SupEnzyme: Combining enzymes with supramolecules for recyclable catalysis

Enzymes are formidable homogeneous biocatalysts, yet their recyclability remains a substantial impediment in the chemical industry. To address this, we introduce a supramolecular engineering approach that chemically conjugates enzymes with supramolecular β-cyclodextrin (β-CD), furnishing them with the capability for on-demand recyclable catalysis. This method generates a supramolecular enzyme, termed SupEnzyme, in which enzymes are endowed with supramolecular plug-and-play functionalities. Consequently, it can function both as a water-soluble homogeneous catalyst and, when interacting with guest polymers, as a recyclable heterogeneous catalyst. The selective introduction of guests and competitive guests allows for dynamic switching between homogeneous and heterogeneous states, showcasing the adaptability of this approach for catalysis and recycling. Moreover, this concept is extended to the integration of two distinct enzymes for recyclable multienzymatic cascades. Hence, this supramolecular strategy is envisioned to lay the foundation for the next generation of chemical enzyme engineering.