Gram-Scale Synthesis of a Laccase-Like Cu36 Nanocluster with Enhanced Catalytic Activity and Stability

Abstract

The widespread development of natural laccase in applications is limited by its sensitivity to environmental conditions and high production costs. We report an atomically precise Cu₃₆ nanoclusterzyme that is composed of a Cu₂₂ core stabilized by seven Cu₂L (L: 2-(2-(diphenylphosphaneyl)phenethyl)quinoline) staple units, three adamantanethiol (S-Adm) ligands, and one acetate ion (CH₃COO^–). This Cu₃₆ nanoclusterzyme demonstrates a laccase-like activity and exhibits dual functionality: (1) it catalyzes oxidation of phenolic pollutants with a maximum rate (4.12 μM·min^–1), which is 2.8 times greater than that of natural laccase and (2) it enables selective detection of epinephrine through a colorimetric response, with a detection limit of 0.43 μg/mL. Importantly, the Cu₃₆ nanoclusterzyme is stable under extreme conditions, including extreme pH values, ionic strength, temperature, and storage time. It also preserves 80% catalytic efficiency after seven cycles and exhibits broad substrate specificity. These results demonstrate the application potential of the efficient Cu₃₆ nanoclusterzyme in the fields of analytical chemistry, environmental protection, and biotechnology.