%0 Journal Article
%T Efficient Synthesis of Metastable Cyclodextrin-Based Polyrotaxanes with Tunable Threading Ratios.
%A Qiao B
%A Zeng Q
%A Li L
%J Angew Chem Int Ed Engl
%V 0
%N 0
%D 2024 Jul 29
%M 39075021
%F 16.823
%R 10.1002/anie.202412839
%X Cyclodextrin-based polyrotaxanes (CD-PRs) are gaining attention for their dynamic sliding rings along the polymer axis, enabling various applications in molecular shuttles, drug delivery, and durable polymers with slidable cross-links. However, the conventional synthesis of CD-PRs with tunable threading ratios is typically laborious, time-consuming, and complicated, which limits their scalability and cost-effectiveness. Herein, we highlight the great potential of planetary centrifugal mixing, a process that significantly accelerates and simplifies the initial synthesis of polypseudorotaxanes (PPRs), followed by a thiol-ene click reaction as an efficient end-capping reaction for the synthesis of PRs. Notably, PRs synthesized with glutathione (GSH) as the end-capping reagent are in a metastable state, where GSH act as a molecular bumper that significantly prevent de-threading of α-CD rings at room temperature. Moreover, the rate of ring de-threading can be precisely controlled by heating, enabling the preparation of metastable PRs with tunable threading ratios over a wide range. The developed strategy is of great significance to the efficient synthesis of CD-PRs, thus marking a significant step towards their practical application in advanced functional materials and devices.