Department of Chemistry and the Ilse Katz Institute for Nanoscale Science &Technology, Ben-Gurion University of the Negev, Beer Sheva 84105, Israel.
Institute of Materials, École Polytechnique Fédérale de Lausanne (EPFL), Lausanne 1015, Switzerland.
Nat Nanotechnol. 2017 Feb;12(2):170-176. doi: 10.1038/nnano.2016.233. Epub 2016 Nov 14.
The uptake of molecular guests, a hallmark of the supramolecular chemistry of cages and containers, has yet to be documented for soluble assemblies of metal nanoparticles. Here we demonstrate that gold nanoparticle-based supraspheres serve as a host for the hydrophobic uptake, transport and subsequent release of over two million organic guests, exceeding by five orders of magnitude the capacities of individual supramolecular cages or containers and rivalling those of zeolites and metal-organic frameworks on a mass-per-volume basis. The supraspheres are prepared in water by adding hexanethiol to polyoxometalate-protected 4 nm gold nanoparticles. Each 200 nm assembly contains hydrophobic cavities between the estimated 27,400 gold building blocks that are connected to one another by nanometre-sized pores. This gives a percolated network that effectively absorbs large numbers of molecules from water, including 600,000, 2,100,000 and 2,600,000 molecules (35, 190 and 234 g l) of para-dichorobenzene, bisphenol A and trinitrotoluene, respectively.
可溶性金属纳米粒子组装体的分子客体摄取尚未见诸于文献,这是超分子笼和容器化学的一个特点。在此,我们证明基于金纳米粒子的超球体能作为疏水客体的主体,用于疏水分子的摄取、传输和随后的释放,所容纳的客体数量超过了单个超分子笼或容器的容纳数量五个数量级,在质量-体积比上可与沸石和金属-有机骨架相媲美。超球体制备于水中,向多金属氧酸盐保护的 4nm 金纳米粒子中添加己硫醇即可。每个 200nm 的组装体包含估计有 27400 个金构筑块之间的疏水性空腔,这些构筑块通过纳米级的孔彼此相连。这赋予了超球一个有效的连续网络,可从水中吸收大量分子,包括分别为 35、190 和 234g/L 的对二氯苯、双酚 A 和三硝基甲苯等 600000、2100000 和 2600000 个分子。