Surface Properties of Octacalcium Phosphate Nanocrystals Are Crucial for Their Bioactivities

[Image: see text] The fundamental structure–biofunction relationship of calcium phosphates (CaPs) remains unclear despite their clinical successes as important biomaterials. Herein, a series of CaP coatings with gradual change of topography and crystallinity is constructed by electrochemical deposition, and the roles of the two basic physicochemical properties are scrutinized for further understanding the mechanism behind the superior bioactivities of octacalcium phosphate (OCP). We observe a distinct modulation on cell proliferation on the prepared CaP coatings for different cells. The magnitude of the modulation seems to depend on the cellular size, and the effect is attributed mainly to the microstructure of the coatings. On the other hand, the crystallinity manifests its significance for the osteogenic property of the OCP coatings. Further transmission electron microscopy analysis and density functional theory calculations reveal a surface rich in HPO(4)(2–) for the high-crystalline OCP nanocrystals. The results highlight that the nanocrystal surface properties of the OCP coatings, including the periodic structure and the HPO(4)(2–) composition, may play significant roles surpassing the ion release effect in determining its osteogenic property, probably via surface spatial and/or chemical recognitions. The present findings shed light on the fundamental understanding of the structure–biofunction relationship for CaP biomaterials.