Two competitive nucleation mechanisms of calcium carbonate biomineralization in response to surface functionality in low calcium ion concentration solution

Four self-assembled monolayer surfaces terminated with -COOH, -OH, -NH2 and -CH3 functional groups are used to direct the biomineralization processes of calcium carbonate (CaCO3) in low Ca (2+) concentration, and the mechanism of nucleation and initial crystallization within 12 h was further explored. On -COOH surface, nucleation occurs mainly via ion aggregation mechanism while prenucleation ions clusters may be also involved. On -OH and -NH2 surfaces, however, nucleation forms via calcium carbonate clusters, which aggregate in solution and then are adsorbed onto surfaces following with nucleation of amorphous calcium carbonate (ACC). Furthermore, strongly negative-charged -COOH surface facilitates the direct formation of calcites, and the -OH and -NH2 surfaces determine the formation of vaterites with preferred crystalline orientations. Neither ACC nor crystalline CaCO3 is observed on -CH3 surface. Our findings present a valuable model to understand the CaCO3 biomineralization pathway in natural system where functional groups composition plays a determining role during calcium carbonate crystallization.