Supramolecular Chiral Nanozymes with High and Switchable Enantioselectivity

Abstract

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 Fe 3 O 4 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–Fe 3 O 4 nanozymes are demonstrated to show better catalytic efficiency toward D‐DOPA, whereas M ‐PANI–Fe 3 O 4 nanozymes show preference to L‐DOPA. Intriguingly, through the simple modulation of the Fe 3 O 4 nanoparticle density on P / M ‐PANI–Fe 3 O 4 , the unprecedented enantioselectivity switch of the as‐designed nanozymes is achieved. Moreover, the select factors of P / M ‐PANI–Fe 3 O 4 toward d / l ‐DOPA are determined to be significantly larger than that of commonly used chiral ligands (such as d / l ‐phenylalanine)‐modified Fe 3 O 4 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.