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摘要: 碳纳米管在水溶液中的稳定分散和与蛋白质分子的作用是实现其生物医学应用的重要研究内容之一。采用混合强酸结合超声处理的方法对多壁碳纳米管(MWCNTs)进行表面氧化处理,得到可以在无表面活性剂条件下稳定分散的MWCNTs水溶液。对该水溶液进行高速和超高速离心,通过扫描电镜、紫外/可见/近红外分光光度仪、激光动态光散射和X-射线光电子能谱分析等方法分别对留在水中和沉淀出来的MWCNTs进行表征。结果表明,经过氧化处理的MWCNTs表面引入了包括羧基在内的含氧基团,长度由初始的50μm变为500nm~800nm,且经过不同离心力作用下得到的上清液中MWCNTs的尺寸分布没有明显差别;MWCNTs水溶液在253nm处有与MWCNTs浓度相关的特征吸收峰,由此建立了测定水溶液中MWCNTs浓度的光谱分析方法。此外,通过十二烷基硫酸钠聚丙烯酰胺(SDS)凝胶电泳和荧光光谱分析方法研究了分散在水中的MWCNTs对单一白蛋白、单一纤维蛋白原、以及两种混合蛋白的吸附作用,探讨了聚乙二醇甲醚(PEG)修饰抑制纤维蛋白原在MWCNTs上吸附的可能性。结果表明,MWCNTs对两种单一蛋白均有吸附,对纤维蛋白原的吸附更加强烈。在双蛋白混合溶液中,MWCNTs对纤维蛋白原分子具有强烈的倾向性吸附作用。经PEG分子修饰后,MWCNTs对纤维蛋白原的吸附程度有所降低。Abstract: Stable dispersions of carbon nanotubes in aqueous solution and their interactions with proteins play a crucial role in the realization of biomedical applications of carbon nanotubes. In this work, multiwalled carbon nanotubes (MWCNTs) were oxidized by a concentrated H2SO4 and HNO3 mixture with the aid of ultrasonication to obtain a surfactant free stable aqueous solution with concentration of MWCNTs of 0.23mg/mL. High and ultra highspeed centrifugation were applied to the aqueous solution to yield MWCNTs in deposits and in supernatants, which were characterized by scanning electron microscopy, dynamic light scattering, UV/VIS/NIR spectrophotometry, and X-ray photoelectron spectroscopy. Results showed that oxygencontaining groups including carboxyl acid group were introduced into the MWCNTs and their length were shortened from ~50μm to 500-800nm. The MWCNTs in the supernatants subjected to different centrifugal rates had the same average length and a similar length distribution pattern. The MWCNT aqueous solutions displayed specific adsorption at 253nm, which was used to determine the amount of MWCNTs dispersed in water by a spectral analysis. The nonspecific adsorption between MWCNTs and single albumin, single fibrinogen, and the dual proteins was investigated using sodium dodecyl sulphate-polyacrylamide gel electrphoresis, and spectrofluorometry. It was demonstrated that MWCNTs preferred to adsorb fibrinogen of albumin. Modification of MWCNTs by polyethylene glycol (PEG)-750 suppressed the fibrinogen adsorption.
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