Origins of Improved Hardness in Bioinspired Aragonite Precipitated Under Simulated Biologic Conditions.

Biogenic aragonite is a composite of mineral and biomolecules that exhibits superior material properties compared to its inorganic analog. This superiority underpins the success of the bioaragonite structures which support coral reefs and shell fisheries, yet the mechanisms improving the physical resilience of bioaragonite are not well understood. In this study, aragonite is synthesised under chemical conditions which simulate those of calcification sites in marine organisms. Aspartic acid, glutamic acid, and glycine in solution are incorporated into the aragonite at concentrations typically observed in marine biominerals and are observed to significantly improve aragonite Vickers hardness. Aspartic acid is incorporated more efficiently than glutamic acid or glycine, but for comparable amounts of amino acid incorporation, glycine improves aragonite hardness significantly more than either aspartic or glutamic acid. Glycine and glutamic acid incorporation reduce the aragonite grain size, thereby improving resilience to indentation via energy dissipation along grain boundaries. In contrast, aspartic acid also improves hardness on a smaller scale, possibly due to crystal structure distortions. These results suggest that amino acid incorporation influences biogenic aragonite hardness via multiple mechanisms and provide a prototype for exploring the influence of more complicated biomineral proteins.