Supramolecular Chiral Nanozymes with High and Switchable Enantioselectivity

Understanding and manipulation of catalytic enantioselectivity have emerged as a paramount challenge for decades. Inspired by nature, nanozymes with enantioselectivity have been designed. However, the role of the spatial arrangement interplayed in enantioselective catalysis is rarely paid attention, let alone the manipulation of enantioselectivity switch under this context. Herein, the supramolecular chiral nanozymes composed of P/M‐polyaniline (P/M‐PANI) nanotwists and Fe3O4 nanoparticles without any chiral molecules are constructed. Taking the catalytic oxidation of 3,4‐dihydroxy‐d / l‐phenylalanine (d / l‐DOPA) as a model reaction, P‐PANI–Fe3O4 nanozymes are demonstrated to show better catalytic efficiency toward D‐DOPA, whereas M‐PANI–Fe3O4 nanozymes show preference to L‐DOPA. Intriguingly, through the simple modulation of the Fe3O4 nanoparticle density on P/M‐PANI–Fe3O4, the unprecedented enantioselectivity switch of the as‐designed nanozymes is achieved. Moreover, the select factors of P/M‐PANI–Fe3O4 toward d / l‐DOPA are determined to be significantly larger than that of commonly used chiral ligands (such as d / l‐phenylalanine)‐modified Fe3O4 nanozymes, indicating the superiority of spatial arrangement‐dominated supramolecular chirality over molecular chirality in enantioselectivity. This finding discloses the role that the spatial arrangement‐directed chiral scaffolds interplay in the enzymatic catalytic process and open a new avenue for the facile design of smart nanozymes with controlled enantioselectivity.