The nano- and meso-scale structure of amorphous calcium carbonate

Clark SM, Colas B, Jacob DE, Neuefeind JC, Wang HW, Page KL, Soper AK, Schodder P, Duchstein P, Apeleo Zubiri B, Yokosawa T, Pipich V, Zahn D, Spiecker E, Wolf S (2022)

Publication Type: Journal article

Publication year: 2022

Journal

Scientific Reports Nature Publishing Group: Open Access Journals - Option B

Book Volume: 12

Journal Issue: 1

DOI: 10.1038/s41598-022-10627-9

Abstract

Understanding the underlying processes of biomineralization is crucial to a range of disciplines allowing us to quantify the effects of climate change on marine organisms, decipher the details of paleoclimate records and advance the development of biomimetic materials. Many biological minerals form via intermediate amorphous phases, which are hard to characterize due to their transient nature and a lack of long-range order. Here, using Monte Carlo simulations constrained by X-ray and neutron scattering data together with model building, we demonstrate a method for determining the structure of these intermediates with a study of amorphous calcium carbonate (ACC) which is a precursor in the bio-formation of crystalline calcium carbonates. We find that ACC consists of highly ordered anhydrous nano-domains of approx. 2 nm that can be described as nanocrystalline. These nano-domains are held together by an interstitial net-like matrix of water molecules which generate, on the mesoscale, a heterogeneous and gel-like structure of ACC. We probed the structural stability and dynamics of our model on the nanosecond timescale by molecular dynamics simulations. These simulations revealed a gel-like and glassy nature of ACC due to the water molecules and carbonate ions in the interstitial matrix featuring pronounced orientational and translational flexibility. This allows for viscous mobility with diffusion constants four to five orders of magnitude lower than those observed in solutions. Small and ultra-small angle neutron scattering indicates a hierarchically-ordered organization of ACC across length scales that allow us, based on our nano-domain model, to build a comprehensive picture of ACC formation by cluster assembly from solution. This contribution provides a new atomic-scale understanding of ACC and provides a framework for the general exploration of biomineralization and biomimetic processes.

Authors with CRIS profile

Philipp Schodder Lehrstuhl für Glas und Keramik Patrick Duchstein Lehrstuhl für Theoretische Chemie Benjamin Apeleo Zubiri Lehrstuhl für Werkstoffwissenschaften (Mikro- und Nanostrukturforschung) Tadahiro Yokosawa Lehrstuhl für Werkstoffwissenschaften (Mikro- und Nanostrukturforschung) Dirk Zahn Professur für Theoretische Chemie Erdmann Spiecker Lehrstuhl für Werkstoffwissenschaften (Mikro- und Nanostrukturforschung) Stephan Wolf Lehrstuhl für Glas und Keramik

Additional Organisation(s)

Lehrstuhl für Werkstoffwissenschaften (Mikro- und Nanostrukturforschung) Interdisziplinäres Zentrum, Center for Nanoanalysis and Electron Microscopy (CENEM)

Involved external institutions

Oak Ridge National Laboratory US United States (USA) (US) Macquarie University AU Australia (AU) Australian National University (ANU) AU Australia (AU) Rutherford Appleton Laboratory GB United Kingdom (GB) Forschungszentrum Jülich / Research Centre Jülich (FZJ) DE Germany (DE)

How to cite

APA:

Clark, S.M., Colas, B., Jacob, D.E., Neuefeind, J.C., Wang, H.-W., Page, K.L.,... Wolf, S. (2022). The nano- and meso-scale structure of amorphous calcium carbonate. Scientific Reports, 12(1). https://dx.doi.org/10.1038/s41598-022-10627-9

MLA:

Clark, Simon M., et al. "The nano- and meso-scale structure of amorphous calcium carbonate." Scientific Reports 12.1 (2022).

BibTeX: Download