Different kinetic pathways of early stage calcium-phosphate cluster aggregation induced by carboxylate-containing polymers.

Acidic proteins are critical to biomineral formation, although their precise mechanistic function remains poorly understood. A number of recent studies have suggested a nonclassical mineralization model that emphasizes the importance of the formation of polymer-stabilized mineral clusters or particles; however, it has been difficult to characterize the precursors experimentally due to their transient nature. Here, we successfully captured stepwise evolution of transient CaP clusters in mineralizing solutions and studied the roles of functional polymers with laser light scattering (LLS) to determine how these polymers influence the stability of nanoclusters. We found that the polymer structure can alter CaP aggregation mechanisms, whereas the polymer concentration strongly influences the rate of CaP aggregation. Our results indicate that the ability of acidic biomolecules to control the formation of relatively stable nanoclusters in the early stages may be critical for intrafibrillar mineralization. More importantly, LLS provided information about the size and the structural evolution of CaP aggregates, which will help define the process of controlled biomineralization.