Modifying the Catalytic Activity of Lipopeptide Assemblies with Nucleobases

Biohybrid catalysts that operate in aqueous media are intriguing for systems chemistry. In this paper, we investigate whether control over the self-assembly of biohybrid catalysts can tune their properties. As a model, we use the catalytic activity of functional hybrid molecules consisting of a catalytic H-dPro-Pro-Glu tripeptide, derivatized with fatty acid and nucleobase moieties. This combination of simple biological components merged the catalytic properties of the peptide with the self-assembly of the lipid, and the structural ordering of the nucleobases. The biomolecule hybrids self-assemble in aqueous media into fibrillar assemblies and catalyze the reaction between butanal and nitrostyrene. The interactions between the nucleobases enhanced the order of the supramolecular structures and affected their catalytic activity and stereoselectivity. The results point to the significant control and ordering that nucleobases can provide in the self-assembly of biologically inspired supramolecular catalysts. Biomolecular conjugates consisting of a catalytic tripeptide, a fatty acid and nucleobase moieties form defined fibrillar assemblies in aqueous media and catalyze the reaction of butanal with nitrostyrene. The interaction between complementary nucleobases enhanced the order in the supramolecular assemblies and influenced the catalytic properties of the peptide-nucleolipids, indicating that nucleobases can be valuable for control over the self-assembly and catalytic properties of biologically inspired supramolecular catalysts.image