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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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).
The authors declare no competing financial interests.
Supplementary information (PDF 3923 kb)
Crystallographic data for CoL3 with perchlorate. (CIF 38 kb)
Crystallographic data for cage 3 with perchlorate. (CIF 96 kb)
Crystallographic data for cage 3 with hexafluorophosphate - laboratory source. (CIF 204 kb)
Crystallographic data for cage 3 with hexafluorophosphate -synchrotron source. (CIF 211 kb)
Crystallographic data for tetrahedron 2. (CIF 45 kb)
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Riddell, I., Smulders, M., Clegg, J. et al. Anion-induced reconstitution of a self-assembling system to express a chloride-binding Co10L15 pentagonal prism. Nature Chem 4, 751–756 (2012). https://doi.org/10.1038/nchem.1407
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