Influence of Polyamines and Related Macromolecules on Silicic Acid Polycondensation: Relevance to “Soluble Silicon Pools”?

The influence of a number of N-containing macromolecules on the polycondensation of silicic acid to form amorphous silica is studied by the combined use of ²⁹Si NMR spectroscopy and the silicomolybdate test. Polymeric additives include poly(allylamine hydrochloride) (PAH), the poly(aminoamide) dendrimer of generation 1 (PAMAM-1), poly(ethyleneimine) (PEI), and poly(vinylpyrrolidone) (PVP). These studies were performed under biologically relevant conditions (pH 5.4 and 7.0) using aqueous solutions of isotope-labeled sodium [²⁹Si]metasilicate as the precursor compound. It was found at pH 5.4 that all additives accelerate silicic acid polycondensation, except for PVP, which exerts a minor silicic acid stabilizing effect. At pH 7.0, polycondensation is much faster in the presence of PAMAM-1, PEI, and PAH. However, PVP significantly stabilizes mono- and disilicic acid. Silica precipitates were also studied by ²⁹Si NMR spectroscopy. The effect observed for PVP is striking and indicates that the silicic acid polycondensation is slowed, although the oligomers are immobilized by the PVP polymer. In contrast, the charged PAH attracts the oligomeric species and enhances the silicic acid polycondensation