负载钯簇的氧化硅基杂化胶束的制备及性能  

Preparation and Performance of Palladium Clusters-Loaded Silica-Based Hybrid Micelles

作　　者：赵子伟 池哲人 孙奇奇 李永生[1] 牛德超 ZHAO Ziwei;CHI Zheren;SUN Qiqi;LI Yongsheng;NIU Dechao(Laboratory of Low-Dimensional Material Chemistry,School of Materials Science and Engineering,East China University of Science and Technology,Shanghai 200237,China)

机构地区：[1]华东理工大学材料科学与工程学院,低维材料化学研究室,上海200237

出　　处：《华东理工大学学报（自然科学版）》2023年第4期498-507,共10页Journal of East China University of Science and Technology

基　　金：国家自然科学基金(52072124)。

摘　　要：利用Pluronic嵌段共聚物F127的自组装特性和3-巯基丙基三甲氧基硅烷(MPTMS)在碱性环境下的水解缩聚反应,制备了具有高稳定性的F127有机氧化硅基杂化胶束Pd@FOMs;借助杂化胶束表面的巯基与钯物种的配位作用,利用“原位限域生长”策略制备得到负载钯纳米团簇的F127有机氧化硅基杂化胶束Pd@FOMs。采用动态光散射、透射电镜表征了Pd@FOMs的水合动力学直径和形貌,使用X射线衍射、红外光谱和拉曼光谱分析了Pd@FOMs的结构,并使用3,3′,5,5′-四甲基联苯胺(TMB)进行显色反应验证了该体系的类过氧化物酶活性。在双氧水作为底物的情况下,Pd@FOMs能够将TMB转化为TMB氧化物,该氧化物在652 nm处存在特征吸收峰;Pd@FOMs的米氏常数(Km)为113.91 mmol/L。此外,测定了Pd@FOMs的光热性能,Pd@FOMs溶液(ρ(Pd)=100 mg/L)在808 nm近红外光(1.0 W/cm^(2))照射300 s后,温度从18.1℃升至52.9℃;Pd@FOMs有着良好的光热稳定性,光热转换效率高达65.76%。细胞实验结果表明,Pd@FOMs能够被肿瘤细胞SMMC-7721摄取,并具备良好的生物安全性和光热毒性,有望作为一种类过氧化物酶成像引导的光热治疗剂用于癌症的高效安全诊疗。Self-assembly of Pluronic block copolymer F127 and the hydrolysis and condensation of(3-mercaptopropyl)trimethoxysilane(MPTMS)in an alkaline environment produced highly stable silica-based hybrid micelles.Subsequently,coordination between palladium species and thiols on the surface of hybrid micelles,palladium clusters-loaded silica-based hybrid micelles(Pd@FOMs)were obtained via the“in-situ confined growth”strategy.The hydrodynamic diameter and morphology of Pd@FOMs were characterized by dynamic light scattering(DLS)and transmission electron microscopy(TEM).The structure of Pd@FOMs was analyzed by X-ray diffraction(XRD),infrared spectroscopy(FT-IR)and Raman spectroscopy.3,3′,5,5′-Tetramethylbenzidine(TMB)was used to verify the peroxidase-like(POD-like)activity of [e-mail] the presence of hydrogen peroxide,Pd@FOMs converted TMB to TMB oxide with a characteristic absorption emerged at 652 nm.The Michaelis constant(Km)of Pd@FOMs was calculated to be 113.91 mmol/L.In addition,the photothermal performance of Pd@FOMs was tested.Under 808 nm laser irradiation(1.0 W/cm^(2))for 5 min,Pd@FOMs with a Pd concentration of 100 mg/L induced temperature rise from 18.1℃to 52.9℃.In addition,Pd@FOMs had good photothermal stability with a high photothermal conversion efficiency of 65.76%.Cellular experiments showed that Pd@FOMs could be effectively endocytosed by SMMC-7721 tumor cells and had good biocompatibility and excellent photothermal toxicity.Thus,Pd@FOMs are expected to be applied as an imaging-guided photothermal therapeutic agent for diagnosis and treatment of tumors.

关 键 词：钯簇 胶束 有机氧化硅 过氧化物酶 光热治疗 

分 类 号：TB33[一般工业技术—材料科学与工程]