Qu Yingjuan, Liu Xiaoli, Zheng Xingwang, Guo Zhihui
School of Chemistry & Chemical Engineering, Shaanxi Normal University, Xi'an, P. R. China.
Anal Sci. 2012;28(6):571-6. doi: 10.2116/analsci.28.571.
In this research, it was found that a composite film could be formed by mixing Nafion with chitosan on the graphite electrode surface. Then, based on the strong absorption of both chitosan for AuCl(4)(-) and Nafion for Ru(bpy)(3)(2+), respectively, the gold nanoparticles and electrochemiluminescence (ECL) active molecules, Ru(bpy)(3)(2+), were effectively incorporated into the composite film of chitosan with Nafion. Lastly, based on the interaction of Ru(bpy)(3)(2+) with Nafion inside the Nafion-chitosan/gold nanoparticles film, Ru(bpy)(3)(2+) was successfully immobilized within this composite film. In this case, a new composite film for fabricating Ru(bpy)(3)(2+)-based ECL sensors was developed. The performances of this composite film were characterized by transmission electron microscopy (TEM), electrochemistry and electrochemiluminescence methods. Our results showed that: firstly, the gold nanoparticles in the resulting composite film could act as conducting pathways to connect Ru(bpy)(3)(2+) sites; the electrode surface accelerated the charge transport through the composite film, and the diffusion coefficient of Ru(bpy)(3)(2+) within this composite film modified electrode was 65 times higher than that of the pure Nafion film modified electrode. Secondly, due to its unique polymeric cationic character and better film-forming properties, chitosan could improve the compact structure of pure Nafion and greatly enhance the mass-transfer speed of Ru(bpy)(3)(2+). Then, the co-reactant tripropylamine (TPA) inside the composite film could offer better ECL performances such as more rapid ECL response speed, longer-term stability and higher sensitivity compared with the performances of pure Nafion film.
在本研究中,发现通过在石墨电极表面将Nafion与壳聚糖混合可形成复合膜。然后,基于壳聚糖对AuCl₄⁻和Nafion对Ru(bpy)₃²⁺的强吸附作用,金纳米颗粒和电化学发光(ECL)活性分子Ru(bpy)₃²⁺被有效地掺入壳聚糖与Nafion的复合膜中。最后,基于Ru(bpy)₃²⁺与Nafion - 壳聚糖/金纳米颗粒膜内Nafion的相互作用,Ru(bpy)₃²⁺成功固定在该复合膜内。在这种情况下,开发了一种用于制备基于Ru(bpy)₃²⁺的ECL传感器的新型复合膜。通过透射电子显微镜(TEM)、电化学和电化学发光方法对该复合膜的性能进行了表征。我们的结果表明:首先,所得复合膜中的金纳米颗粒可作为连接Ru(bpy)₃²⁺位点的导电通路;电极表面加速了电荷通过复合膜的传输,并且Ru(bpy)₃²⁺在该复合膜修饰电极内的扩散系数比纯Nafion膜修饰电极高65倍。其次,由于壳聚糖独特的聚合物阳离子特性和更好的成膜性能,它可以改善纯Nafion的致密结构,并大大提高Ru(bpy)₃²⁺的传质速度。然后,与纯Nafion膜的性能相比,复合膜内的共反应剂三丙胺(TPA)可提供更好的ECL性能,如更快的ECL响应速度、更长的稳定性和更高的灵敏度。