Bioinspired control of colloidal silica in vitro by dual polymeric assemblies of zwitterionic phosphomethylated chitosan and polycations or polyanions.

This paper focuses on the effects of biological and synthetic polymers on the formation of amorphous silica. A concise review of relevant literature related to biosilicification is presented. The importance of synergies between polyelectrolytes on the inhibition of silicic acid condensation is discussed. A specific example of a zwitterionic polymer phosphonomethylated chitosan (PCH) is further analyzed for its inhibitory activity. Specifically, the ability of PCH to retard silicic acid condensation at circumneutral pH in aqueous supersaturated solutions is explored. It was discovered that in short-term studies (0-8 h) the inhibitory activity is PCH dosage-independent, but for longer condensation times (>24 h) there is a clear increase in inhibition upon PCH dosage increase. Soluble silicic acid levels reach 300 ppm after 24 h in the presence of 160 ppm PCH. Furthermore, the effects of either purely cationic (polyethyleneimine, PEI) or purely anionic (carboxymethylinulin, CMI) polyelectrolytes on the inhibitory activity of PCH is systematically studied. It was found that the action of inhibitor blends is not cumulative. PCH/PEI blends stabilize the same level of silicic acid as PCH alone in both short-term (8 h) and long-term (72 h) experiments. PCH/CMI combinations on the other hand can only achieve short-term inhibition of silicic acid polymerization, but fail to extend this over the first 8 h. PCH and its combinations with PEI or CMI affect silica particle morphology, studied by SEM. Spherical particles and their aggregates, irregularly shaped particles and porous structures are obtained depending on additive or additive blend. It was demonstrated by FT-IR that PCH is trapped in the colloidal silica matrix.