环糊精和RAFT试剂准轮烷的合成和表征
通过相转移法、Steglich酯化法和酰氯法合成了3种具有三硫代碳酸酯结构的RAFT试剂,S-1-十二烷基-S′-(α,α′-二甲基-α′′-乙酸)三硫代碳酸酯(DDMAT)、S-1-十二烷基-S′-(α,α′-二甲基-α′′-乙酸)三硫代碳酸酯封端三缩四乙二醇(TEG-CTA)和双(S-1-十二烷基-S′-(α, α′-二甲基-α′′-乙酸))三硫代碳酸酯封端聚丙二醇(PPG-CTA)。将α、β和γ环糊精作为大环主体,在水中通过共沉淀法与之包合形成了一种新型的准(聚)轮烷结构,通过核磁共振氢谱、X射线衍射分析、红外光谱、热重分析对产物的结构进行了表征和分析。研究结果表明三组准(聚)轮烷均可以稳定形成,但包合位点不同。其中,β-CD能进入到PPG-CTA链段中部且不脱出,几乎与链段全覆盖,具有优异的穿线比。
hree novel reversible addition-fragmentation chain transfer (RAFT) agents with trithiocarbonate structures were successfully synthesized through phase-transfer, Steglich esterification, and acyl chloride methods: S-1-dodecyl-S\'-(α,α′-dimethyl-α′′-acetic acid) trithiocarbonate (DDMAT), tetraethylene glycol terminated with S-1-dodecyl-S\'-(α,α′-dimethyl-α′′-acetic acid) trithiocarbonate (TEG-CTA), and polypropylene glycol bis-terminated with S-1-dodecyl-S\'-(α,α′-dimethyl-α′′-acetic acid) trithiocarbonate (PPG-CTA). These RAFT agents were subsequently complexed with α-, β-, and γ-cyclodextrins (CDs) via co-precipitation in aqueous media to construct innovative pseudo(poly)rotaxane architectures with RAFT-initiating capabilities. Comprehensive structural characterization employing 1H NMR spectroscopy, X-ray diffraction (XRD), Fourier-transform infrared spectroscopy (FT-IR), and thermogravimetric analysis (TGA) confirmed the stable formation of all three pseudo(poly)rotaxane systems with distinct inclusion patterns and threading ratios. Notably, β-CD exhibited superior complexation behavior with PPG-CTA, demonstrating complete penetration into the central segment of the polymer chain without dissociation. This unique host-guest interaction achieved nearly full coverage of the polymer chain, indicating an optimal threading ratio. The established structure-property relationships provide valuable insights for designing advanced supramolecular RAFT systems with tailored molecular recognition features.
师景辰、杨丽煦
重庆大学化学化工学院,重庆 041331重庆大学化学化工学院,重庆 041331
化学生物化学生物物理学
准轮烷准聚轮烷环糊精包合物
pseudorotaxanepolypseudorotaxanecyclodextrininclusion complex
师景辰,杨丽煦.环糊精和RAFT试剂准轮烷的合成和表征[EB/OL].(2025-04-23)[2025-05-05].http://www.paper.edu.cn/releasepaper/content/202504-191.点此复制
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