Microscopic structure of the polymer-induced liquid precursor for calcium carbonate

Yifei Xu, Koen C. H. Tijssen, Paul H. H. Bomans, Anat Akiva, Heiner Friedrich, Arno P. M. Kentgens () and Nico A. J. M. Sommerdijk ()
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Yifei Xu: Eindhoven University of Technology
Koen C. H. Tijssen: Radboud University Nijmegen
Paul H. H. Bomans: Eindhoven University of Technology
Anat Akiva: Eindhoven University of Technology
Heiner Friedrich: Eindhoven University of Technology
Arno P. M. Kentgens: Radboud University Nijmegen
Nico A. J. M. Sommerdijk: Eindhoven University of Technology

Nature Communications, 2018, vol. 9, issue 1, 1-12

Abstract: Abstract Many biomineral crystals form complex non-equilibrium shapes, often via transient amorphous precursors. Also in vitro crystals can be grown with non-equilibrium morphologies, such as thin films or nanorods. In many cases this involves charged polymeric additives that form a polymer-induced liquid precursor (PILP). Here, we investigate the CaCO3 based PILP process with a variety of techniques including cryoTEM and NMR. The initial products are 30–50 nm amorphous calcium carbonate (ACC) nanoparticles with ~2 nm nanoparticulate texture. We show the polymers strongly interact with ACC in the early stages, and become excluded during crystallization, with no liquid–liquid phase separation detected during the process. Our results suggest that “PILP” is actually a polymer-driven assembly of ACC clusters, and that its liquid-like behavior at the macroscopic level is due to the small size and surface properties of the assemblies. We propose that a similar biopolymer-stabilized nanogranular phase may be active in biomineralization.

Date: 2018
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DOI: 10.1038/s41467-018-05006-w

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