In recent decades, there has been increased attention to the role of layer-by-layer assembled bio-polymer 3D structures (capsules, beads, and microgels) for biomedical applications. Such free-standing multilayer structures are formed via hard templating onto sacrificial cores such as vaterite CaCO3 crystals. Immobilization of these structures onto solid surfaces (e.g., implants and catheters) opens the way for the formulation of advanced bio-coating with a patterned surface. However, the immobilization step is challenging. Multiple approaches based mainly on covalent binding have been developed to localize these multilayer 3D structures at the surface. This work reports a novel strategy to formulate multilayer surface-supported microgels (ss-MG) directly on the surface via hard templating onto ss-CaCO3 pre-grown onto the surface via the direct mixing of Na2CO3 and CaCl2 precursor solutions. ss-MGs were fabricated using biopolymers: polylysine (PLL) as polycation and three polyanions-hyaluronic acid (HA), heparin sulfate (HS), and alginate (ALG). ss-MG biodegradation was examined by employing the enzyme trypsin. Our studies indicate that the adhesion of the ss-MG to the surface and its formation yield directly correlate with the mobility of biopolymers in the ss-MG, which decreases in the sequence of ALG > HA > HS-based ss-MGs. The adhesion of HS-based ss-MGs is only possible via heating during their formation. Dextran-loading increases ss-MG formation yield while reducing ss-MG shrinking. ss-MGs with higher polymer mobility possess slower biodegradation rates, which is likely due to diffusion limitations for the enzyme in more compact annealed ss-MGs. These findings provide valuable insights into the mechanisms underlying the formation and biodegradation of surface-supported biopolymer structures.
Keywords: calcium carbonate; enzyme; layer-by-layer; multilayer; polyelectrolyte.