Gauthier-Jaques Martin, Theato Patrick
Soft Matter Synthesis Laboratory, Institute for Biological Interfaces 3 (IBG-3), Karlsruhe Institute of Technology (KIT), Hermann-von-Helmholtz-Platz 1, 76344 Eggenstein-Leopoldshafen, Germany.
Institute for Chemical Technology and Polymer Chemistry (ITCP), Karlsruhe Institute of Technology (KIT), Engesserstraße 18, 76131 Karlsruhe, Germany.
ACS Macro Lett. 2020 May 19;9(5):700-705. doi: 10.1021/acsmacrolett.0c00248. Epub 2020 Apr 29.
The development of complex topologies such as macromolecular cages constitutes a fascinating aspect of polymer chemistry. In the present work, a novel strategy involving self-closing bifunctional end-groups, which under specific conditions, are allowed to assemble themselves into a predefined thermodynamically favored macrostructure, was designed to fulfill the topological conversion of -shaped polymers to their respective -shaped polymers. A series of four different well-defined four-arm -shaped poly(ε-caprolactone) polymers varying in molar masses were successfully synthesized, end-functionalized, and closed into -shaped polymers by formation of [3]triazolophane macrocycle units. The obtained -shaped polymers feature interesting properties that depend drastically on the chain length of the arms and seem to differ from previous reported polymer cages.
诸如大分子笼等复杂拓扑结构的发展构成了聚合物化学中一个引人入胜的方面。在本工作中，设计了一种涉及自封闭双官能端基的新策略，在特定条件下，这些端基能够自行组装成预定义的热力学有利宏观结构，以实现Y形聚合物到其相应的笼形聚合物的拓扑转化。成功合成了一系列四种不同的、具有明确摩尔质量的四臂Y形聚（ε-己内酯）聚合物，对其进行端基官能化，并通过形成[3]三唑并环辛烷大环单元将其封闭成笼形聚合物。所得到的笼形聚合物具有有趣的性质，这些性质极大地取决于臂的链长，并且似乎与先前报道的聚合物笼不同。
