铪基纳米金属有机骨架材料制备及X射线增强化学动力协同治疗应用

以铪簇作为金属有机骨架的连接点、刚性双羧基配体2,2’-联吡啶-5,5’-二羧酸作为连接器、乙酸或三氟乙酸和水作为结构调节剂，通过溶剂热法合成得到八面体结构(Hf-MOFs-1)和片状结构(Hf-MOFs-2)的铪基纳米金属有机骨架(Hf-nMOFs)，再经Fe3+修饰得到多功能金属有机骨架材料(Hf-Fe-MOFs-1和Hf-Fe-MOFs-2)。模拟肿瘤微环境体系中羟基自由基检测结果表明，X射线照射能显著促进Hf-Fe-MOFs-1和Hf-Fe-MOFs-2材料产生羟基自由基，且片状Hf-Fe-MOFs-2羟基自由基产生能力高于八面体Hf-Fe-MOFs-1。进一步地，在细胞层面证实了材料能够成功被细胞摄入并实现低剂量X射线促进的化学动力学协同治疗。

Preparation of nanoscale hafnium-containing metal-organic frameworks for X-ray-promoted chemodynamic synergistic therapy

Nanoscale hafnium-containing metal-organic frameworks (Hf-nMOFs) with octahedral (Hf-MOFs-1) and sheet-like (Hf-MOFs-2) structures were synthesized by a solvothermal method using hafnium clusters as the connection point of the MOF, rigid dicarboxylic ligand 2,2''-bipyridyl-5,5''-dicarboxylic acid as the connector, acetic acid or trifluoroacetic acid and water as the structural regulator. Subsequently, a post-modification method was used to incorporate Fe³⁺ into the backbone of Hf-nMOFs, leading to the creation of multifunctional nMOFs, designated as Hf-Fe-MOFs-1 and Hf-Fe-MOFs-2. In a mimic tumor microenvironment, the detection of hydroxyl radicals showed that X-ray irradiation significantly increased the generation efficiency of hydroxyl radicals in both Hf-Fe-MOFs-1 and Hf-Fe-MOFs-2, with a more generation ability of sheet-like Hf-Fe-MOFs-2 than that of octahedral Hf-Fe-MOFs-1. Additionally, cellular assays demonstrated successful uptake of the Hf-nMOFs by cells and confirmed their efficacy in achieving low-dose X-ray-promoted chemodynamic synergistic therapy.