Chiral gypsum with high-performance mechanical properties induced by self-assembly of chiral amino acid on an amorphous mineral

Abstract

Functional chiral suprastructures are common in biology, including in biomineralization, and they are frequently found in many hardened structures of both marine and terrestrial invertebrates, and even in pathologic human otoconia of the inner ear. However, the biological processes by which they form remain unclear. Here, we show that chiral hierarchical suprastructures of calcium sulfate dihydrate (gypsum) can be induced by the chiral Aspartic acid (Asp). Left-handed (clockwise) morphology of gypsum is induced by the D-enantiomer of Asp, while right-handed (counterclockwise) morphology is induced by the L-enantiomer. A layer-by-layer, oriented inclination mineral growth model controlled by continuous self-assembly of chiral Asp enantiomers on an amorphous calcium sulfate mineral surface of gypsum platelet layers is postulated to produce these chiral architectures. This hybrid amorphous-crystallized chiral and hierarchical suprastructure of gypsum displays outstanding mechanical properties, including high-performance strength and toughness. Furthermore, the induction of chiral gypsum suprastructures can be more generally extended from specific acidic amino acids to other (nonamino acid) molecules. These findings contribute to our understanding of the molecular mechanisms by which biomineral-associated enantiomers exert structural control over chiral architectures commonly seen in biominerals and in biomimetically synthesized functional materials.

Keywords

amorphous / chirality / gypsum / mechanical property / self-assembly

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