Ion-association complexes unite classical and non-classical theories for the biomimetic nucleation of calcium phosphate

Wouter J. E. M. Habraken, Jinhui Tao, Laura J. Brylka, Heiner Friedrich, Luca Bertinetti, Anna S. Schenk, Andreas Verch, Vladimir Dmitrovic, Paul H. H. Bomans, Peter M. Frederik, Jozua Laven, Paul van der Schoot, Barbara Aichmayer, Gijsbertus de With, James J. DeYoreo () and Nico A. J. M. Sommerdijk ()
Additional contact information
Wouter J. E. M. Habraken: Eindhoven University of Technology, Laboratory of Materials and Interface Chemistry and Soft Matter Cryo-TEM Research Unit
Jinhui Tao: Molecular Foundry, Lawrence Berkeley Laboratory
Laura J. Brylka: Eindhoven University of Technology, Laboratory of Materials and Interface Chemistry and Soft Matter Cryo-TEM Research Unit
Heiner Friedrich: Eindhoven University of Technology, Laboratory of Materials and Interface Chemistry and Soft Matter Cryo-TEM Research Unit
Luca Bertinetti: Max Planck Institute of Colloids and Interfaces, Research Campus Golm
Anna S. Schenk: Max Planck Institute of Colloids and Interfaces, Research Campus Golm
Andreas Verch: Max Planck Institute of Colloids and Interfaces, Research Campus Golm
Vladimir Dmitrovic: Eindhoven University of Technology, Laboratory of Materials and Interface Chemistry and Soft Matter Cryo-TEM Research Unit
Paul H. H. Bomans: Eindhoven University of Technology, Laboratory of Materials and Interface Chemistry and Soft Matter Cryo-TEM Research Unit
Peter M. Frederik: Eindhoven University of Technology, Laboratory of Materials and Interface Chemistry and Soft Matter Cryo-TEM Research Unit
Jozua Laven: Eindhoven University of Technology, Laboratory of Materials and Interface Chemistry and Soft Matter Cryo-TEM Research Unit
Paul van der Schoot: Eindhoven University of Technology, Group Theory of Polymers and Soft Matter
Barbara Aichmayer: Max Planck Institute of Colloids and Interfaces, Research Campus Golm
Gijsbertus de With: Eindhoven University of Technology, Laboratory of Materials and Interface Chemistry and Soft Matter Cryo-TEM Research Unit
James J. DeYoreo: Molecular Foundry, Lawrence Berkeley Laboratory
Nico A. J. M. Sommerdijk: Eindhoven University of Technology, Laboratory of Materials and Interface Chemistry and Soft Matter Cryo-TEM Research Unit

Nature Communications, 2013, vol. 4, issue 1, 1-12

Abstract: Abstract Despite its importance in many industrial, geological and biological processes, the mechanism of crystallization from supersaturated solutions remains a matter of debate. Recent discoveries show that in many solution systems nanometre-sized structural units are already present before nucleation. Still little is known about the structure and role of these so-called pre-nucleation clusters. Here we present a combination of in situ investigations, which show that for the crystallization of calcium phosphate these nanometre-sized units are in fact calcium triphosphate complexes. Under conditions in which apatite forms from an amorphous calcium phosphate precursor, these complexes aggregate and take up an extra calcium ion to form amorphous calcium phosphate, which is a fractal of Ca2(HPO4)32− clusters. The calcium triphosphate complex also forms the basis of the crystal structure of octacalcium phosphate and apatite. Finally, we demonstrate how the existence of these complexes lowers the energy barrier to nucleation and unites classical and non-classical nucleation theories.

Date: 2013
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DOI: 10.1038/ncomms2490

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