Colloidal pathways of amorphous calcium carbonate formation lead to distinct water environments and conductivity

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Authors

  • Maxim B. Gindele
  • Sanjay Vinod-Kumar
  • Johannes Rochau
  • Daniel Boemke
  • Eduard Groß
  • Venkata Subba Rao Redrouthu
  • Denis Gebauer
  • Guinevere Mathies

Research Organisations

External Research Organisations

  • University of Konstanz
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Details

Original languageEnglish
Article number80
Number of pages14
JournalNature Communications
Volume15
Publication statusPublished - 2 Jan 2024

Abstract

CaCO3 is the most abundant biomineral and a major constituent of incrustations arising from water hardness. Polycarboxylates play key roles in controlling mineralization. Herein, we present an analytical and spectroscopic study of polycarboxylate-stabilized amorphous CaCO3 (ACC) and its formation via a dense liquid precursor phase (DLP). Polycarboxylates facilitate pronounced, kinetic bicarbonate entrapment in the DLP. Since bicarbonate is destabilized in the solid state, DLP dehydration towards solid ACC necessitates the formation of locally calcium deficient sites, thereby inhibiting nucleation. Magic-angle spinning (MAS) nuclear magnetic resonance (NMR) spectroscopy of poly-aspartate-stabilized ACC reveals the presence of two distinct environments. The first contains immobile calcium and carbonate ions and structural water molecules, undergoing restricted, anisotropic motion. In the second environment, water molecules undergo slow, but isotropic motion. Indeed, conductive atomic force microscopy (C-AFM) reveals that ACC conducts electrical current, strongly suggesting that the mobile environment pervades the bulk of ACC, with dissolved hydroxide ions constituting the charge carriers. We propose that the distinct environments arise from colloidally stabilized interfaces of DLP nanodroplets, consistent with the pre-nucleation cluster (PNC) pathway.

Cite this

Colloidal pathways of amorphous calcium carbonate formation lead to distinct water environments and conductivity. / Gindele, Maxim B.; Vinod-Kumar, Sanjay; Rochau, Johannes et al.
In: Nature Communications, Vol. 15, 80, 02.01.2024.

Research output: Contribution to journalArticleResearchpeer review

Gindele, M. B., Vinod-Kumar, S., Rochau, J., Boemke, D., Groß, E., Redrouthu, V. S. R., Gebauer, D., & Mathies, G. (2024). Colloidal pathways of amorphous calcium carbonate formation lead to distinct water environments and conductivity. Nature Communications, 15, Article 80. https://doi.org/10.1038/s41467-023-44381-x
Gindele MB, Vinod-Kumar S, Rochau J, Boemke D, Groß E, Redrouthu VSR et al. Colloidal pathways of amorphous calcium carbonate formation lead to distinct water environments and conductivity. Nature Communications. 2024 Jan 2;15:80. doi: 10.1038/s41467-023-44381-x
Gindele, Maxim B. ; Vinod-Kumar, Sanjay ; Rochau, Johannes et al. / Colloidal pathways of amorphous calcium carbonate formation lead to distinct water environments and conductivity. In: Nature Communications. 2024 ; Vol. 15.
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abstract = "CaCO3 is the most abundant biomineral and a major constituent of incrustations arising from water hardness. Polycarboxylates play key roles in controlling mineralization. Herein, we present an analytical and spectroscopic study of polycarboxylate-stabilized amorphous CaCO3 (ACC) and its formation via a dense liquid precursor phase (DLP). Polycarboxylates facilitate pronounced, kinetic bicarbonate entrapment in the DLP. Since bicarbonate is destabilized in the solid state, DLP dehydration towards solid ACC necessitates the formation of locally calcium deficient sites, thereby inhibiting nucleation. Magic-angle spinning (MAS) nuclear magnetic resonance (NMR) spectroscopy of poly-aspartate-stabilized ACC reveals the presence of two distinct environments. The first contains immobile calcium and carbonate ions and structural water molecules, undergoing restricted, anisotropic motion. In the second environment, water molecules undergo slow, but isotropic motion. Indeed, conductive atomic force microscopy (C-AFM) reveals that ACC conducts electrical current, strongly suggesting that the mobile environment pervades the bulk of ACC, with dissolved hydroxide ions constituting the charge carriers. We propose that the distinct environments arise from colloidally stabilized interfaces of DLP nanodroplets, consistent with the pre-nucleation cluster (PNC) pathway.",
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