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

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  • Wouter J. E. M. Habraken

    (Eindhoven University of Technology, Laboratory of Materials and Interface Chemistry and Soft Matter Cryo-TEM Research Unit
    Max Planck Institute of Colloids and Interfaces, Research Campus Golm)

  • 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)

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.

Suggested Citation

  • 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, 2013. "Ion-association complexes unite classical and non-classical theories for the biomimetic nucleation of calcium phosphate," Nature Communications, Nature, vol. 4(1), pages 1-12, June.
    • Handle: RePEc:nat:natcom:v:4:y:2013:i:1:d:10.1038_ncomms2490
    DOI: 10.1038/ncomms2490
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    Cited by:

    1. Guo, Dan & Cao, Xuewen & Ding, Gaoya & Zhang, Pan & Liu, Yang & Bian, Jiang, 2022. "Crystallization and nucleation mechanism of heavy hydrocarbons in natural gas," Energy, Elsevier, vol. 239(PB).
    2. Xiao, Yang & Ma, Changjian & Li, Mengyao & Zhangzhong, Lili & Song, Peng & Li, Yunkai, 2023. "Interaction and adaptation of phosphorus fertilizer and calcium ion in drip irrigation systems: the perspective of emitter clogging," Agricultural Water Management, Elsevier, vol. 282(C).
    3. Zhu, Jingyun & Liu, Guannan & Luo, Ning & Gu, Jiayi & Liu, Hu & Ye, Dayu, 2023. "A new fractal model for quantitatively investigating the contribution of microstructural evolution to geothermal extraction," Renewable Energy, Elsevier, vol. 211(C), pages 42-54.

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