{"title":"Cyclodextrin-Catalyzed Diels–Alder Reaction for the Syntheses of Cyclodextrin Polyrotaxanes, Molecular Tubes, and Molecular Shuttles","authors":"Ying Sun, Yongmin Zhang, Mengke Liang, Jia Li, Xiqun Jiang* and Wei Wu*, ","doi":"10.1021/acs.macromol.4c00892","DOIUrl":null,"url":null,"abstract":"<p >The existing synthesis methods of cyclodextrin (CD) polyrotaxanes (PRs) are generally tedious and low-yield. Herein, we report an efficient synthesis strategy for α-, β-, and γ-CD PRs. A Diels–Alder (DA) reaction between 9-anthracenemethanol and maleimide was used as the capping reaction since the adduct was large enough to lock α- and β-CDs and the reaction could be catalyzed by CDs, achieving high yields in aqueous medium under mild conditions. For the synthesis of γ-CD PRs, we introduced maleimide-modified second-generation polylysine dendrons at both ends of the polymer axle to slow the dethreading during the capping reaction and increase the number of the end-capping groups. Through the microwave-assistant retro-DA reaction, we synthesized α-, β-, and γ-CD molecular tubes with desirable yields. We further expanded the strategy to the synthesis of β-CD rotaxane-based molecular shuttles and achieved fluorescence modulation using the light-driven shuttle movement of the CD ring along the axle.</p>","PeriodicalId":51,"journal":{"name":"Macromolecules","volume":null,"pages":null},"PeriodicalIF":5.1000,"publicationDate":"2024-05-31","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":null,"platform":"Semanticscholar","paperid":null,"PeriodicalName":"Macromolecules","FirstCategoryId":"92","ListUrlMain":"https://pubs.acs.org/doi/10.1021/acs.macromol.4c00892","RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q1","JCRName":"POLYMER SCIENCE","Score":null,"Total":0}
引用次数: 0
Abstract
The existing synthesis methods of cyclodextrin (CD) polyrotaxanes (PRs) are generally tedious and low-yield. Herein, we report an efficient synthesis strategy for α-, β-, and γ-CD PRs. A Diels–Alder (DA) reaction between 9-anthracenemethanol and maleimide was used as the capping reaction since the adduct was large enough to lock α- and β-CDs and the reaction could be catalyzed by CDs, achieving high yields in aqueous medium under mild conditions. For the synthesis of γ-CD PRs, we introduced maleimide-modified second-generation polylysine dendrons at both ends of the polymer axle to slow the dethreading during the capping reaction and increase the number of the end-capping groups. Through the microwave-assistant retro-DA reaction, we synthesized α-, β-, and γ-CD molecular tubes with desirable yields. We further expanded the strategy to the synthesis of β-CD rotaxane-based molecular shuttles and achieved fluorescence modulation using the light-driven shuttle movement of the CD ring along the axle.
期刊介绍:
Macromolecules publishes original, fundamental, and impactful research on all aspects of polymer science. Topics of interest include synthesis (e.g., controlled polymerizations, polymerization catalysis, post polymerization modification, new monomer structures and polymer architectures, and polymerization mechanisms/kinetics analysis); phase behavior, thermodynamics, dynamic, and ordering/disordering phenomena (e.g., self-assembly, gelation, crystallization, solution/melt/solid-state characteristics); structure and properties (e.g., mechanical and rheological properties, surface/interfacial characteristics, electronic and transport properties); new state of the art characterization (e.g., spectroscopy, scattering, microscopy, rheology), simulation (e.g., Monte Carlo, molecular dynamics, multi-scale/coarse-grained modeling), and theoretical methods. Renewable/sustainable polymers, polymer networks, responsive polymers, electro-, magneto- and opto-active macromolecules, inorganic polymers, charge-transporting polymers (ion-containing, semiconducting, and conducting), nanostructured polymers, and polymer composites are also of interest. Typical papers published in Macromolecules showcase important and innovative concepts, experimental methods/observations, and theoretical/computational approaches that demonstrate a fundamental advance in the understanding of polymers.