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Hierarchical Calcite Crystals with Occlusions of a Simple Polyelectrolyte Mimic Complex Biomineral Structures

  1. Anna S. Schenk1,†,
  2. Igor Zlotnikov1,
  3. Boaz Pokroy2,
  4. Notburga Gierlinger3,
  5. Admir Masic1,
  6. Paul Zaslansky1,‡,
  7. Andrew N. Fitch4,
  8. Oskar Paris5,
  9. Till H. Metzger1,
  10. Helmut Cölfen6,
  11. Peter Fratzl1,*,
  12. Barbara Aichmayer1,*

Article first published online: 2 JUL 2012

DOI: 10.1002/adfm.201201158

Issue

Advanced Functional Materials

Advanced Functional Materials

Volume 22, Issue 22, pages 4668–4676, November 21, 2012

Additional Information

How to Cite

Schenk, A. S., Zlotnikov, I., Pokroy, B., Gierlinger, N., Masic, A., Zaslansky, P., Fitch, A. N., Paris, O., Metzger, T. H., Cölfen, H., Fratzl, P. and Aichmayer, B. (2012), Hierarchical Calcite Crystals with Occlusions of a Simple Polyelectrolyte Mimic Complex Biomineral Structures. Adv. Funct. Mater., 22: 4668–4676. doi: 10.1002/adfm.201201158

Author Information

  1. 1

    Max Planck Institute of Colloids and Interfaces, Department of Biomaterials, 14424 Potsdam, Germany

  2. 2

    Faculty of Materials Engineering and the Russell Berrie, Nanotechnology Institute, Technion, Israel Institute of Technology, Haifa 32000, Israel

  3. 3

    University of Natural Resources and Life Sciences, Department of Material Sciences and Process Engineering, 1190 Vienna, Austria

  4. 4

    European Synchrotron Radiation Facility, 38043 Grenoble Cedex, France

  5. 5

    Montanuniversitaet Leoben, Institute of Physics, 8700 Leoben, Austria

  6. 6

    University of Konstanz, Department of Chemistry, 78457 Konstanz, Germany

  1. †

    School of Chemistry, University of Leeds, LS2 9JT, Leeds, UK

  2. ‡

    Julius Wolff Institut, Charité - Universitätsmedizin Berlin, Campus Virchow Klinikum, Augustenburger Platz 1, 13353 Berlin, Germany

*Max Planck Institute of Colloids and Interfaces, Department of Biomaterials, 14424 Potsdam, Germany.

Publication History

  1. Issue published online: 9 NOV 2012
  2. Article first published online: 2 JUL 2012
  3. Manuscript Revised: 7 JUN 2012
  4. Manuscript Received: 26 APR 2012

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Keywords:

  • biomimetics;
  • polymer-mediated crystallization;
  • calcium carbonate;
  • mesocrystals;
  • hierarchical structures

Abstract

Biominerals are complex inorganic-organic structures that often show excellent mechanical properties. Here a bio-inspired study of a remarkably simple synthetic system is presented in which only one charged polymer additive (poly(sodium 4-styrenesulfonate)) is able to induce hierarchical structuring of calcite similar to biominerals. The interaction of the negatively charged polymer with the nucleation and growth of the mineral, in particular via selective adsorption to internal and external (001) facets of the calcite lattice, implies structural features from the micrometer down to the nanometer level. The crystals exhibit a distinct rounded morphology and a controlled orientation. Moreover, the polymer molecules are occluded within the crystals with different concentrations in well-defined regions. This leads to the induction of a mesoscale structure based on 100 nm sized mineral building blocks with granular substructure and rough surface, as well as small modifications of the crystallographic structure. Such a combination of hierarchically organized structural features has previously only been reported for biogenic calcite, which is typically grown in a complex process involving multiple organic additives. It is also shown that the organic occlusions in the calcite-PSS hybrid crystals strongly affect the mechanical performance, as known for some biominerals.

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