负载铜纳米簇的氧化硅基杂化胶束制备及其化学动力学治疗  

Preparation and Chemodynamic Therapy of Copper Nanoclusters-Loaded Silica-Based Hybrid Micelles

作　　者：孙奇奇 李永生[1] 牛德超 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）》2022年第4期475-484,共10页Journal of East China University of Science and Technology

基　　金：国家自然科学基金(52072124);上海市东方学者资助计划。

摘　　要：利用3-巯基丙基三甲氧基硅烷(MPTMS)的水解缩聚反应对两亲性嵌段共聚物聚苯乙烯-b-聚丙烯酸(PS-b-PAA)胶束壳层进行固定,得到巯基改性的有机氧化硅胶束。进一步利用巯基与铜离子的配位作用,通过一种原位还原策略制备得到了铜纳米簇负载的有机氧化硅胶束。采用透射电子显微镜、动态光散射、X射线光电子能谱、拉曼光谱等表征方法对纳米粒子的形貌和结构进行分析,模拟生理条件检测其稳定性,并通过亚甲基蓝(MB)降解实验探究其生成羟基自由基(•OH)的能力,同时利用细胞毒性实验探究该胶束的生物安全性和对肿瘤细胞的杀伤作用。结果表明,该功能胶束体系具有pH响应和谷胱甘肽(GSH)消耗特性,可有效催化H_(2)O_(2)生成具有高细胞毒性的•OH,从而可作为一类新型纳米芬顿试剂用于肿瘤的安全、有效治疗。A simple in-situ reduction strategy was developed to synthesize copper nanoclusters-loaded and organosilica-stabilized polystyrene-b-polyacrylic acid(PS-b-PAA)micelles(Cu-POMs).Firstly,the structure of PS-b-PAA micelles were fixed by MPTMS to obtain thiol-modified organosilica micelles(POMs).Subsequently,considering the coordination ability of copper ions with thiol groups,Cu-POMs were successfully prepared.The morphology and hydrodynamic size of Cu-POMs were detected by transmission electron microscopy(TEM)and dynamic light scattering(DLS),respectively.Raman spectroscopy was used to detect the functional groups of Cu-POMs.The valence of Cu in Cu-POMs was analyzed by X-ray photoelectron spectroscopy(XPS).The stability of Cu-POMs in simulating physiological conditions was investigated by DLS.Besides,the ability to generate hydroxyl radical(•OH)through Fenton-like reaction of Cu-POMs was verified by the methylene blue(MB)degradation experiment.Finally,the cytotoxicity experiments were used to evaluate biosafety and killing effect on tumor cells of Cu-POMs.The results showed that Cu-POMs had pH-responsive and glutathione(GSH)depletion properties,which could effectively catalyze H_(2)O_(2)to generate highly cytotoxic•OH.Consequently,it is highly expected that Cu-POMs can be used as a new class of nano-Fenton reagents for the efficient and safe tumor treatment.

关 键 词：化学动力学疗法 类芬顿反应 原位还原 有机硅胶束 

分 类 号：TB33[一般工业技术—材料科学与工程]