Optimized silicate nanozymes with atomically incorporated iron and manganese for intratumoral coordination-enhanced once-for-all catalytic therapy.

ABSTRACT

Although plant-derived cancer therapeutic products possess great promise in clinical translations, they still suffer from quick degradation and low targeting rates. Herein, based on the oxygen vacancy (OV)-immobilization strategy, an OV-enriched biodegradable silicate nanoplatform with atomically dispersed Fe/Mn active species and polyethylene glycol modification was innovated for loading gallic acid (GA) (noted as FMMPG) for intratumoral coordination-enhanced multicatalytic cancer therapy. The OV-enriched FMMPG nanozymes with a narrow band gap (1.74 eV) can be excited by a 650 nm laser to generate reactive oxygen species. Benefiting from the Mn-O bond in response to the tumor microenvironment (TME), the silicate skeleton in FMMPG collapses and completely degrades after 24 h. The degraded metal M (M = Fe, Mn) ions and released GA can in situ produce a stable M-GA nanocomplex at tumor sites. Importantly, the formed M-GA with strong reductive ability can transform H2O2 into the fatal hydroxyl radical, causing serious oxidative damage to the tumor. The released Fe3+ and Mn2+ can serve as enhanced contrast agents for magnetic resonance imaging, which can track the chemodynamic and photodynamic therapy processes. The work offers a reasonable strategy for a TME-responsive degradation and intratumoral coordination-enhanced multicatalytic therapy founded on bimetallic silicate nanozymes to achieve desirable tumor theranostic outcomes.