Metal Ions Trigger the Gelation of Cysteine-Containing Peptide-Appended Coordination Cages

Angew Chem Int Ed Engl. 2024 May 3:e202406909. doi: 10.1002/anie.202406909. Online ahead of print.

Abstract

We report a series of coordination cages that incorporate peptide chains at their vertices, prepared through subcomponent self-assembly. Three distinct heterochiral tripeptide subcomponents were incorporated, each exhibiting an L-D-L stereoconfiguration. Through this approach, we prepared and characterized three tetrahedral metal-peptide cages that incorporate thiol and methylthio groups. The gelation of these cages wasprobed through the binding of additional metal ions, with the metal-peptide cages acting as junctions, owing to the presence of sulfur atoms on the peripheral peptides. Gels were obtained with cages bearing cysteine at the C-terminus. Our strategy for developing functional metal-coordinated supramolecular gels with a modular design may result in the development of materials useful for chemical separations or drug delivery.

Keywords: Peptides; chirality; metal-organic cages; self-assembly; supramolecular gel.