Biomimetic Synthesis of Macroscopic-Scale Calcium Carbonate Thin Films. Evidence for a Multistep Assembly Process

Biologically controlled mineralization features an orchestrated balance among various controlling factors such as spatial delineation, template promotion, crystal growth modification and cessation, and so on. Highly ordered calcium carbonate lamellae formed in the nacreous layers of mollusk (aragonite), the foliated calcitic layers of mollusk (calcite), or the semi-nacre of brachiopods (calcite) are excellent examples of the outcome of such synergistic control. Mimicking the concerted interplay of template promotion and growth inhibition as often utilized in biomineralization, we have synthesized macroscopic and continuous calcium carbonate thin films with thickness ranging from 0.4 to 0.6 μm. The thin films were prepared at air/subphase interfaces by promoting mineral deposition with amphiphilic porphyrin templates, coupled with growth inhibition by the use of poly(acrylic acid) as a soluble inhibitor. Films formed at 22 °C were found to have a biphasic structure containing both amorphous and crystalline...