Suspending Polyrotaxane Dissociation via Photo‐Reversible Capping of Terminals
Suspending Polyrotaxane Dissociation via Photo‐Reversible Capping of Terminals
复制标题
通过光可逆封端来暂停聚轮烷解离
DOI：
10.1002/marc.201900323
复制
发表时间：
2019
影响因子：
4.6
通讯作者：
Yui Nobuhiko
中科院分区：
文献类型：
--
作者：
Arisaka Yoshinori;Yui Nobuhiko
可逆共价键产生具有功能特性的聚合物材料，例如自愈合、形状记忆、应力松弛和刺激响应性。在这里，设计了可光可逆封端的聚轮烷，并证明了其超分子结构的开关控制解离。聚轮烷是通过在聚乙二醇的两端封端二硫代苯甲酸酯并通过多个α-环糊精来合成的。由于二硫代苯甲酸酯阻止了α-环糊精的脱螺纹，因此通过其光裂解诱导了超分子解离。随后，裂解的二硫代苯甲酸酯在黑暗中自发地重新封端聚轮烷末端。因此，超分子解离可以通过二硫代苯甲酸酯终止剂的光可逆封端来调节。这些具有二硫代苯甲酸酯终止剂的聚轮烷是用于光控制物理性质和结构的有前途的功能材料。
Reversible covalent bonds yield polymeric materials with functional characteristics such as self‐healing, shape memory, stress relaxation, and stimuli‐responsiveness. Here, photo‐reversibly cappable polyrotaxanes are designed and the on–off controlled dissociation of their supramolecular architectures is demonstrated. The polyrotaxanes are synthesized by capping dithiobenzoates at both terminals of polyethylene glycol threaded through multiple α‐cyclodextrins. Since dethreading of the α‐cyclodextrins is prevented by the dithiobenzoate stoppers, the supramolecular dissociation is induced by their photo‐cleavage. Subsequently, the cleaved dithiobenzoates spontaneously re‐cap the polyrotaxane terminals in darkness. Thus, the supramolecular dissociation can be modulated by photo‐reversible capping of the dithiobenzoate stoppers. These polyrotaxanes with dithiobenzoate stoppers are promising functional materials for photo‐controlling physical properties and structures.