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Spectroscopy

Unexpected interactions

Nature volume 470, pages 469–470 (2011)Cite this article

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Unpaired electrons can exert effects that allow interatomic contacts in molecules to be detected more easily using nuclear magnetic resonance. One such effect reveals unusual interactions between certain atoms in a protein.

In folded proteins, it is quite easy to find places where the distance between the hydrogen atom in a carbon–hydrogen (C–H) bond and a sulphur atom in a nearby cysteine amino-acid residue is less than 4 ångströms. But no one had suggested that this might be evidence of a weak hydrogen-bond-like interaction — until now. Reporting in the Journal of the American Chemical Society, Westler et al.1 describe unexpectedly large shifts of peaks associated with certain carbon nuclei in the nuclear magnetic resonance (NMR) spectrum of the protein rubredoxin. The shifts correspond to 13C nuclei that are close to sulphur atoms covalently bound to the iron atom in the protein's active site. The authors attribute the shifts to C–H···S–Fe interactions (where the dotted line indicates a non-covalent interaction and S–Fe indicates a covalent sulphur–iron bond), and conclude that these interactions may make a small but non-negligible contribution to the stability of the protein's three-dimensional structure.

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Figure 1: Overlapping orbitals in a through-bond interaction.

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Authors and Affiliations

  1. Ivano Bertini and Claudio Luchinat are at the Magnetic Resonance Center and Department of Chemistry, University of Florence, 50019 Sesto Fiorentino, Italy.,

    Ivano Bertini & Claudio Luchinat

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  1. Ivano Bertini
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  2. Claudio Luchinat
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Correspondence to Ivano Bertini or Claudio Luchinat.

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Bertini, I., Luchinat, C. Unexpected interactions. Nature 470, 469–470 (2011). https://doi.org/10.1038/470469a

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