Department of Chemistry and Advanced Optoelectronic Technology Center, National Cheng Kung University, Tainan 701, Taiwan.
Chemistry. 2012 Mar 26;18(13):4107-14. doi: 10.1002/chem.201103024. Epub 2012 Feb 17.
A solution approach based on Au(CN)(2)(-) chemistry is reported for the formation of nanoparticles. The covalent character of the Au(CN)(2)(-) precursor was exploited in the formation of sub-10 nm nanospheres (≈2.4 nm) and highly monodisperse icosahedral Au nanoparticles (≈8 nm) at room temperature in a one-pot aqueous synthesis. The respective spherical and icosahedral Au morphologies can be controlled by either the absence or presence of the polymer polyvinylpyrrolidone (PVP). Using Au(CN)(2)(-) as a metal ion source, our findings suggest that the addition of citrate ions is necessary to enhance the particle formation rate as well as to generate a more homogeneous colloidal dispersion. Because of the presence of oxygen and the operation of a CN(-) etching process associated with Au(CN)(2)(-) complex formation, an interesting reversible formation-dissolution process was observed, which allowed us to repeatedly prepare spherical and icosahedral Au nanoparticles. Time-dependent TEM images and UV/Vis spectra were carefully acquired to study the reversibility of this formation-dissolution process. In view of the accompanying generation of toxic cyanide anions, we have developed a protocol to recycle cyanide in the presence of citrate ions through ferric ferrocyanide formation. After completion of particle formation, the residual solutions containing citrate ions and cyanide ions were processed to stain iron oxide nanoparticles endocytosized in cells. Additionally, the as-prepared 8 nm Au icosahedra could be isolated and grown to larger 57 nm-sized icosahedra using the seed-mediated growth approach.
本文报道了一种基于 Au(CN)(2)(-)化学的纳米粒子形成的解决方案。在一锅水相合成中,利用 Au(CN)(2)(-)前体的共价性质,在室温下形成了亚 10nm 的纳米球(≈2.4nm)和高度单分散的二十面体 Au 纳米粒子(≈8nm)。分别通过不存在或存在聚合物聚乙烯吡咯烷酮(PVP)来控制相应的球形和二十面体 Au 形态。使用 Au(CN)(2)(-)作为金属离子源,我们的发现表明,添加柠檬酸盐离子对于提高颗粒形成速率以及产生更均匀的胶体分散是必要的。由于存在氧气和与 Au(CN)(2)(-)配合物形成相关的 CN(-)刻蚀过程,观察到了一个有趣的可逆形成-溶解过程,这使我们能够反复制备球形和二十面体 Au 纳米粒子。仔细获取了时间依赖性 TEM 图像和 UV/Vis 光谱,以研究该形成-溶解过程的可逆性。鉴于伴随产生的有毒氰化物阴离子,我们开发了一种在存在柠檬酸盐离子的情况下通过形成铁氰化亚铁来回收氰化物的方案。在颗粒形成完成后,处理含有柠檬酸盐离子和氰化物离子的残余溶液,以对细胞内内化的氧化铁纳米粒子进行染色。此外,通过种子介导的生长方法,可以将制备的 8nm Au 二十面体分离并生长为更大的 57nm 尺寸的二十面体。