Article | Published:

Anion-induced reconstitution of a self-assembling system to express a chloride-binding Co10L15 pentagonal prism

Nature Chemistry volume 4, pages 751756 (2012) | Download Citation

  • An Erratum to this article was published on 24 September 2012

This article has been updated

Abstract

Biochemical systems are adaptable, capable of reconstitution at all levels to achieve the functions associated with life. Synthetic chemical systems are more limited in their ability to reorganize to achieve new functions; they can reconfigure to bind an added substrate (template effect) or one binding event may modulate a receptor's affinity for a second substrate (allosteric effect). Here we describe a synthetic chemical system that is capable of structural reconstitution on receipt of one anionic signal (perchlorate) to create a tight binding pocket for another anion (chloride). The complex, barrel-like structure of the chloride receptor is templated by five perchlorate anions. This second-order templation phenomenon allows chemical networks to be envisaged that express more complex responses to chemical signals than is currently feasible.

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Change history

  • 14 August 2012

    In the version of this Article previously published, in the final paragraph of the Methods section the accession number CCDC 878882 should have read CCDC 879992. This has been corrected in the online Article.

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Acknowledgements

This work was supported by the Engineering and Physical Sciences Research Council (EPSRC), the Netherlands Organization for Scientific Research (M.M.J.S.) and the Marie Curie International Incoming Fellowship Scheme of the Seventh European Union Framework Program (J.K.C.). We thank the EPSRC Mass Spectrometry Service at Swansea for MALDI/time-of-flight experiments, D. Howe for help in running the NMR experiments and C. Sporikou for the synthesis of 6,6′-diformyl-3,3′-bipyridine. The authors thank Diamond Light Source (UK) for synchrotron beam time on I19 (MT7114).

Author information

Affiliations

  1. Department of Chemistry, University of Cambridge, Lensfield Road, Cambridge CB2 1EW, UK

    • Imogen A. Riddell
    • , Maarten M. J. Smulders
    • , Jack K. Clegg
    • , Yana R. Hristova
    • , Boris Breiner
    •  & Jonathan R. Nitschke
  2. School of Chemistry and Molecular Biosciences, The University of Queensland, Brisbane St Lucia, Queensland 4072, Australia

    • Jack K. Clegg
  3. Department of Chemistry, Randolph-Macon College, Ashland, Virginia 23005, USA

    • John D. Thoburn

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Contributions

Synthetic and spectroscopic work was carried out by I.A.R. Experiments were conceived by I.A.R., J.R.N., M.M.J.S., Y.R.H. and J.K.C. X-ray data were collected, solved and refined by J.K.C. Mass spectrometry was performed by B.B. and I.A.R. Data analysis was performed by I.A.R., M.M.J.S, J.D.T. and J.R.N. All authors contributed to the writing of the paper.

Competing interests

The authors declare no competing financial interests.

Corresponding author

Correspondence to Jonathan R. Nitschke.

Supplementary information

PDF files

  1. 1.

    Supplementary information

    Supplementary information

Crystallographic information files

  1. 1.

    Supplementary information

    Crystallographic data for CoL3 with perchlorate.

  2. 2.

    Supplementary information

    Crystallographic data for cage 3 with perchlorate.

  3. 3.

    Supplementary information

    Crystallographic data for cage 3 with hexafluorophosphate - laboratory source.

  4. 4.

    Supplementary information

    Crystallographic data for cage 3 with hexafluorophosphate -synchrotron source.

  5. 5.

    Supplementary information

    Crystallographic data for tetrahedron 2.

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DOI

https://doi.org/10.1038/nchem.1407

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