School of Chemistry and Chemical Engineering, State Key Laboratory of Metal Matrix Composites, Shanghai Jiao Tong University, 800 Dongchuan Road, Shanghai 200240, PR China.
Chemistry. 2010 Nov 8;16(42):12710-7. doi: 10.1002/chem.201001084.
A self-assembly approach to tuning the optical properties of a star copolymer is reported herein. The star copolymer HCP-star-PEG with a hyperbranched conjugated polymer (HCP) core and many linear poly(ethylene glycol) (PEG) arms has been prepared successfully. The HCP core was synthesized by Wittig coupling of N-(n-hexyl)-3,6-diformylcarbazole and 1,3,5-bis[(triphenylphosphonio)methyl]benzene tribromide. Subsequently, the linear PEG arms were grafted onto the HCP core by acylhydrazone connection. It was found that the optical properties of HCP-star-PEG in chloroform solution changed on addition of acid. Both (1)H NMR and UV/Vis spectroscopic investigations confirmed that the variation of the optical properties was related to the complexation of the acid and the imine bond in the acylhydrazone group. HCP-star-PEG self-assembled into core-shell micelles in the mixed solvent of chloroform and acetonitrile, which affected the protonation of the imine bond. Therefore the optical properties of HCP-star-PEG can be readily controlled by self-assembly.
本文报道了一种通过自组装来调节星型共聚物光学性质的方法。成功制备了具有超支化共轭聚合物(HCP)核和许多线性聚(乙二醇)(PEG)臂的星型共聚物 HCP-star-PEG。HCP 核通过 N-(正己基)-3,6-二醛基咔唑和 1,3,5-三[(三苯基膦)甲基]苯三溴化物的 Wittig 偶联反应合成。随后,通过酰腙连接将线性 PEG 臂接枝到 HCP 核上。结果发现,HCP-star-PEG 在氯仿溶液中的光学性质在加入酸后发生变化。1H NMR 和紫外/可见光谱研究证实,光学性质的变化与酸与酰腙基团中亚胺键的络合有关。HCP-star-PEG 在氯仿和乙腈的混合溶剂中自组装成核壳型胶束,这影响了亚胺键的质子化。因此,HCP-star-PEG 的光学性质可以通过自组装来轻松控制。