Abstract
Many living organisms contain biominerals and composites with finely tuned properties, reflecting a remarkable level of control over the nucleation, growth and shape of the constituent crystals1,2,3,4,5,6. Peptides and proteins play an important role in achieving this control1,7,8. But the general view that organic molecules affect mineralization through stereochemical recognition, where geometrical and chemical constraints dictate their binding to a mineral, seems difficult to reconcile4 with a mechanistic understanding, where crystallization is controlled by thermodynamic and kinetic factors9. Indeed, traditional crystal growth models emphasize the inhibiting effect of so-called ‘modifiers’ on surface-step growth, rather than stereochemical matching to newly expressed crystal facets. Here we report in situ atomic force microscope observations and molecular modelling studies of calcite growth in the presence of chiral amino acids that reconcile these two seemingly divergent views. We find that enantiomer-specific binding of the amino acids to those surface-step edges that offer the best geometric and chemical fit changes the step-edge free energies, which in turn results in macroscopic crystal shape modifications. Our results emphasize that the mechanism underlying crystal modification through organic molecules is best understood by considering both stereochemical recognition and the effects of binding on the interfacial energies of the growing crystal.
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Acknowledgements
We thank S. Zepeda, S. Orme and J. Bearinger for assistance with AFM data collection, P. Fenter for performing the SXRD studies, A. Nelson and C. Evans for help with XPS, S. Sikes for helpful discussions and L. Addadi for a careful reading of the manuscript. This work was performed under the auspices of the US Department of Energy by Lawrence Livermore National Laboratory and was supported by a grant to Georgia Institute of Technology from the Division of Geosciences and Engineering, Office of Basic Energy Sciences, Department of Energy.
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Orme, C., Noy, A., Wierzbicki, A. et al. Formation of chiral morphologies through selective binding of amino acids to calcite surface steps. Nature 411, 775–779 (2001). https://doi.org/10.1038/35081034
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DOI: https://doi.org/10.1038/35081034
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