Transmembrane ion channels formed by a star of David [2]catenane and a molecular pentafoil knot

David August, Stefan Borsley, Scott L Cockroft, Flavio della Sala, David Leigh, Simon J. Webb

Research output: Contribution to journalArticlepeer-review

Abstract

A (FeII)6-coordinated triply interlocked (“Star of David”) [2]catenane (612 link) and a (FeII)5-coordinated pentafoil (51) knot are found to selectively transport anions across phospholipid bilayers. Allostery, topology, and building block stoichiometry all play important roles in the efficacy of the ionophoric activity. Multiple FeII cation coordination by the interlocked molecules is crucial: the demetalated catenane exhibits no anion binding in solution nor any transmembrane ion transport properties. However, the topologically trivial, Lehn-type cyclic hexameric FeII helicates—which have similar anion binding affinities to the metalated Star of David catenane in solution—also display no ion transport properties. The unanticipated difference in behavior between the open- and closed-loop structures may arise from conformational restrictions in the linking groups that likely enhances the rigidity of the channel-forming topologically complex molecules. The (FeII)6-coordinated Star of David catenane, derived from a hexameric cyclic helicate, is 2 orders of magnitude more potent in terms of ion transport than the (FeII)5-coordinated pentafoil knot, derived from a cyclic pentamer of the same building block. The reduced efficacy is reminiscent of multisubunit protein ion channels assembled with incorrect monomer stoichiometries.
Original languageEnglish
JournalJournal of the American Chemical Society
Early online date21 Oct 2020
DOIs
Publication statusE-pub ahead of print - 21 Oct 2020

Fingerprint

Dive into the research topics of 'Transmembrane ion channels formed by a star of David [2]catenane and a molecular pentafoil knot'. Together they form a unique fingerprint.

Cite this