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Chiral recognition in dimerization of adsorbed cysteine observed by scanning tunnelling microscopy

Nature volume 415, pages 891–893 (2002)Cite this article

Abstract

Stereochemistry plays a central role in controlling molecular recognition and interaction: the chemical and biological properties of molecules depend not only on the nature of their constituent atoms but also on how these atoms are positioned in space. Chiral specificity is consequently fundamental in chemical biology and pharmacology1,2 and has accordingly been widely studied. Advances in scanning probe microscopies now make it possible to probe chiral phenomena at surfaces at the molecular level. These methods have been used to determine the chirality of adsorbed molecules3,4,5, and to provide direct evidence for chiral discrimination in molecular interactions6 and the spontaneous resolution of adsorbates into extended enantiomerically pure overlayers3,7,8,9. Here we report scanning tunnelling microscopy studies of cysteine adsorbed to a (110) gold surface, which show that molecular pairs formed from a racemic mixture of this naturally occurring amino acid are exclusively homochiral, and that their binding to the gold surface is associated with local surface restructuring. Density-functional theory10 calculations indicate that the chiral specificity of the dimer formation process is driven by the optimization of three bonds on each cysteine molecule. These findings thus provide a clear molecular-level illustration of the well known three-point contact model11,12 for chiral recognition in a simple bimolecular system.

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Figure 1: Schematic drawings of a cysteine molecule and the gold (110) surface, and STM images of cysteine pairs on gold (110).
Figure 2: STM images showing absorbate-induced removal of gold atoms.
Figure 3: DFT results for cysteine pairs on the Au(110) surface.
Figure 4: Illustration of the three-point contact model for enantioselectivity in intermolecular interactions.

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Acknowledgements

This work was supported by the Danish National Research Foundation through the Center for Atomic-scale Materials Physics (CAMP) and by the Danish Natural Science Research Council.

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  1. Interdisciplinary Nanoscience Center at University of Aarhus (iNANO) and Institute of Physics and Astronomy, University of Aarhus, Aarhus C, DK-8000, Denmark

    Angelika Kühnle, Trolle R. Linderoth, Bjørk Hammer & Flemming Besenbacher

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  1. Angelika Kühnle
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Correspondence to Flemming Besenbacher.

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Kühnle, A., Linderoth, T., Hammer, B. et al. Chiral recognition in dimerization of adsorbed cysteine observed by scanning tunnelling microscopy. Nature 415, 891–893 (2002). https://doi.org/10.1038/415891a

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