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Additional file 1. Figure S1. Synthesis process of hollow MnO2. Figure S2. UV–vis-NIR spectra of MnO2-Ce6-HA and MnO2-MTZ-HA. Figure S3. Physiological stability evaluation: Digital images of H-MnO2 and MnO2-C/M-HA dispersed in H2O, PBS and DMEM solution for 24 h. Figure S4. TEM image of H-MnO2 at pH 7.4 and pH 5.5. Figure S5. Fluorescence microscopic images of 4T1 cells incubated with Free Ce6 or MnO2-Ce6-HA at different time points. Scale bar: 50 μm. Figure S6. Cell viability of 4T1 with different concentrations of MTZ with or without 660 nm (1.0 W·cm-2, 15 min) for 24 h. Figure S7. Cell viability of 4T1 with different concentrations of MnO2-HA for 24 h. Figure S8. Cell viability of 4T1 with different concentrations of MnO2-C/M-HA with or without 660 nm (1.0 W·cm-2, 15 min) for 24 h. Figure S9. The cytotoxicity of 4T1 cells of varying formulations with or without 660 nm (1.0 W·cm-2, 15 min) for 24 h in hypoxia. Figure S10. Fluorescence microscope images of ROS generation by DCFH-DA staining in cells in hypoxia. Scale bar: 100 μm. Figure S11. Intracellular ATP level after various treatments. Figure S12. Schematic diagram of co-culture by non-contact communication cell chip. Figure S13. Local structure of non-contact communication cell chip. Figure S15. Immunofluorescence of CD11c in 3D-cell cultures of BMDCs. Scale bar: 50 μm. Figure S15. Immunofluorescence of CD80/CD86 in 3D-cell cultures of BMDCs. Scale bar: 50 μm. Figure S16. Ex vivo fluorescence images (12 h post-injection) of 4T1 tumor-bearing mice organs or tissue treated with free Ce6 and MnO2-C/M-HA. Figure S17. H&E staining of heart, liver, spleen, lung, and kidney at the end of antitumor study. Scale bar: 100 μm. Figure S18. Hemolysis rate by incubating RBCs with MnO2-HA and MnO2-C/M-HA at different concentrations (25-100 µg/mL) for 4 h. Figure S19. Blood biochemical indices of healthy mice at day 1, 4 and 7 after intravenous injection of MnO2-C/M-HA. Figure S20. The whole tumor staining of TUNEL. Scale bar: 1000 μm. Figure S21. Immunohistochemical assay of CRT and HMGB1 in the tumor tissues after various treatments. Scale bar: 200 µm. Figure S22. Representative flow cytometry plots showing mature DCs (CD11c+CD80+CD86+) after various treatments. Figure S23. Representative flow cytometry plots showing cytotoxic T lymphocytes (CD3+CD8+) after various treatments. Table S1. Antibodies were used for WB, FC or IF/IHC in this study.