Supramolecular Peptide Assemblies Efficiently Catalyze the Retroaldol Reaction.

We have shown that de novo designed peptides spontaneously self-assemble to create supramolecular assemblies capable of carrying out the retroaldol reaction of the model substrate methodol with high efficiency and in a sequence-dependent manner. Amyloid-like assemblies formed by short, 7- and 8-residue peptides allow for pKa modulation of amino groups by more than 3 units, akin to what is observed in natural proteins, to support efficient catalysis. Our results further highlight the role that peptide assemblies might have played during the evolution of enzymatic function and, from a more applied perspective, will facilitate the development of new catalytic nanomaterials capable of promoting complex chemical transformations.