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The Study of Chiral Adsorption Systems Using Synchrotron-Based Structural and Spectroscopic Techniques: Stereospecific Adsorption of Serine on Au-Modified Chiral Cu{531} Surfaces

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Abstract

We apply modern synchrotron-based structural techniques to the study of serine adsorbed on the pure and Au-modified intrinsically chiral Cu{531} surface. XPS and NEXAFS data in combination with DFT show that on the pure surface both enantiomers adsorb in μ4 geometries (with de-protonated β-OH groups) at low coverage and in μ3 geometries at saturation coverage. Significantly larger enantiomeric differences are seen for the μ4 geometries, which involve substrate bonds of three side groups of the chiral center, i.e. a three-point interaction. The μ3 adsorption geometry, where only the carboxylate and amino groups form substrate bonds, leads to smaller but still significant enantiomeric differences, both in geometry and the decomposition behavior. When Cu{531} is modified by the deposition of 1 and 2 ML Au the orientations of serine at saturation coverage are significantly different from those on the clean surface. In all cases, however, a μ3 bond coordination is found at saturation involving different numbers of Au atoms, which leads to relatively small enantiomeric differences.

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Acknowledgments

The research leading to these results has received funding from the European Community’s Seventh Framework Programme (FP7/2007-2013) under Grant agreement No. 226716, through the Marie Curie Early Stage Training Network “MONET” (No. MEST-CT-2005-020908) and the EPSRC. The authors would also like to acknowledge the support during the experiments provided by the staff of BESSY II, in particular D. Batchelor and thank S. J. Jenkins and A. Ievins for making the results of their DFT calculations available.

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Authors and Affiliations

  1. Department of Chemistry, University of Reading, Whiteknights, Reading, RG6 6AD, UK

    Tugce Eralp, Alix Cornish, Andrey Shavorskiy & Georg Held

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  1. Tugce Eralp
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  2. Alix Cornish
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  3. Andrey Shavorskiy
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  4. Georg Held
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Correspondence to Georg Held.

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Eralp, T., Cornish, A., Shavorskiy, A. et al. The Study of Chiral Adsorption Systems Using Synchrotron-Based Structural and Spectroscopic Techniques: Stereospecific Adsorption of Serine on Au-Modified Chiral Cu{531} Surfaces. Top Catal 54, 1414–1428 (2011). https://doi.org/10.1007/s11244-011-9757-z

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