Zhang Wei, Zhang Shuailin, Guo Qingyun, Lu Xinlin, Liu Yuchu, Mao Jialin, Wesdemiotis Chrys, Li Tao, Li Yiwen, Cheng Stephen Z D
Department of Polymer Science, College of Polymer Science and Polymer Engineering, The University of Akron, Akron, Ohio 44325-3909, United States.
Department of Chemistry, The University of Akron, Akron, Ohio 44325-3601, United States.
ACS Macro Lett. 2018 Jun 19;7(6):635-640. doi: 10.1021/acsmacrolett.8b00275. Epub 2018 May 17.
We have successfully synthesized a series of monodispersed chain-like giant molecules with precisely controlled macromolecular composition and sequence based on polyhedral oligomeric silsesquioxane (POSS) nanoparticles using an orthogonal "click" strategy. Their nonspherical supramolecular structures, such as lamellae, double gyroids, and hexagonal packed cylinders, are mainly determined by the composition (namely, the number of incorporated amphiphilic nanoparticles). In addition, by precisely alternating the sequence of arranged nanoparticles in the giant molecules with identical chemical compositions, the domain sizes of their supramolecular structures could be fine-tuned. This is attributed to the macromolecular conformational differences caused by collective hydrogen bonding interactions in each set of sequence isomeric giant molecules. This work has demonstrated multilevel manipulation of supramolecular structures of giant molecules: coarse tuning by composition and fine-tuning by sequence.
我们采用正交“点击”策略，成功合成了一系列基于多面体低聚倍半硅氧烷（POSS）纳米粒子的、具有精确控制的大分子组成和序列的单分散链状大分子。它们的非球形超分子结构，如片层、双螺旋体和六方堆积圆柱体，主要由组成（即掺入的两亲性纳米粒子的数量）决定。此外，通过精确交替具有相同化学组成的大分子中排列的纳米粒子序列，可以微调其超分子结构的域尺寸。这归因于每组序列异构大分子中集体氢键相互作用引起的大分子构象差异。这项工作展示了对大分子超分子结构的多级操纵：通过组成进行粗调，通过序列进行微调。
