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An artificial biomineral formed by incorporation of copolymer micelles in calcite crystals

Nature Materials volume 10, pages 890–896 (2011)Cite this article

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Abstract

Biominerals exhibit morphologies, hierarchical ordering and properties that invariably surpass those of their synthetic counterparts. A key feature of these materials, which sets them apart from synthetic crystals, is their nanocomposite structure, which derives from intimate association of organic molecules with the mineral host. We here demonstrate the production of artificial biominerals where single crystals of calcite occlude a remarkable 13?wt% of 20?nm anionic diblock copolymer micelles, which act as ‘pseudo-proteins’. The synthetic crystals exhibit analogous texture and defect structures to biogenic calcite crystals and are harder than pure calcite. Further, the micelles are specifically adsorbed on {104} faces and undergo a change in shape on incorporation within the crystal lattice. This system provides a unique model for understanding biomineral formation, giving insight into both the mechanism of occlusion of biomacromolecules within single crystals, and the relationship between the macroscopic mechanical properties of a crystal and its microscopic structure.

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Figure 1: Schematic diagram of the encapsulation of copolymer micelles within calcite single crystals.
Figure 2: TEM images of the copolymer micelles before and subsequent to incorporation in a calcite crystal.
Figure 3: SEM images of calcite crystals precipitated in the presence of copolymer micelles produced at a copolymer concentration of 70?μg?ml−1.
Figure 4: High-resolution synchrotron powder XRD data of calcite crystals occluding polymer micelles.
Figure 5: TEM analysis of a thin section cut through the nanocomposite crystal.
Figure 6: SEM and AFM images and AFM profiles of nano-indentation marks on a calcite control crystal and a nanocomposite crystal after nanoindentation.

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Acknowledgements

Y-Y.K., K.G. and A.N.K. would like to thank the EPSRC for funding (grant numbers EP/E037364/2 and EP/G000868X/1). B.P., S.B. and S.P. would like to acknowledge the use of the European Synchrotron Radiation Facility and the ID31 staff for synchrotron high-resolution powder diffraction experiments. They also are grateful to E. Zolotoyabko for discussions and thank the Technion Executive Vice President for research grant no 2014208. We would also like to thank M. Ward at the Leeds Electron Microscopy and Spectroscopy Centre for assistance with focused ion beam sample preparation for TEM analysis. S.J.E. would like to thank the EPSRC for funding (grant number EP/E039138/1) and Dr J. Hay (Agilent, USA) for useful discussions relating to the nanoindentation measurements, while R.K. thanks the JEOL York Nanocentre for making its TEM facilities available. S.P.A. thanks the EPSRC for funding (grant number EP/G007950/1).

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  1. Stephen J. Eichhorn

    Present address: Present address: College of Engineering, Mathematics and Physical Sciences,Harrison Building, Streatham Campus, University of Exeter, North Park Road, Exeter EX4 4QF, UK,

Authors and Affiliations

  1. School of Chemistry, University of Leeds, Woodhouse Lane, Leeds LS2 9JT, UK

    Yi-Yeoun Kim, Kathirvel Ganesan, Alexander N. Kulak & Fiona C. Meldrum

  2. Department of Chemistry, University of Sheffield, Brook Hill, Sheffield S3 7HF, UK

    Pengcheng Yang & Steven P. Armes

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

    Shirly Borukhin, Sasha Pechook & Boaz Pokroy

  4. School of Materials and the Northwest Composites Centre, Paper Science Building, Sackville Street, University of Manchester, Manchester M13 9PL, UK

    Luis Ribeiro & Stephen J. Eichhorn

  5. Department of Physics, University of York, Heslington YO5 10DD, UK

    Roland Kröger

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Contributions

Y-Y.K., K.G. and A.N.K. grew the crystals, and carried out SEM analysis. Y-Y.K. also performed all IR and image analysis, the TGA analysis and assisted R.K. in performing the FIB and TEM work. P.Y. synthesized and characterized the block copolymers under the supervision of S.P.A., while L.R. performed the nanoindentation studies and analysis under the supervision of S.J.E. S.B., S.P. and B.P. carried out the synchrotron XRD experiments, while B.P. analysed the data obtained. F.C.M. led the project, supervised Y-Y.K., K.G. and A.N.K. and wrote the paper with assistance from her co-authors.

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Correspondence to Stephen J. Eichhorn or Fiona C. Meldrum.

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Kim, YY., Ganesan, K., Yang, P. et al. An artificial biomineral formed by incorporation of copolymer micelles in calcite crystals. Nature Mater 10, 890–896 (2011). https://doi.org/10.1038/nmat3103

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