Institut Charles Sadron, 23 rue du Loess, BP 84037, 67034 Strasbourg Cedex 2, France.
ACS Nano. 2012 Oct 23;6(10):8498-507. doi: 10.1021/nn302206h. Epub 2012 Sep 13.
Size-selective organization of 2 nm dodecanethiol stabilized gold nanoparticles (AuNPs) into periodic 1D arrays by using the surface topographical features of a soft template is described. The template consists of micrometer length nanotapes organized into nanosheets with periodic valleys running along their length and is generated by the hierarchical self-assembly of a diamide molecule (BHPB) in cyclohexane. The AuNP ordering achieved simply by mixing the preformed template with the readily available ~2 nm dodecanethiol stabilized AuNPs is comparable to those obtained using programmable DNA and functional block copolymers. The observed periodicity of the AuNP arrays provided valuable structural clues about the organization of nanotapes into nanosheets. Self-assembling BHPB molecules in the presence of AuNPs by heating and cooling the two components led to a comparatively disordered organization because the template structure was changed under these conditions. Moreover, the template could not order larger AuNPs (5 nm) into a similar 1D array, owing to the steric restriction imposed by the dimension of the valleys on the template. Interestingly, this geometric constraint led to AuNP size sorting when a polydisperse sample (2.5 ± 0.9 nm) was used for organization, with AuNPs attached to the template edges being larger (≥2.2 ± 0.9 nm) than those associated to the inner valleys (1.6 ± 0.8 nm). This is a unique example of size-sorting induced by the surface topographical features of a soft template.
通过使用软模板的表面形貌特征,将2nm 十二硫醇稳定的金纳米粒子(AuNPs)选择性地组装成周期性的 1D 阵列。该模板由微米长度的纳米带组成,这些纳米带排列成纳米片,纳米片上沿其长度方向排列有周期性的凹槽,是由酰胺分子(BHPB)在环己烷中的分级自组装产生的。通过将预成型的模板与现成的2nm 十二硫醇稳定的 AuNPs 简单混合,即可实现 AuNP 的有序排列,其有序程度可与使用可编程 DNA 和功能嵌段共聚物获得的有序程度相媲美。AuNP 阵列的观察到的周期性为纳米带在纳米片中的组织提供了有价值的结构线索。通过加热和冷却两种组分,在存在 AuNP 的情况下自组装 BHPB 分子会导致相对无序的组织,因为在这些条件下模板结构会发生变化。此外,由于模板凹槽的尺寸对 AuNP 的尺寸造成了限制,因此模板无法将更大的 AuNP(~5nm)有序地组装成类似的 1D 阵列。有趣的是,当使用多分散样品(2.5±0.9nm)进行组织时,这种几何约束导致 AuNP 尺寸分选,附着在模板边缘的 AuNP 较大(≥2.2±0.9nm),而与内部凹槽相关的 AuNP 较小(1.6±0.8nm)。这是软模板表面形貌特征诱导尺寸分选的一个独特示例。