Phosphorescence Enzyme-Mimics for Time-Resolved Sensitive Diagnostics and Environment-Adaptive Specific Catalytic Therapeutics.

Enzyme mimics (EMs) with intrinsic catalysis activity have attracted enormous interest in biomedicine. However, there is a lack of environmentally adaptive EMs for sensitive diagnosis and specific catalytic therapeutics in simultaneous manners. Herein, the coordination modulation strategy is designed to synthesize silicon-based phosphorescence enzyme-mimics (SiPEMs). Specifically, the atomic-level engineered Co-N 4 structure in SiPEMs enables the environment-adaptive peroxidase, oxidase, and catalase-like activities. More intriguingly, the internal Si-O networks are able to stabilize the triplet state, exhibiting long-lived phosphorescence with lifetime of 124.5 ms, suitable for millisecond-range time-resolved imaging of tumor cells and tissue in mice (with high signal-to-background ratio values of ∼60.2 for in vitro and ∼611 for in vivo ). Meanwhile, the SiPEMs act as an oxidative stress amplifier, allowing the production of ·OH via cascade reactions triggered by the tumor microenvironment (∼136-fold enhancement in peroxidase catalytic efficiency); while the enzyme-mimics can scavenge the accumulation of reactive oxygen species to alleviate the oxidative damage in normal cells, they are therefore suitable for environment-adaptive catalytic treatment of cancer in specific manners. We innovate a systematic strategy to develop high-performance enzymemics, constructing a promising breakthrough for replacing traditional enzymes in cancer treatment applications.