DESIRE · DESign of enzyme-InspiREd multivalent catalysts through functional patterning of nanosystems

Developing artificial enzyme mimics represents a promising strategy to overcome some of the limitations of enzymes such as low tolerance to experimental conditions, poor substrate versatility or poor adaptability to abiotic reactions. Supramolecular approaches to creating organized ensembles of molecules allowed for constructing enzyme-mimicking assemblies displaying collective properties in terms of affinity and reactivity. Despite these advances some critical challenges, such as achieving synergy between multiple functional and structural components to enhance the catalytic performance and selectivity of artificial enzyme-mimics, remain untackled. Self‐assembly of peptides on the surface of metal nanoparticles has recently emerged as a powerful strategy towards creating arrays of functional groups in a defined geometry and space. This strategy provides the opportunity to induce cooperativity between the functionalities in the assembly which would be a highly sought for property in an enzyme-mimicking system. The proposed DESIRE project aims at developing new enzyme-mimicking assemblies where a supramolecular approach is used to preorganise simple catalytic units in order to achieve enzyme-like efficiency and selectivity. The designed enzyme-inspired multivalent catalysts will be obtained by a fine-tuning involving orientation, local hydrophobicity and spatial proximity of amino acids and short peptide ligands which coated on the surface of monolayer-protected nanoparticles or embedded within functional polymers. This should allow to create hydrophobic regions decorated with catalytic moieties in the nanostructures reminiscent of the catalytic pockets in enzymes. The catalytic performance of the constructed systems will be evaluated in selected chemical transformations: aldol reaction and cleavage of ester bonds.