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Microscopic origin of chiral shape induction in achiral crystals

Abstract

In biomineralization, inorganic materials are formed with remarkable control of the shape and morphology. Chirality, as present in the biomolecular world, is therefore also common for biominerals. Biomacromolecules, like proteins and polysaccharides, are in direct contact with the mineral phase and act as modifiers during nucleation and crystal growth. Owing to their homochirality—they exist only as one of two possible mirror-symmetric isomers—their handedness is often transferred into the macroscopic shape of the biomineral crystals, but the way in which handedness is transmitted into achiral materials is not yet understood at the atomic level. By using the submolecular resolution capability of scanning tunnelling microscopy, supported by photoelectron diffraction and density functional theory, we show how the chiral ‘buckybowl’ hemibuckminsterfullerene arranges copper surface atoms in its vicinity into a chiral morphology. We anticipate that such new insight will find its way into materials synthesis techniques.

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Figure 1: Initial steps of chiral faceting of Cu(110) by hemifullerene.
Figure 2: Determination of the absolute handedness of hemifullerene molecules.
Figure 3: Structure models for homochiral step edges.
Figure 4: Single M-hemifullerene-(-R)-kink complex.

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Acknowledgements

Financial support from the Swiss National Science Foundation, the National Natural Science Foundation of China (61574170), the US National Science Foundation and the US Department of Energy is gratefully acknowledged. K.P. and W.A.H. acknowledge Engineering and Physical Sciences Research Council support for the UK Car-Parrinello consortium (grant reference EP/K013610/1). K.P. acknowledges a Hungarian Eötvös Fellowship. W.A.H. acknowledges support from the Royal Society London. R.F. thanks A. Müller, C. A. Pignedoli and O. Gröning for the implementation of the multipole expansion algorithms used for the XPD-SSC analysis. We thank A. Tkatchenko for fruitful discussions. The XPD experiments were performed on the SIM beamline at the Swiss Light Source, Paul Scherrer Institut, Villigen, Switzerland.

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R.F. and K.-H.E. conceived the experiments. W.X., T.G. and R.F. performed the experiments and data analysis. K.P., Y.Z., E.B. and W.A.H. conducted the theoretical modelling. L.P. and L.T.S. conducted the chemical synthesis. W.X., K.-H.E. and R.F. wrote the manuscript with contributions from all the authors.

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Correspondence to Roman Fasel.

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Xiao, W., Ernst, KH., Palotas, K. et al. Microscopic origin of chiral shape induction in achiral crystals. Nature Chem 8, 326–330 (2016). https://doi.org/10.1038/nchem.2449

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