Biomimetic Control of Calcite Morphology with Homopolyanions

Biomineralization is an intricate process that relies on precise physiological control of solution and interface properties. Despite much research of the process, mechanistic details of biomineralization are only beginning to be understood, and studies of additives seldom investigate a wide space of chemical conditions in mineralizing solutions. We present a ternary diagram-based method that globally identifies the changing roles and effects of polymer additives in mineralization. Simple polyanions were demonstrated to induce a great variety of morphologies, each of which can be selectively and reproducibly fabricated. This chemical and physical analysis also aided in identifying conditions that selectively promote heterogeneous nucleation and controlled cooperative assembly, manifested here in the form of highly organized cones. Similar complex shapes of CaCO3 have previously been synthesized using double hydrophilic block copolymers. We have found the biomimetic mineralization process to occur interfacially and by the assembly of precursor modules, which generate large mesocrystals with high dependence on pH and substrate surface.