Growth and mechanisms of enamel-like hierarchical nanostructures on single crystalline hydroxyapatite micro-ribbons.

In vitro growth of enamel-like microstructured hydroxyapatite (HAP) crystals is highly expected for developing novel biomaterials/scaffolds. It is also essential for a clearer understanding of in vivo biomineralization process. In this paper, hierarchical HAP structures are controllably fabricated by growth of nanocrystals on single crystalline micro-ribbon substrates in vitro at biophysical conditions. HAP crystals grown on the substrate change from disordered aggregations of nano-flakes to well-oriented nano-needles, branched bundles of nano-needles, and finally highly porous aggregates, with increase of F- concentrations. The flexibility of the size, morphology, and microstructure control highlights a method to produce hierarchical HAP structures for potential applications in dental restoration or bone implant. We demonstrate that the mutual effects of F- on the crystallinity of HAP and on the supersaturation of the solutions control the morphology and assembly properties of the products. Moreover, the products excellently mimic real tooth enamel structures formed with different F- intakes. The work represents an appropriate simplified model system for an in-depth understanding of the microscopic mechanisms of the effects of F- on enamel growth, and the relationship of enamel microstructures and dental diseases.