Rotaxanating metallo-supramolecular nano-cylinder helicates to switch DNA junction binding
Research output: Contribution to journal › Article › peer-review
A class of rotaxane is created, not by encapsulating a conventional linear thread, but rather by wrapping a large cucurbituril macrocycle about a three-dimensional, cylindrical, nanosized, self-assembled supramolecular helicate as the axle. The resulting pseudo-rotaxane is readily converted into a proper interlocked rotaxane by adding branch points to the helicate strands that form the surface of the cylinder (like branches and roots on a tree trunk). The supramolecular cylinder that forms the axle is itself a member of a unique and remarkable class of helicate metallo-drugs that bind Y-shaped DNA junction structures and induce cell death. While pseudo-rotaxanation does not modify the DNA-binding properties, proper, mechanically-interlocked rotaxanation transforms the DNA-binding and biological activity of the cylinder. The ability of the cylinder to de-thread from the rotaxane (and thus to bind DNA junction structures) is controlled by the extent of branching: fully-branched cylinders are locked inside the cucurbituril macrocycle, while cylinders with incomplete branch points can de-thread from the rotaxane in response to competitor guests. The number of branch points can thus afford kinetic control over the drug de-threading and release.
|Number of pages||10|
|Journal||Journal of the American Chemical Society|
|Early online date||20 Nov 2020|
|Publication status||Published - 9 Dec 2020|