Heterojunction engineered bioactive chlorella for cascade promoted cancer therapy

The hypoxic tumor microenvironment is one of most major hurdles restraining the anti-tumor efficiency of photodynamic therapy (PDT). Herein, active photosynthetic Chlorophyceae (Chlorella, Chl) functionalized with black phosphorus nanosheets (BPNSs) through polyaspartic acid (PASP) and Fe³⁺ mediating "Lego building method" are utilized for photocatalyzed oxygen-evolving to realize photosynthesis enhanced synergistic photodynamic/chemodynamic/immune therapy. The Chl cells with inherent photosynthesis and distinct metabolites are able to ameliorate tumor hypoxia, enhance immune cells infiltration, and stimulate the proliferation and maturation of immune cells. BPNSs loaded on the surface of Chl cells construct a type-II heterojunction with the chlorophyll in Chl cells, which improves the conversion efficiency of light through thoroughly separating photo-excited electrons and holes for ¹O₂ generation and O₂ evolution, respectively. Additionally, the lock between "Lego bricks", Fe³⁺, can both consume glutathione (GSH) and catalyze Fenton reaction with H₂O₂ to generate ·OH, mediating chemodynamic therapy (CDT). Moreover, Chl@BP-Fe also exhibited high biocompatibility and potential biodegradability, guaranteeing high potential for clinic applications of this synergistic photodynamic/chemodynamic/immune therapy.