Stable Pre-nucleation Calcium Carbonate Clusters Define Liquid-Liquid Phase Separation

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Angewandte Chemie International Edition. Wiley. 2020, 59(15), pp. 6155-6159. ISSN 1521-3773. eISSN 1433-7851. Available under: doi: 10.1002/anie.201915350
Zusammenfassung

Liquid‐liquid phase separation (LLPS) is an intermediate step during the precipitation of calcium carbonate, and is assumed to play a key role in biomineralization processes. Here, we developed a model where homogeneous phase ion association thermodynamics determines the liquid‐liquid miscibility gap of the aqueous calcium carbonate system, verified experimentally using potentiometric titrations, and kinetic studies based on stopped‐flow ATR‐FTIR spectroscopy. The proposed mechanism explains varying solubilities of solid amorphous calcium carbonates, reconciling previously inconsistent literature values. Accounting for liquid‐liquid amorphous polymorphism, the model also provides clues to the mechanism of polymorph selection. It is general and should be tested for other systems than calcium carbonate, providing a new perspective on the physical chemistry of LLPS mechanisms—based on stable pre‐nucleation clusters rather than un‐/metastable fluctuations—in biomineralization, and beyond.

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540 Chemie
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calcium carbonate, phase diagram, liquid-liquid phase separation, non-classical nucleation, pre-nucleation clusters
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ISO 690AVARO, Jonathan Thomas, Stefan L. P. WOLF, Karin HAUSER, Denis GEBAUER, 2020. Stable Pre-nucleation Calcium Carbonate Clusters Define Liquid-Liquid Phase Separation. In: Angewandte Chemie International Edition. Wiley. 2020, 59(15), pp. 6155-6159. ISSN 1521-3773. eISSN 1433-7851. Available under: doi: 10.1002/anie.201915350
BibTex
@article{Avaro2020-04-06Stabl-48224,
  year={2020},
  doi={10.1002/anie.201915350},
  title={Stable Pre-nucleation Calcium Carbonate Clusters Define Liquid-Liquid Phase Separation},
  number={15},
  volume={59},
  issn={1521-3773},
  journal={Angewandte Chemie International Edition},
  pages={6155--6159},
  author={Avaro, Jonathan Thomas and Wolf, Stefan L. P. and Hauser, Karin and Gebauer, Denis}
}
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