Macromolecular Materials and Engineering, 2023 (SCI-Expanded)
Organohydrogels (OHGs) are soft materials with antagonistic hydrophilic and hydrophobic domains that have great interest for many different applications. This study presents the preparation of mechanically strong OHGs with shape-memory function by incorporating semicrystalline organo-microgels within the pores of silk fibroin (SF) scaffolds. In the first step, SF cryogels with various pore diameters between 26 ± 8 and 17 ± 4 µm are synthesized by cryogelation of aqueous SF solutions at concentrations between 5 and 20 w/v%. In the second step, the pores of SF scaffolds are filled with an organogel precursor solution containing n-octadecyl acrylate (C18A), acrylic acid, N,N'-methylene(bis)acrylamide, and an initiator. Once the free-radical polymerization took place inside the pores, OHGs containing organo-microgels of various sizes are obtained. The incorporation of the organogel component in the cryogels generates crystalline areas due to the side-by-side packed C18 side chains. OHGs' melting temperature and crystallinity level can be varied from 42 to 54 °C and from 2 to 16%, respectively. The stiffness of OHGs increases from 5.9 ± 0.5 to 18 ± 1 MPa with increasing SF concentration from 5 to 20 w/v%, which is attributed to the decreasing pore size of the cryogels and increasing thickness of the pore walls.