Shape-preserving amorphous-to-crystalline transformation of CaCO 3 revealed by in situ TEM
Abstract
Organisms use inorganic ions and macromolecules to regulate crystallization from amorphous precursors, endowing natural biominerals with complex morphologies and enhanced properties. The mechanisms by which modifiers enable these shape-preserving transformations are poorly understood. We used in situ liquid-phase transmission electron microscopy to follow the evolution from amorphous calcium carbonate to calcite in the presence of additives. A combination of contrast analysis and infrared spectroscopy shows that Mg ions, which are widely present in seawater and biological fluids, alter the transformation pathway in a concentration-dependent manner. The ions bring excess (structural) water into the amorphous bulk so that a direct transformation is triggered by dehydration in the absence of morphological changes. Molecular dynamics simulations suggest Mg-incorporated water induces structural fluctuations, allowing transformation without the need to nucleate a separate crystal. Thus, the obtained calcite retains the original morphology of the amorphous state, biomimetically achieving the morphological control of crystals seen in biominerals.
- Authors:
- Publication Date:
- Sponsoring Org.:
- USDOE
- OSTI Identifier:
- 1597119
- Grant/Contract Number:
- AC05-76RL01830
- Resource Type:
- Published Article
- Journal Name:
- Proceedings of the National Academy of Sciences of the United States of America
- Additional Journal Information:
- Journal Name: Proceedings of the National Academy of Sciences of the United States of America Journal Volume: 117 Journal Issue: 7; Journal ID: ISSN 0027-8424
- Publisher:
- Proceedings of the National Academy of Sciences
- Country of Publication:
- United States
- Language:
- English
Citation Formats
Liu, Zhaoming, Zhang, Zhisen, Wang, Zheming, Jin, Biao, Li, Dongsheng, Tao, Jinhui, Tang, Ruikang, and De Yoreo, James J. Shape-preserving amorphous-to-crystalline transformation of CaCO 3 revealed by in situ TEM. United States: N. p., 2020.
Web. doi:10.1073/pnas.1914813117.
Liu, Zhaoming, Zhang, Zhisen, Wang, Zheming, Jin, Biao, Li, Dongsheng, Tao, Jinhui, Tang, Ruikang, & De Yoreo, James J. Shape-preserving amorphous-to-crystalline transformation of CaCO 3 revealed by in situ TEM. United States. doi:10.1073/pnas.1914813117.
Liu, Zhaoming, Zhang, Zhisen, Wang, Zheming, Jin, Biao, Li, Dongsheng, Tao, Jinhui, Tang, Ruikang, and De Yoreo, James J. Mon .
"Shape-preserving amorphous-to-crystalline transformation of CaCO 3 revealed by in situ TEM". United States. doi:10.1073/pnas.1914813117.
@article{osti_1597119,
title = {Shape-preserving amorphous-to-crystalline transformation of CaCO 3 revealed by in situ TEM},
author = {Liu, Zhaoming and Zhang, Zhisen and Wang, Zheming and Jin, Biao and Li, Dongsheng and Tao, Jinhui and Tang, Ruikang and De Yoreo, James J.},
abstractNote = {Organisms use inorganic ions and macromolecules to regulate crystallization from amorphous precursors, endowing natural biominerals with complex morphologies and enhanced properties. The mechanisms by which modifiers enable these shape-preserving transformations are poorly understood. We used in situ liquid-phase transmission electron microscopy to follow the evolution from amorphous calcium carbonate to calcite in the presence of additives. A combination of contrast analysis and infrared spectroscopy shows that Mg ions, which are widely present in seawater and biological fluids, alter the transformation pathway in a concentration-dependent manner. The ions bring excess (structural) water into the amorphous bulk so that a direct transformation is triggered by dehydration in the absence of morphological changes. Molecular dynamics simulations suggest Mg-incorporated water induces structural fluctuations, allowing transformation without the need to nucleate a separate crystal. Thus, the obtained calcite retains the original morphology of the amorphous state, biomimetically achieving the morphological control of crystals seen in biominerals.},
doi = {10.1073/pnas.1914813117},
journal = {Proceedings of the National Academy of Sciences of the United States of America},
number = 7,
volume = 117,
place = {United States},
year = {2020},
month = {2}
}
DOI: 10.1073/pnas.1914813117
Web of Science
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