEECIND/01363/2018 – J.M.M.R. (DOI 10.54499/CEECIND/01363/2018/CP1559/CT0022), respectively. The authors would also to acknowledge Professor Isabel Duarte from University of Aveiro, for all the help, availability, and execution of the μ-CT measurements. The authors also acknowledge Hitachi (Germany) for providing the acquired image presented in Figure 4b during the equipment trial. Some figure elements were used and adapted from

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