Calcium carbonate nucleation driven by ion binding in a biomimetic matrix revealed by in situ electron microscopy

Paul J.M. Smeets, Kang Rae Cho, Ralph G.E. Kempen, Nico A.J.M. Sommerdijk*, James J. De Yoreo

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

355 Scopus citations

Abstract

The characteristic shapes, structures and properties of biominerals arise from their interplay with a macromolecular matrix1,2. The developing mineral interacts with acidic macromolecules, which are either dissolved in the crystallization medium or associated with insoluble matrix polymers3, that affect growth habits and phase selection or completely inhibit precipitation in solution4-6. Yet little is known about the role of matrix-immobilized acidic macromolecules in directing mineralization. Here, by using in situ liquid-phase electron microscopy to visualize the nucleation and growth of CaCO3 in a matrix of polystyrene sulphonate (PSS), we show that the binding of calcium ions to form Ca-PSS globules is a key step in the formation of metastable amorphous calcium carbonate (ACC), an important precursor phase in many biomineralization systems7. Our findings demonstrate that ion binding can play a significant role in directing nucleation, independently of any control over the free-energy barrier to nucleation.

Original languageEnglish (US)
Pages (from-to)394-399
Number of pages6
JournalNature materials
Volume14
Issue number4
DOIs
StatePublished - Apr 2015

Funding

We thank V. Altoe and S. Aloni for the use of, and assistance with, the JEOL-2100F, J. Tao for help with confocal Raman microscopy, and H. Friedrich and M. Nielsen for help with TEM data analysis. This research was supported by the US Department of Energy, Office of Basic Energy Sciences, at Lawrence Berkeley National Laboratory and at the Pacific Northwest National Laboratory (PNNL). Characterization of PSS globule formation was supported by the Materials Science and Engineering Division. Investigation of calcium carbonate nucleation was supported by the Division of Chemical Sciences, Geosciences, and Biosciences. Transmission electron microscopy was performed at the Molecular Foundry, Lawrence Berkeley National Laboratory, which is supported by the Office of Basic Energy Sciences, Scientific User Facilities Division. PNNL is operated by Battelle for the US Department of Energy under Contract DE-AC05-76RL01830. The work of P.J.M.S. and N.A.J.M.S. is supported by a VICI grant of the Dutch Science Foundation, NWO, The Netherlands.

ASJC Scopus subject areas

  • General Chemistry
  • General Materials Science
  • Condensed Matter Physics
  • Mechanics of Materials
  • Mechanical Engineering

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