National Centre for Sensor Research, School of Chemical Sciences, Dublin City University, Dublin 9, Ireland.
Langmuir. 2010 Jan 19;26(2):1325-33. doi: 10.1021/la902258s.
The formation of a three-dimensional assembly of gold nanoparticles driven by host-guest interactions is described. Assembly is achieved via host-guest interactions between cyclodextrin-modified gold nanoparticles which associate with the adamantane unit of a redox active metal complex Os(CAIPA)(3)(2), where CAIPA is 2-(4-carboxyphenyl)imidazo[4,5-f][1,10]-phenanthroline-1-adamantylamine. The electrochemical properties of thin films formed on glassy carbon electrodes have been probed using cyclic voltammetry. In aqueous LiClO(4), the homogeneous charge transport diffusion coefficient, D(CT), is (8.4 +/- 0.4) x 10(-9) cm(2) s(-1) for both oxidation and reduction of the osmium complexes. Significantly, this charge transport rate is significantly larger than that obtained for a solid deposit of Os(CAIPA)(3)(2) alone where D(CT) is 2.3 x 10(-10) cm(2) s(-1). The higher D(CT) value observed for the nanoparticle arrays suggests that the incorporated nanoparticles facilitate electron transfer between the bound osmium centers.
描述了一种由主体-客体相互作用驱动的金纳米粒子的三维组装。组装是通过主-客体相互作用实现的,其中环糊精修饰的金纳米粒子与氧化还原活性金属配合物Os(CAIPA)(3)(2)的金刚烷单元结合,其中 CAIPA 是 2-(4-羧基苯基)咪唑[4,5-f][1,10]-菲咯啉-1-金刚烷基胺。使用循环伏安法探测了在玻璃碳电极上形成的薄膜的电化学性质。在含水 LiClO(4)中,对于 Os 配合物的氧化和还原,均相电荷传输扩散系数 D(CT)为(8.4 +/- 0.4) x 10(-9) cm(2) s(-1)。值得注意的是,与单独的Os(CAIPA)(3)(2)固体沉积物相比,这个电荷传输速率显著更大,其中 D(CT)为 2.3 x 10(-10) cm(2) s(-1)。对于纳米粒子阵列观察到的更高的 D(CT)值表明,掺入的纳米粒子促进了结合的 Os 中心之间的电子转移。