A Sub-Nanostructural Transformable Nanozyme for Tumor Photocatalytic Therapy

The structural change-mediated catalytic activity regulation plays a significant role in the biological functions of natural enzymes. However, there is virtually no artificial nanozyme reported that can achieve natural enzyme-like stringent spatiotemporal structure-based catalytic activity regulation. Here, we report a sub-nanostructural transformable gold@ceria (STGC-PEG) nanozyme that performs tunable catalytic activities via near-infrared (NIR) light-mediated sub-nanostructural transformation. The gold core in STGC-PEG can generate energetic hot electrons upon NIR irradiation, wherein an internal sub-nanostructural transformation is initiated by the conversion between CeO(2) and electron-rich state of CeO(2−x), and active oxygen vacancies generation via the hot-electron injection. Interestingly, the sub-nanostructural transformation of STGC-PEG enhances peroxidase-like activity and unprecedentedly activates plasmon-promoted oxidase-like activity, allowing highly efficient low-power NIR light (50 mW cm(−2))-activated photocatalytic therapy of tumors. Our atomic-level design and fabrication provide a platform to precisely regulate the catalytic activities of nanozymes via a light-mediated sub-nanostructural transformation, approaching natural enzyme-like activity control in complex living systems. [Image: see text] SUPPLEMENTARY INFORMATION: The online version contains supplementary material available at 10.1007/s40820-022-00848-y.