Target-triggered cascade assembly of a catalytic network as an artificial enzyme for highly efficient sensing

Determining the catalytic activity of artificial enzymes is an ongoing challenge. In this work, we design a porphyrin-based enzymatic network through the target-triggered cascade assembly of catalytic nanoparticles. The nanoparticles are synthesized via the covalent binding of hemin to amino-coated gold nanoparticles and then the axial coordination of the Fe center with a dual-functional imidazole or pyridine derivative. The network, which is specifically formed by coordination polymerization triggered by Hg²⁺ as the target, shows high catalytic activity due to the triple amplification of enzymatic activity during the cascade assembly. The catalytic dynamics are comparable to those of natural horseradish peroxidase. The catalytic characteristics can be ultrasensitively regulated by the target, leading to a selective methodology for the analysis of sub-attomolar Hg²⁺. It has also been used for "signal-on" imaging of reactive oxygen species in living cells. This work provides a new avenue for the design of enzyme mimics, and a powerful biocatalyst with signal switching for the development of biosensing protocols.