Temporally Controlled Multienzyme Catalysis Using a Dissipative Supramolecular Nanozyme

The development of superior functional enzyme mimics (nanozymes) is essential for practical applications, including point-of-care diagnostics, biotechnological applications, biofuels, and environmental remediation. Nanozymes with the ability to control their catalytic activity in response to external fuels offer functionally valuable platforms mimicking nonequilibrium systems in nature. Herein, we fabricated a supramolecular coordination bonding-based dynamic vesicle that exhibits multienzymatic activity. The supramolecular nanozyme shows effective laccase-like catalytic activity with a K_M value better than the native enzyme and higher stability in harsh conditions. Besides, the nanostructure demonstrates an efficient peroxidase-like activity with NADH peroxidase-like properties. Generation of luminescence from luminol and oxidation of dopamine are efficiently catalyzed by the nanozyme with high sensitivity, which is useful for point-of-care detections. Notably, the active nanozyme exhibits dynamic laccase-mimetic activity in response to pH variation, which has never been explored before. While a neutral/high pH leads to the self-assembly, a low pH disintegrates the assembled nanostructures and consequently turns off the nanozyme activity. Altogether, the self-assembled Cu²⁺-based vesicular nanostructure presents a pH-fueled dissipative system demonstrating effective temporally controlled multienzymatic activity.