In the manuscript, we developed a novel strategy to effectively improve the visible light absorption of Ti-based MOF by extending the conjugated degree of organic ligands in Ti-based MOFs. The freebased 5,10,15,20-tetraphenylporphyrin (H 2 TCPP) as organic linkers was used to facilely synthesize Ti-based MOFs (Ti-TiTCPP MOFs). The structural, morphologic and optical properties of Ti-TiTCPP MOFs were investigated. Ti-TiTCPP MOFs was applied to photocatalytic degradation of rhodamine B(RhB) and the photocatalytic degradation performances of Ti-TiTCPP MOFs were compared with that of NH 2 -MIL-125(Ti) MOFs under mercury lamp , xenon lamp and daylight lamp irradiation, respectively. The results showed the photocatalytic degradation performances of Ti-TiTCPP MOFs are superior to that of NH 2 -MIL-125(Ti) MOFs in visible region. Furthermore, the photocatalytic degradation mechanism of Ti-TiTCPP MOFs was investigated in detail based on the electrochemical and photoelectrochemical results associated with previously reported photocatalytic degradation mechanisms of NH 2 -MIL-125(Ti). The possible electrochemical and photoelectrochemical reactions and the changes of Gibbs free energy were analyzed. The degradation possible pathways of RhB and the emerging main intermediate contaminants were carefully analyzed by HPLC-HRMS under the present different solution parameters. And then the photocatalytic system based on Ti-TiTCPP MOFs was successfully applied to deal with real industrial textile wastewaters.
Sonodynamic therapy (SDT) has emerged as a promising strategy for treating tumors owing to its non-invasiveness and high tissue-penetrating depth. Improving the efficiency of electron-hole separation of sonosensitizers and alleviation of the hypoxic tumor microenvironment remain major challenges. Metal-organic frameworks (MOFs) have greatly potential in SDT application, however, exploring new sonosensitizers with high reactive oxygen species (ROS) generation and improving the efficacy through a synergistic effect in combination with other therapeutic modalities remain major challenges. Furthermore, the immunosuppressive tumor microenvironment (TME) is characterized by hypoxia, which limit the efficacy of O 2 -dependent cancer treatments including SDT and immunotherapy. Herein, we fabricated a defect-rich titanium-based MOFs using propionic acid-mediated self-templated hierarchical etching. Reductive platinum nanoparticles were embedded onto the surface of MOFs to enhance the spatial separation of electron-hole pairs and improve the quantum yield of ultrasound-generated singlet oxygen ( 1 O 2 ). Finally, perfluorobromooctane was encapsulated in the MOFs to function as an oxygen carrier to develop an oxygen self-feeding nanosensitizer. In vitro and in vivo assays demonstrated that this nanoplatform could produce high levels of 1 O 2 under ultrasound irradiation, which led to enhanced SDT. Moreover, this nanoplatform also relieved the immunosuppressive TME by overcoming hypoxia and enhancing immunogenic cell death to promote the infiltration of tumor-specific cytotoxic T cells into the immunologically “cold” tumor. Therefore, combination of nanoplatform-mediated SDT with anti-PDL1 antibodies effectively inhibited the primary tumors, as well as the metastatic tumors. This study provides an insightful strategy for improving SDT and broadens the application of MOF-based sonosensitizers for sono-immunotherapy.
危险品化学品经营许可证（带存储）