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...

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Main Authors: 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
Format: Article
Language:English
Published: Wiley 2024-12-01
Series:SmartMat
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Online Access:https://doi.org/10.1002/smm2.1302
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author 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
author_facet 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
author_sort Haibin Li
collection DOAJ
description 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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spelling doaj-art-cdd9edff3f35467bb863561bb24759712025-08-20T01:58:04ZengWileySmartMat2688-819X2024-12-0156n/an/a10.1002/smm2.1302Chiral gypsum with high‐performance mechanical properties induced by self‐assembly of chiral amino acid on an amorphous mineralHaibin Li0Zhiheng Sun1Yue Liu2Yi Xing3Jing Gao4Aihong Shi5Yadong Yu6Jin Long7Dong‐Po Song8Chao Jin9Marc D. McKee10Jun‐An Ma11Wenge Jiang12Department of Chemistry, Tianjin Key Laboratory of Molecular Optoelectronic Sciences, and Tianjin Collaborative Innovation Center of Chemical Science & Engineering Tianjin University Tianjin ChinaDepartment of Chemistry, Tianjin Key Laboratory of Molecular Optoelectronic Sciences, and Tianjin Collaborative Innovation Center of Chemical Science & Engineering Tianjin University Tianjin ChinaDepartment of Chemistry, Tianjin Key Laboratory of Molecular Optoelectronic Sciences, and Tianjin Collaborative Innovation Center of Chemical Science & Engineering Tianjin University Tianjin ChinaDepartment of Chemistry, Tianjin Key Laboratory of Molecular Optoelectronic Sciences, and Tianjin Collaborative Innovation Center of Chemical Science & Engineering Tianjin University Tianjin ChinaDepartment of Chemistry, Tianjin Key Laboratory of Molecular Optoelectronic Sciences, and Tianjin Collaborative Innovation Center of Chemical Science & Engineering Tianjin University Tianjin ChinaDepartment of Chemistry, Tianjin Key Laboratory of Molecular Optoelectronic Sciences, and Tianjin Collaborative Innovation Center of Chemical Science & Engineering Tianjin University Tianjin ChinaSchool of Chemical Engineering and Technology Tianjin University Tianjin ChinaDepartment of Chemistry, Tianjin Key Laboratory of Molecular Optoelectronic Sciences, and Tianjin Collaborative Innovation Center of Chemical Science & Engineering Tianjin University Tianjin ChinaTianjin Key Laboratory of Composite and Functional Materials, School of Materials Science and Engineering Tianjin University Tianjin ChinaTianjin Key Laboratory of Low Dimensional Materials Physics and Processing Technology, School of Science Tianjin University Tianjin ChinaFaculty of Dental Medicine and Oral Health Sciences McGill University Montreal CanadaDepartment of Chemistry, Tianjin Key Laboratory of Molecular Optoelectronic Sciences, and Tianjin Collaborative Innovation Center of Chemical Science & Engineering Tianjin University Tianjin ChinaDepartment of Chemistry, Tianjin Key Laboratory of Molecular Optoelectronic Sciences, and Tianjin Collaborative Innovation Center of Chemical Science & Engineering Tianjin University Tianjin ChinaAbstract 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.https://doi.org/10.1002/smm2.1302amorphouschiralitygypsummechanical propertyself‐assembly
spellingShingle 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
Chiral gypsum with high‐performance mechanical properties induced by self‐assembly of chiral amino acid on an amorphous mineral
SmartMat
amorphous
chirality
gypsum
mechanical property
self‐assembly
title Chiral gypsum with high‐performance mechanical properties induced by self‐assembly of chiral amino acid on an amorphous mineral
title_full Chiral gypsum with high‐performance mechanical properties induced by self‐assembly of chiral amino acid on an amorphous mineral
title_fullStr Chiral gypsum with high‐performance mechanical properties induced by self‐assembly of chiral amino acid on an amorphous mineral
title_full_unstemmed Chiral gypsum with high‐performance mechanical properties induced by self‐assembly of chiral amino acid on an amorphous mineral
title_short Chiral gypsum with high‐performance mechanical properties induced by self‐assembly of chiral amino acid on an amorphous mineral
title_sort chiral gypsum with high performance mechanical properties induced by self assembly of chiral amino acid on an amorphous mineral
topic amorphous
chirality
gypsum
mechanical property
self‐assembly
url https://doi.org/10.1002/smm2.1302
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