The accurate dissection of binding energies into their microscopic components is challenging, especially in solution. Here we study the binding of noble gases (He–Xe) with the macrocyclic receptor cucurbit[5]uril in water by displacement of methane and ethane as 1H NMR probes. We dissect the hydration free energies of the noble gases into an attractive dispersive component and a repulsive one for formation of a cavity in water. This allows us to identify the contributions to host–guest binding and to conclude that the binding process is driven by differential cavitation energies rather than dispersion interactions. The free energy required to create a cavity to accept the noble gas inside the cucurbit[5]uril is much lower than that to create a similarly sized cavity in bulk water. The recovery of the latter cavitation energy drives the overall process, which has implications for the refinement of gas-storage materials and the understanding of biological receptors.

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  • 16 October 2018

    In the version of this Article originally published online, Fig. 2e was missing its data points; this has now been corrected in all versions of the Article.


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W.M.N. thanks A. Ben-Naim for helpful discussions, A. Barba-Bon for control experiments and the DFG (grant no. NA 681/8 within the SPP 1807 ‘Control of London dispersion interactions in molecular chemistry’) for financial support. N.V. thanks A. Mavrantonakis for helpful discussions. S.H. acknowledges support from the China Scholarship Council. F.B. thanks the DFG Emmy Noether programme (BI 1805/2-1). T.T.D. thanks D. Parsons for helpful discussions and acknowledges support from the US Department of Energy, Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences, and Biosciences.

Author information


  1. Department of Life Sciences and Chemistry, Jacobs University Bremen, Bremen, Germany

    • Suhang He
    • , Nina Vankova
    • , Lyuben Zhechkov
    • , Thomas Heine
    •  & Werner M. Nau
  2. Institute of Nanotechnology, Karlsruhe Institute of Technology (KIT), Eggenstein-Leopoldshafen, Germany

    • Frank Biedermann
  3. Wilhelm-Ostwald-Institut für Physikalische und Theoretische Chemie, Universität Leipzig, Leipzig, Germany

    • Nina Vankova
    • , Lyuben Zhechkov
    •  & Thomas Heine
  4. Helmholtz-Zentrum Dresden-Rossendorf, Forschungsstelle Leipzig, Leipzig, Germany

    • Thomas Heine
  5. Institute of Chemistry, The Hebrew University of Jerusalem, Jerusalem, Israel

    • Roy E. Hoffman
  6. Division of Molecular Biosciences, Imperial College London, London, UK

    • Alfonso De Simone
  7. Physical Science Division, Pacific Northwest National Laboratory, Richland, WA, USA

    • Timothy T. Duignan


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F.B. initiated this project with W.M.N. The manuscript was written by S.H., F.B. and W.M.N., and commented on by all authors. All gas binding experiments by 1H NMR were conducted by S.H. and F.B. in the laboratories of W.M.N. 3He NMR experiments were carried out by R.E.H. and water-suppression NMR experiments were carried out by A.D.S. Quantum-chemical calculations were carried out by N.V., L.Z. and T.H. and CSM–D calculations by T.T.D.

Competing interests

The authors declare no competing interests.

Corresponding authors

Correspondence to Frank Biedermann or Nina Vankova or Thomas Heine or Timothy T. Duignan or Werner M. Nau.

Supplementary Information

  1. Supplementary Information

    Experimental section; Supplementary computations; Supplementary Figures 1–10

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