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Lone pair–π interactions in biological systems: occurrence, function, and physical origin

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Abstract

Lone pair–π interactions are now recognized as a supramolecular bond whose existence in biological systems is documented by a growing number of examples. They are commonly attributed to electrostatic forces. This review attempts to highlight some recent discoveries evidencing the important role which lone pair–π interactions, and anion–π interactions in particular, play in stabilizing the structure and affecting the function of biomolecules. Special attention is paid to studies exploring the physical origin of these at first glance counterintuitive interactions between a lone pair of electrons of one residue and the π-cloud of another. Recent theoretical work went beyond the popular electrostatic model and inquired the extent to which orbital interactions have to be taken into account. In at least one biologically relevant case—that of anion–flavin interactions—a substantial charge-transfer component has been shown to operate.

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Notes

  1. For an exhaustive and plausible comparison of different energy decomposition schemes, see Phipps et al. (2015).

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Acknowledgements

I would like to thank my students and colleagues whom I was lucky to work with and whose names figure in the corresponding references. This work was supported by the Czech Science Foundation (grant no. 14-14654S). Computational resources were provided by the MetaCentrum under the program LM2010005 and by CERIT-SC under the program Centre CERIT Scientific Cloud, part of the Operational Program Research and Development for Innovations (reg. no. CZ.1.05/3.2.00/08.0144).

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Authors and Affiliations

  1. Department of Condensed Matter Physics, Faculty of Science, Masaryk University, Kotlářská 2, 61137, Brno, Czech Republic

    Jiří Kozelka

  2. INSERM, U 1134, DSIMB, 75739, Paris, France

    Jiří Kozelka

  3. Université Paris Diderot, Sorbonne Paris Cité, UMR_S 1134, 75739, Paris, France

    Jiří Kozelka

  4. Institut National de la Transfusion Sanguine (INTS), 75739, Paris, France

    Jiří Kozelka

  5. Laboratoire d’Excellence GR-Ex, 75739, Paris, France

    Jiří Kozelka

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Correspondence to Jiří Kozelka.

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Special Issue: Regional Biophysics Conference 2016.

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Kozelka, J. Lone pair–π interactions in biological systems: occurrence, function, and physical origin. Eur Biophys J 46, 729–737 (2017). https://doi.org/10.1007/s00249-017-1210-1

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