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

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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 solution4,5,6. 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.

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Figure 1: Rapid vaterite formation in the absence of PSS.
Figure 2: Analysis of the formation, morphology and chemistry of as-prepared Ca–PSS globules.
Figure 3: Nucleation of amorphous calcium carbonate from Ca–PSS globules imaged in LP-TEM.
Figure 4: Mechanism of CaCO3 mineral formation in the biomimetic matrix.

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Acknowledgements

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.

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Contributions

P.J.M.S. carried out most experiments and co-wrote the manuscript. K.R.C. provided expertise and support in the AFM measurements. P.J.M.S. and J.J.D.Y. performed the growth rate and diffusion analysis. R.G.E.K. contributed to developing and using the MATLAB procedure for growth rate determinations. N.A.J.M.S. and J.J.D.Y. designed the research and co-wrote the manuscript. All authors discussed the results and revised the manuscript.

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Correspondence to Nico A. J. M. Sommerdijk or James J. De Yoreo.

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Smeets, P., Cho, K., Kempen, R. et al. Calcium carbonate nucleation driven by ion binding in a biomimetic matrix revealed by in situ electron microscopy. Nature Mater 14, 394–399 (2015). https://doi.org/10.1038/nmat4193

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