Fluorapatite nanorod arrays with enamel-like bundle structure regulated by iron ions

Abstract

Pigmented rodent tooth enamel is mainly composed of parallel hydroxyapatite nanorods and a small amount of organic matrix. These hydroxyapatite nanorods tend to be carbonated and contain traces of iron, fluorine, and magnesium. The pigmented rodent tooth enamel which contains trace iron is stronger and more resistant to acid corrosion than unpigmented rodent enamel, which could provide inspiration for the preparation and synthesis of high performance and corrosion resistant artificial materials. However, the regulatory role and mechanical enhancement of iron ions in enamel growth are unclear. Here, we synthesized enamel-like fluorapatite nanorod arrays in vitro using a mineralization technique at room-temperature. To investigate the regulatory effect of iron ions on the fluorapatite nanorod arrays (FAP-Fe), the phosphate solution is slowly transfused dropwise in the calcium ion solution, and different concentrations of iron ions are added to the calcium ion solution in advance. We demonstrated that fluorapatite nanorod arrays (FAP) can be epitaxially grown from amorphous calcium phosphate nanoparticles and iron ions can improve the microstructure of FAP nanorod arrays and obtain the same enamel bundle structure as the natural enamel. Moreover, high concentration of iron ions can inhibit the crystallization of fluorapatite. The FAP-Fe nanorod arrays controlled by 0.02 mM Fe³⁺ have good mechanical properties. Their hardness is 1.34 ± 0.02 GPa and Young's modulus is 65.3 ± 0.4 GPa, respectively. This work is helpful to understand the role of trace elements in natural enamel in the regulation of enamel formation and to provide a theoretical foundation for the preparation of high strength artificial composites, which can play a greater role in the fields of biological alternative materials, anti-oil coating, oil/water separation, anti-bioadhesion and so on.