Fe掺杂CuS纳米颗粒的合成及其在光热/化学动力学联合治疗中的应用

Synthesis of Fe-doped CuS nanoparticles for the combination of photothermal and chemodynamic therapy

以乙酰丙酮铜和硫粉为铜源和硫源,在油酸(OA)‑油胺(OM)‑十八烯(ODE)体系中合成了近红外吸收的硫化铜(CuS)纳米颗粒,并通过改变硫元素活化状态的方式调节其吸收峰到适合光热治疗的1064 nm附近。通过阳离子交换法进一步制备了Fe、Mn等元素掺杂的CuS纳米颗粒,并保持其吸收峰位置几乎不变。使用微乳法进行聚乙二醇(PEG)化修饰后,这些纳米颗粒在水溶液中表现出良好的分散性和稳定性。分别测试了CuS纳米颗粒在Fe^(3+)掺杂前后的光热性能及羟基自由基(·OH)生成能力。结果表明,PEG修饰后Fe^(3+)掺杂的CuS纳米颗粒(CuS∶Fe‑PEG)在1064 nm处的质量消光系数为37.5 L·g^(-1)·cm^(-1),光热转换效率可达43.7%。虽然光热性能略低于未掺杂的CuS‑PEG,但其·OH生成能力有大幅提升。细胞实验也表明,在弱酸性条件下,CuS∶Fe‑PEG具有更好的肿瘤细胞抑制能力,在1064 nm激光照射下能够有效杀死肿瘤细胞,可用于光热/化学动力学联合治疗。

Copper sulfide(CuS)nanoparticles with strong absorption in the near‑infrared region were synthesized in oleic acid(OA)‑oleylamine(OM)‑octadecene(ODE)system using copper acetylacetonate and sulfur powder as copper and sulfur sources respectively.By adjusting the activation solvent for the sulfur powder,the absorption peak can be tuned to around 1064 nm which was beneficial for photothermal therapy.The Fe and Mn elements doped CuS nanoparticles were further prepared by the cation exchange approach,and the absorption peak can be retained after the reaction.Then,these hydrophobic nanoparticles were transferred into an aqueous solution by the microemulsion method,the obtained PEGylated(PEG=poly(ethylene glycol))nanoparticles exhibited excellent dispersity and colloidal stability.Their photothermal performance and the hydroxyl radical(·OH)production before and after Fe^(3+)‑doping were investigated thereafter.The mass extinction coefficient of Fe^(3+)‑doped CuS nanoparticles after PEGylation(CuS∶Fe‑PEG)at 1064 nm was 37.5 L·g^(-1)·cm^(-1),with a high photothermal conversion efficiency of around 43.7%.Although these values were slightly decreased compared with undoped CuS‑PEG,their ability to produce·OH was significantly improved.A higher inhibition ratio of cancer cells was observed with CuS∶Fe‑PEG nanoparticles under weak acid condition.And under 1064 nm laser,these nanoparticles can kill cancer cells more effectively.Therefore,the prepared CuS∶Fe‑PEG nanoparticles can be used for the combination of photothermal and chemodynamic therapy.