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Shape-preserving amorphous-to-crystalline transformation of CaCO3 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.

SUBMITTER: Liu Z 

PROVIDER: S-EPMC7035502 | biostudies-literature | 2020 Feb

REPOSITORIES: biostudies-literature

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Shape-preserving amorphous-to-crystalline transformation of CaCO<sub>3</sub> revealed by in situ TEM.

Liu Zhaoming Z   Zhang Zhisen Z   Wang Zheming Z   Jin Biao B   Li Dongsheng D   Tao Jinhui J   Tang Ruikang R   De Yoreo James J JJ  

Proceedings of the National Academy of Sciences of the United States of America 20200203 7


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 spectr  ...[more]

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