Nanocarbon Framework-Supported Ultrafine Mo₂C@MoO Nanoclusters for Photothermal-Enhanced Tumor-Specific Tandem...

Recent advances in the synthesis of multifunctional nanomaterials create new opportunities for the rational design of multimodal chemodynamic therapy (CDT) agents. Precisely tailoring the nanostructure and composition of CDT nanoagents for maximum efficacy remains a challenge. Herein, we report the successful synthesis of nanocarbon framework-supported ultrafine Mo₂C@MoO nanoclusters (C/Mo₂C@MoO) via a pyrolysis of a Mo/ZIF-8 MOF precursor at 900 °C followed by mild surface oxidation. The developed C/Mo₂C@MoO composite demonstrated outstanding performance in photothermal-enhanced tumor-specific tandem catalysis therapy. Specifically, C/Mo₂C@MoO efficiently catalyzed the conversion of endogenous H₂O₂ to cytotoxic ¹O₂ via a Russell mechanism, while also converting the O₂ byproduct to cytotoxic ·O₂^- via an oxidase-like mechanism. A high dispersion of active Mo⁵⁺ sites in the exposed MoO shell enhanced the reactive oxygen species (ROS)-generating efficiency of C/Mo₂C@MoO. Moreover, the Mo₂C core in the ultrafine Mo₂C@MoO nanoclusters allowed NIR-II (1064 nm)-driven photothermal heating, which significantly boosted the CDT process through photothermal effects. Additionally, the CDT process relied on a redox cycle involving Mo⁵⁺/Mo⁶⁺ species, which could be sustained by glutathione (GSH) consumption. Given these advantages, C/Mo₂C@MoO demonstrated remarkable synergistic therapeutic efficacy for cancer treatment (both in vitro and in vivo) through tumor microenvironment-stimulated generation of multiple ROS and NIR-II photothermal activity.