Giant surfactants provide a versatile platform for sub-10-nm nanostructure engineering
Giant surfactants provide a versatile platform for sub-10-nm nanostructure engineering
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DOI：
10.1073/pnas.1302606110
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发表时间：
2013-06-18
影响因子：
11.1
通讯作者：
Cheng, Stephen Z. D.
中科院分区：
文献类型：
--
作者：
Yu, Xinfei;Yue, Kan;Cheng, Stephen Z. D.
不同长度尺度的结构工程是设计具有受控宏观性能的新材料的核心。在这里，我们介绍了一类独特的自组装材料，这种材料建立在形状和体积持久的分子纳米颗粒和其他结构基元(如聚合物)的基础上，可以被视为相应小分子对应物的尺寸放大版本。其中，通过将致密的、极性的分子纳米粒子与不同组成和结构的柔性聚合物尾部在特定的位置进行点击，合成了具有精确分子结构的“巨型表面活性剂”。巨型表面活性剂具有小分子表面活性剂的结构特征，但具有更大的尺寸，它弥合了小分子表面活性剂和嵌段共聚物之间的差距，并在自组装行为方面展示了两种材料的二元性。通过精密合成控制这些巨型表面活性剂的结构变化，进一步表明它们的自组装对一级化学结构非常敏感，导致在集体物理相互作用和几何约束下，在体态、薄膜态和溶液态下得到高度多样化的热力学稳定的纳米结构，特征尺寸约为10 nm或更小。结果表明，这类材料为设计特征尺寸小于10纳米的纳米结构提供了一个通用的平台。这些发现不仅在科学上对理解自组装的化学和物理原理感兴趣，而且在技术上也是相关的，例如在纳米晶片技术和微电子学方面。
The engineering of structures across different length scales is central to the design of novel materials with controlled macroscopic properties. Herein, we introduce a unique class of self-assembling materials, which are built upon shape-and volume-persistent molecular nanoparticles and other structural motifs, such as polymers, and can be viewed as a size-amplified version of the corresponding small-molecule counterparts. Among them, "giant surfactants" with precise molecular structures have been synthesized by "clicking" compact and polar molecular nanoparticles to flexible polymer tails of various composition and architecture at specific sites. Capturing the structural features of small-molecule surfactants but possessing much larger sizes, giant surfactants bridge the gap between small-molecule surfactants and block copolymers and demonstrate a duality of both materials in terms of their self-assembly behaviors. The controlled structural variations of these giant surfactants through precision synthesis further reveal that their self-assemblies are remarkably sensitive to primary chemical structures, leading to highly diverse, thermodynamically stable nanostructures with feature sizes around 10 nm or smaller in the bulk, thin-film, and solution states, as dictated by the collective physical interactions and geometric constraints. The results suggest that this class of materials provides a versatile platform for engineering nanostructures with sub-10-nm feature sizes. These findings are not only scientifically intriguing in understanding the chemical and physical principles of the self-assembly, but also technologically relevant, such as in nanopatterning technology and microelectronics.