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Sequential switch of biomineral crystal morphology using trivalent ions

Nature Materials volume 3, pages 239243 (2004) | Download Citation



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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  1. 1.

    Biomineralization and biomimetic materials chemistry. J. Mater. Chem. 5, 935–946 (1995).

  2. 2.

    et al. Critical transitions in the biofabrication of abalone shells and flat pearls. Chem. Mater. 8, 679–690 (1996).

  3. 3.

    & Design strategies in mineralized biological materials. J. Mater. Chem. 7, 689–702 (1997).

  4. 4.

    et al. Control of crystal phase switching and orientation by soluble mollusc-shell proteins. Nature 381, 56–58 (1996).

  5. 5.

    et al. The hole truth: Intracrystalline proteins and calcium oxalate kidney stones. Mol. Urol. 4, 391–402 (2000).

  6. 6.

    et al. Scanning electron microscopy and molecular modeling of inhibition of calcium oxalate monohydrate crystal growth by citrate and phosphocitrate. Calcif. Tissue Int. 56, 297–304 (1995).

  7. 7.

    et al. Innovative materials processing strategies: A biomimetic approach. Science 255, 1098–1105 (1992).

  8. 8.

    et al. Ceramic thin-film formation on functionalized interfaces through biomimetic processing. Science 264, 48–55 (1994).

  9. 9.

    & Molecular manipulation of microstructures: Biomaterials, ceramics, and semiconductors. Science 277, 1242–1248 (1997).

  10. 10.

    et al. Continuous self-assembly of organic-inorganic nanocomposite coatings that mimic nacre. Nature 394, 256–260 (1998).

  11. 11.

    , , & First steps in harnessing the potential of biomineralization as a route to new high-performance composite materials. Acta Mater. 46, 733–736 (1998).

  12. 12.

    , , & Biomimetic synthesis of ordered silica structures mediated by block copolypeptides. Nature 403, 289–292 (2000).

  13. 13.

    et al. Direct observation of the transition from calcite to aragonite growth as induced by abalone shell proteins. Biophys. J. 79, 3307–3312 (2000).

  14. 14.

    , , , & Biomimetic arrays of oriented helical ZnO nanorods and columns. J. Am. Chem. Soc. 124, 12954–12955 (2002).

  15. 15.

    , , & Nanostructured artificial nacre. Nature Mater. 2, 413–418 (2003).

  16. 16.

    Mechanism of stone formation. Semin. Nephrol. 16, 364–74 (1996).

  17. 17.

    in Lanthanide Probes in Life, Chemical and Earth Sciences (eds Bünzli, J.-C.G. & Choppin, G.R.) 219–293 (Elsevier, Amsterdam, 1989).

  18. 18.

    , & In situ analysis of europium calcium oxalate crystallization using luminescence microspectroscopy. J. Phys. Chem. B 103, 3411–3416 (1999).

  19. 19.

    The crystal structures of whewellite and weddellite; re-examination and comparison. Am. Mineral. 65, 327–334 (1980).

  20. 20.

    , & Adhesion between molecules and calcium oxalate crystals: Critical interactions in kidney stone formation. J. Am. Chem. Soc. 125, 2854–2855 (2003).

  21. 21.

    , , , & Recovery of surfaces from impurity poisoning during crystal growth. Nature 399, 442–445 (1999).

  22. 22.

    Vibrational studies of calcium oxalate monohydrate (whewellite) and an anhydrous phase of calcium oxalate. J. Mol. Struct. 63, 157–166 (1980).

  23. 23.

    & Coprecipitation of rare earths with calcium oxalate. J. Inorg. Nucl. Chem. 10, 103–9 (1959).

  24. 24.

    Modern Crystallography III: Crystal Growth (Springer, Berlin, 1984).

  25. 25.

    et al. Physical chemical studies of calcium oxalate crystallization. Am. J. Kidney Dis. 17, 392–5 (1991).

  26. 26.

    Interaction of divalent cobalt, zinc, cadmium, and barium with the calcite surface during layer growth. Geochim. Cosmochim. Acta 60, 1543–1552 (1996).

  27. 27.

    , & The role of Mg2+ as an impurity in calcite growth. Science 290, 1134–1137 (2000).

  28. 28.

    & Calcium oxalate trihydrate phase control by structurally-specific carboxylic acids. J. Cryst. Growth 135, 235–45 (1994).

  29. 29.

    & EQUIL: A general computational method for the calculation of solution equilibria. Anal. Chem. 44, 1940–1950 (1972).

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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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    • Michael J. Lochhead

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

    • Viola Vogel

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


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

    • Lara A. Touryan
    • , Michael J. Lochhead
    •  & Viola Vogel
  2. Center for Process Analytical Chemistry, University of Washington, Seattle, Washington, 98195, USA

    • Brian J. Marquardt


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The authors declare no competing financial interests.

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Correspondence to Viola Vogel.

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