Layer-By-Layer Dendritic Growth of Hyperbranched Thin Films for Surface Sol-Gel Syntheses of Conformal, Functional, Nanocrystalline Oxide Coatings on Complex 3D (Bio)silica Templates

Here, a straightforward and general method for the rapid dendritic amplification of accessible surface functional groups on hydroxylated surfaces is described, with focus on its application to 3D biomineral surfaces. Reaction of hydroxyl-bearing silica surfaces with an aminosilane, followed by alternating exposure to a dipentaerythritol-derived polyacrylate solution and a polyamine solution, allows the rapid, layer-by-layer (LBL) build-up of hyperbranched polyamine/polyacrylate thin films. Characterization of such LBL-grown thin films by AFM, ellipsometry, XPS, and contact angle analyses reveals a stepwise and spatially homogeneous increase in film thickness with the number of applied layers. UV-Vis absorption analyses after fluorescein isothiocyanate labeling indicate that significant amine amplification is achieved after the deposition of only 2 layers with saturation achieved after 3-5 layers. Use of this thin-film surface amplification technique for hydroxyl-enrichment of biosilica templates facilitates the conformal surface sol-gel deposition of iron oxide that, upon controlled thermal treatment, is converted into a nanocrystalline (similar to 9.5 nm) magnetite (Fe3O4) coating. The specific adsorption of arsenic onto such magnetite-coated frustules from flowing, arsenic-bearing aqueous solutions is significantly higher than for commercial magnetite nanoparticles (<= 50 nm in diameter).