Journal
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
Volume 55, Issue 28, Pages 8117-8120Publisher
WILEY-V C H VERLAG GMBH
DOI: 10.1002/anie.201603176
Keywords
amorphous calcium carbonate; biomineralization; NMR spectroscopy; polyamorphism; water
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Funding
- Fonds der Chemischen Industrie
- Swedish Energy Agency
- Swedish Research Council
- Knut and Alice Wallenberg Foundation
- NSERC
- NSERC Canada
- U.S. DOE [DEAC02-06CH11357]
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Temperature and pH value can affect the short-range order of proto-structured and additive-free amorphous calcium carbonates (ACCs). Whereas a distinct change occurs in proto-vaterite (pv) ACC above 45 degrees C at pH 9.80, proto-calcite (pc) ACC (pH 8.75) is unaffected within the investigated range of temperatures (7-65 degrees C). IR and NMR spectroscopic studies together with EXAFS analysis showed that the temperature-induced change is related to the formation of proto-aragonite (pa) ACC. The data strongly suggest that the binding of water molecules induces dipole moments across the carbonate ions in pa-ACC as in aragonite, where the dipole moments are due to the symmetry of the crystal structure. Altogether, a (pseudo-)phase diagram of the CaCO3 polyamorphism in which water plays a key role can be formulated based on variables of state, such as the temperature, and solution parameters, such as the pH value.
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