21:T456,Controlling the size and morphology of metal-organic frameworks (MOF) has received increasing research interest but remains a great challenge. In this work, we demonstrate a trace-water-induced competitive coordination procedure to controllably synthesize porphyrinic MOFs including needle-shaped nanomaterials, hollow nanotubes, and nanocubes, using 5,10,15,20-tetrakis(4-carboxyphenyl) porphyrin as organic linkers and Zr⁴⁺ as inorganic building blocks. These three MOFs exhibited shape-dependent singlet oxygen (¹O₂) production under 655 nm laser irradiation. The designed nanocubes were functionalized by coating a MnO₂ shell, which can effectively generate ¹O₂ in the tumor microenvironment (TME) to improve photodynamic therapy (PDT). Moreover, they reacted with GSH, and the resulted Mn²⁺ions generated hydroxyl radicals (·OH) for chemodynamic therapy (CDT). Therefore, the designed MOFs@MnO₂ nanoparticles were responsive to the hypoxic TME to improve the efficiency of PDT and incorporate CDT for tumor ablation.22:T50d,Chemodynamic therapy (CDT) offers a promising alternative to conventional cancer treatment. However, the limited acidity and H2O2 concentration in tumor microenvironment (TME) severely impair the anticancer effects of CDT. In this study, we report a microemulsion-assisted coassembly method to prepare iron(III) tetraphenylporphyrin (FeTPP) and magnetic (Fe3O4) nanocomposite material (FeTPP@Fe3O4), using photoactive FeTPP and Fe3O4 nanocrystals as building blocks. The self-assembling nature of FeTPP results in disordered aggregation and fluorescence quenching, leading to a high light-to-heat conversion efficiency. Continuously, the photo-thermal effect enhances the catalytic decomposition of hydrogen peroxide (H2O2) in the Fenton reaction on Fe3O4 nanocrystals to generate highly toxic hydroxyl radicals (·OH) to destroy cancer cells. This cascade reaction produces a synergistic therapeutic effect between CDT and photothermal therapy (PTT), which significantly amplifies the therapeutic effect and enhances the treatment outcome of cancer patients. The highly efficient tumor catalytic therapy in vivo results confirmed that this nanomedicine treatment is an excellent biocompatible catalytic nanomedicine therapy achieved through a photo-enhanced Fenton reaction activity approach.

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