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Sequential switch of biomineral crystal morphology using trivalent ions

Nature Materials volume 3, pages 239–243 (2004)Cite this article

Abstract

Many biominerals are laminated such that crystal shape or habit changes from layer to layer thus yielding exquisitely designed composite materials with tightly controlled properties. Although lamination in biominerals is usually performed using peptides and proteins, here we introduce a new strategy by which sequential addition or depletion of inorganic trivalent ions in a supersaturated solution can be used to switch the surface morphology of calcium oxalate monohydrate (COM) back and forth, resulting in either the growth of flat crystalline sheets or of nanostructures oriented perpendicular to the surface. We propose that the occupation of a Ca2+ site by Eu3+ ion switches the orientation of the COM unit cell. The need to compensate the third charge forces coordination of Eu3+ to an additional oxalate ion (−OOC-COO−) in an orientation that is not compatible with the initial unit cell. This mechanism of switching the orientation of the unit cell is unique, as it does not involve the use of expensive and thermally labile biomolecules. Suggestions of how to extend this strategy to engineer non-biological nanocomposites are given.

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Figure 1: COM crystal growth.
Figure 2: Calcium oxalate monohydrate crystal growth in the presence of Eu3+.
Figure 3: Luminescence spectra confirm that the nanostructures grown on COM in the presence of Eu3+ have a COM unit cell.
Figure 4: Switching crystal surface morphology.
Figure 5: Proposed switching mechanism.

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Acknowledgements

We are grateful to Allison Campbell of the Pacific Northwest National Labs (PNNL, Richland, Washington, USA) for early discussion on the calcium oxalate work, and Dong Qin and Greg Golden of the University of Washington Nanotech User Facility for assistance with AFM and SEM images. The work was supported by a University of Washington Center for Nanotechnology Graduate Research Award, a National Science Foundation Integrative Graduate Education and Research Traineeship (NSF-IGERT) Fellowship and the PNNL/UW Joint Institute for Nanoscience.

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Author notes

  1. Michael J. Lochhead

    Present address: Accelr8 Technology Corporation, 303 East 17th Avenue, Suite 108, Denver, Colorado, 80203, USA

  2. Viola Vogel

    Present address: Department of Materials, Swiss Federal Institute of Technology (ETH), Hönggerberg, CH-8093, Zürich, Switzerland

Authors and Affiliations

  1. Department of Bioengineering, University of Washington, Seattle, 98195, Washington, USA

    Lara A. Touryan, Michael J. Lochhead & Viola Vogel

  2. Center for Process Analytical Chemistry, University of Washington, Seattle, 98195, Washington, USA

    Brian J. Marquardt

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  1. Lara A. Touryan
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  2. Michael J. Lochhead
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  4. Viola Vogel
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Correspondence to Viola Vogel.

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Touryan, L., Lochhead, M., Marquardt, B. et al. Sequential switch of biomineral crystal morphology using trivalent ions. Nature Mater 3, 239–243 (2004). https://doi.org/10.1038/nmat1096

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