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Adsorption-induced auto-amplification of enantiomeric excess on an achiral surface

Nature Chemistry volume 7, pages 520–525 (2015)Cite this article

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Abstract

The homochirality of biomolecules is a signature of life on Earth and has significant implications in, for example, the production of pharmaceutical compounds. It has been suggested that biomolecular homochirality may have arisen from the amplification of a spontaneously formed small enantiomeric excess (e.e.). Many minerals exhibit naturally chiral surfaces and so adsorption has been proposed as one possible mechanism for such an amplification of e.e. Here we show that when gas-phase mixtures of D- and L-aspartic acid are exposed to an achiral Cu(111) surface, a small e.e. in the gas phase, e.e.g, leads to an amplification of the e.e. on the surface, e.e.s, under equilibrium conditions. Adsorption-induced amplification of e.e. does not require a chiral surface. The dependence of e.e.s on e.e.g has been modelled successfully using a Langmuir-like adsorption isotherm that incorporates the formation of homochiral adsorbate clusters on the surface.

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Figure 1: TPR spectra of D- and *L-Asp on the Cu(111) surface at saturation coverage.
Figure 2: Asp coverage ratios, θD/θ*L, on the achiral Cu(111) surface as a function of exposure time to D/*L-Asp mixtures with partial pressure ratios of PD/P*L = (1/2), 1 and 2.
Figure 3: Relationships between e.e.g of the Asp mixtures in the gas phase and the e.e.s in the adsorbed phase on an achiral Cu(111) surface under equilibrium adsorption conditions at 460 K.

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Acknowledgements

This work was funded by the US Department of Energy through Grant No. DE-FG02-12ER16330. A.J.G. acknowledges the hospitality of the Fritz-Haber Institute during the writing of this manuscript.

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Authors and Affiliations

  1. Department of Chemical Engineering, Carnegie Mellon University, Pittsburgh, 15213, Pennsylvania, USA

    Yongju Yun & Andrew J. Gellman

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  1. Yongju Yun
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Contributions

Y.Y. made the initial observation of auto-amplification on a Cu{653} surface. A.J.G. and Y.Y. designed the experiments that demonstrated auto-amplification on the achiral Cu(111) surface. These were performed solely by Y.Y. A.J.G. and Y.Y. analysed the results and prepared the manuscript jointly.

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Correspondence to Andrew J. Gellman.

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Yun, Y., Gellman, A. Adsorption-induced auto-amplification of enantiomeric excess on an achiral surface. Nature Chem 7, 520–525 (2015). https://doi.org/10.1038/nchem.2250

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