Details
| Translated title of the contribution | Stabile Calciumcarbonat‐Pränukleationscluster bestimmen die Flüssig‐flüssig‐Phasenseparation |
|---|---|
| Original language | English |
| Pages (from-to) | 6155-6159 |
| Number of pages | 5 |
| Journal | Angewandte Chemie International Edition |
| Volume | 59 |
| Issue number | 15 |
| Early online date | 13 Jan 2020 |
| Publication status | Published - 1 Apr 2020 |
| Externally published | Yes |
Abstract
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.
Keywords
- calcium carbonate, liquid–liquid phase separation, nonclassical nucleation, phase diagram, prenucleation clusters
ASJC Scopus subject areas
- Chemical Engineering(all)
- Catalysis
- Chemistry(all)
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In: Angewandte Chemie International Edition, Vol. 59, No. 15, 01.04.2020, p. 6155-6159.
Research output: Contribution to journal › Article › Research › peer review
}
TY - JOUR
T1 - Stable Prenucleation Calcium Carbonate Clusters Define Liquid–Liquid Phase Separation
AU - Avaro, Jonathan T.
AU - Wolf, Stefan L. P.
AU - Hauser, Karin
AU - Gebauer, Denis
N1 - Funding Information: We gratefully acknowledge financial support from the Deutsche Forschungsgemeinschaft (SFB 1214, A2).
PY - 2020/4/1
Y1 - 2020/4/1
N2 - 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.
AB - 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.
KW - calcium carbonate
KW - liquid–liquid phase separation
KW - nonclassical nucleation
KW - phase diagram
KW - prenucleation clusters
UR - http://www.scopus.com/inward/record.url?scp=85082497824&partnerID=8YFLogxK
U2 - 10.1002/ange.201915350
DO - 10.1002/ange.201915350
M3 - Article
VL - 59
SP - 6155
EP - 6159
JO - Angewandte Chemie International Edition
JF - Angewandte Chemie International Edition
SN - 1433-7851
IS - 15
ER -