Peng Huisheng, Lu Yunfeng
Department of Chemical and Biomolecular Engineering, Tulane University, New Orleans, Louisiana 70118, USA.
Langmuir. 2006 Jun 20;22(13):5525-7. doi: 10.1021/la053047c.
This work demonstrates the formation of micrometer-sized supramolecular assemblies with tunable morphologies using a homopolymer, poly(4-vinylpyridine), and a small organic acid, 5,7-dodecadiynedioic acid, as the building molecules. Three different morphologies (hollow spheres, solid spheres, and rods) were obtained, depending on the molar ratio of the building molecules. It is proposed that hydrogen bonding between P4VP and DCDA and the pi-pi stacking of the diacetylenic moieties are responsible for the formation of these assemblies. Interestingly, ordered hexagonal and lamellar mesostructures were also formed within the microstructure during the co-assembly process. As a result, UV irradiation of the supramolecular assemblies polymerized the diacetylenic moieties, resulting in cross-linked and responsive blue polydiacetylenic assemblies that can change color to red upon external stimuli (e.g., thermal stimuli). This work provides a novel concept of the synthesis of responsive supramolecular assemblies from a homopolymer and small organic molecules.
这项工作展示了使用均聚物聚（4-乙烯基吡啶）和小分子有机酸5,7-十二碳二炔二酸作为构建分子，形成具有可调形态的微米级超分子聚集体。根据构建分子的摩尔比，获得了三种不同的形态（空心球、实心球和棒状）。有人提出，P4VP和DCDA之间的氢键以及二乙炔部分的π-π堆积是这些聚集体形成的原因。有趣的是，在共组装过程中，微观结构内还形成了有序的六方和层状介观结构。结果，超分子聚集体的紫外线照射使二乙炔部分聚合，形成交联且有响应的蓝色聚二乙炔聚集体，该聚集体在外部刺激（如热刺激）下可变色为红色。这项工作提供了一种从均聚物和小分子有机合成响应性超分子聚集体的新概念。
