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

SmartMat Pub Date : 2024-07-02 DOI:10.1002/smm2.1302
Haibin Li, Zhiheng Sun, Yue Liu, Yi Xing, Jing Gao, Aihong Shi, Yadong Yu, Jin Long, Dong‐Po Song, Chao Jin, Marc D. McKee, Jun‐An Ma, Wenge Jiang
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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.
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手性氨基酸在无定形矿物上的自组装诱导出具有高性能机械性能的手性石膏
功能性手性超结构在生物学中很常见,包括在生物矿化过程中,它们经常出现在海洋和陆地无脊椎动物的许多硬化结构中,甚至出现在病态的人类内耳耳膜中。然而,它们形成的生物过程仍不清楚。在这里,我们展示了手性天冬氨酸(Asp)可以诱导二水硫酸钙(石膏)的手性分层超结构。石膏的左旋(顺时针)形态由 Asp 的 d 对映体诱导,而右旋(逆时针)形态则由 l 对映体诱导。在石膏板层的无定形硫酸钙矿物表面,手性 Asp 对映体通过连续自组装控制逐层定向倾斜矿物生长模型,从而产生了这些手性结构。这种无定形-结晶手性和分层混合结构的石膏具有出色的机械性能,包括高性能的强度和韧性。此外,手性石膏超微结构的诱导可以从特定的酸性氨基酸扩展到其他(非氨基酸)分子。这些发现有助于我们理解生物矿物相关对映体对生物矿物和生物模拟合成功能材料中常见的手性结构进行结构控制的分子机制。
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