Institute for Organic Chemistry, University of Duisburg-Essen, 45141, Essen, Germany.
Chemistry. 2018 Jun 26;24(36):9061-9065. doi: 10.1002/chem.201705209. Epub 2018 Jun 1.
Formation of polymeric materials on the surface of supramolecular assemblies is rather challenging because of the often weak noncovalent interactions between the self-assembled template and the monomers before polymerization. We herein show that the introduction of a supramolecular anion recognition motif, the guanidiniocarbonyl pyrrole cation (GCP), into a short Fmoc-dipeptide 1 leads to self-assembled spherical nanoparticles in aqueous solution. Negatively charged diacetylene monomers can be attached onto the surface of these nanoparticles, which, after UV polymerization, leads to the formation of a polymer shell around the self-assembled template. The hybrid supramolecular and polymeric nanoparticles demonstrate intriguing thermal hysteresis phenomena. The template nanoparticles could be disassembled upon treatment with organic base, which cleaved the Fmoc moiety on 1. This strategy thus showed that a supramolecular anion recognition motif allows the post-assembly formation of polymeric nanomaterials from anionic monomers around a cationic self-assembled template.
在超分子组装体表面形成聚合材料颇具挑战性，因为在聚合之前，自组装模板和单体之间的非共价相互作用往往较弱。本文中，我们表明，在短的 Fmoc-二肽 1 中引入超分子阴离子识别基元胍基羰基吡咯阳离子（GCP），会在水溶液中形成自组装的球形纳米颗粒。带负电荷的二炔单体可以附着在这些纳米颗粒的表面，经紫外线聚合后，在自组装模板周围形成聚合物壳。这种杂化的超分子和聚合纳米颗粒表现出有趣的热滞现象。模板纳米颗粒可以用有机碱处理而解组装，该处理会切断 1 上的 Fmoc 部分。因此，该策略表明超分子阴离子识别基元允许在带正电荷的自组装模板周围，由阴离子单体通过后组装形成聚合纳米材料。
