Stable Prenucleation Calcium Carbonate Clusters Define Liquid-Liquid Phase Separation
Stable Prenucleation Calcium Carbonate Clusters Define Liquid-Liquid Phase Separation
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DOI：
10.1002/anie.201915350
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发表时间：
2020-02-25
影响因子：
16.6
通讯作者：
Gebauer, Denis
中科院分区：
文献类型：
--
作者：
Avaro, Jonathan T.;Wolf, Stefan L. P.;Gebauer, Denis
液-液相分离（LLPS）是碳酸钙沉淀过程中的中间步骤，在生物矿化过程中起着关键作用。在这里，我们已经开发了一个模型，在均相离子缔合热力学确定的水溶液碳酸钙系统的液-液溶解性间隙，实验验证电位滴定，停流ATR-FTIR光谱和动力学研究的基础上。建议的机制解释了固体无定形碳酸钙的可变溶解度，调和以前不一致的文献值。考虑到液-液非晶多晶现象，该模型也为多晶型选择机制提供了线索。这是一般性的，应该测试系统以外的碳酸钙，提供一个新的角度对物理化学的LLPS机制的基础上稳定的核前集群，而不是非/亚稳态波动的生物矿化，超越。
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 have developed a model where ion association thermodynamics in homogeneous phases determine 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 the variable 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 systems other than calcium carbonate to provide a new perspective on the physical chemistry of LLPS mechanisms based on stable prenucleation clusters rather than un-/metastable fluctuations in biomineralization, and beyond.