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可生物降解两亲性聚[(R)-3-羟基丁酸酯]-交替-聚乙二醇多嵌段共聚物的合成、表征及形态学研究

Synthesis, characterization, and morphology studies of biodegradable amphiphilic poly[(R)-3-hydroxybutyrate]-alt-poly(ethylene glycol) multiblock copolymers.

作者信息

Li Xu, Liu Kerh Li, Li Jun, Tan Eunice Phay Shing, Chan Lee Meng, Lim Chwee Teck, Goh Suat Hong

机构信息

Institute of Materials Research and Engineering, National University of Singapore, 3 Research Link, Singapore.

出版信息

Biomacromolecules. 2006 Nov;7(11):3112-9. doi: 10.1021/bm060675f.

Abstract

Novel biodegradable amphiphilic alternating block copolymers based on poly[(R)-3-hydroxybutyrate] (PHB) as biodegradable and hydrophobic block and poly(ethylene glycol) (PEG) as hydrophilic block (PHB-alt-PEG) were successfully synthesized through coupling reaction. Their chemical structures have been characterized by using gel permeation chromatography, (1)H nuclear magnetic resonance, and Fourier transform infrared spectroscopy. Differential scanning calorimetry (DSC) analysis revealed that both PHB and PEG blocks in PHB-alt-PEG block copolymers can crystallize to form separate crystalline phase except in those with a short PEG block (M(n) 600) only PHB crystalline phase has been observed. However, due to the mutual interference from each other, the melting transition of both PHB and PEG crystalline phases shifted to lower temperature with lower crystallinity in comparison with corresponding pure PHB and PEG. The crystallization behavior of PHB block and PEG block has also been studied by X-ray diffraction, and the results were in good agreement with those deduced from DSC study. The surface morphologies of PHB-alt-PEG block copolymer thin films spin-coated on mica have been visualized by atomic force microscopy with tapping mode, indicating formation of laterally regular lamellar surface patterns. Static water contact angle measurement revealed that surface hydrophilicity of these spin-coated thin films increases with increasing PEG block content.

摘要

通过偶联反应成功合成了一种新型的可生物降解两亲性交替嵌段共聚物,该共聚物以聚(R)-3-羟基丁酸酯作为可生物降解的疏水嵌段,聚乙二醇(PEG)作为亲水嵌段(PHB-alt-PEG)。通过凝胶渗透色谱、核磁共振氢谱(1)H和傅里叶变换红外光谱对其化学结构进行了表征。差示扫描量热法(DSC)分析表明,PHB-alt-PEG嵌段共聚物中的PHB和PEG嵌段都能结晶形成单独的晶相,除了那些PEG嵌段较短(M(n) 600)的共聚物,仅观察到PHB晶相。然而,由于相互干扰,与相应的纯PHB和PEG相比,PHB和PEG晶相的熔融转变都向较低温度移动,结晶度也较低。通过X射线衍射研究了PHB嵌段和PEG嵌段的结晶行为,结果与DSC研究推断的结果吻合良好。采用轻敲模式的原子力显微镜观察了旋涂在云母上的PHB-alt-PEG嵌段共聚物薄膜的表面形貌,表明形成了横向规则的层状表面图案。静态水接触角测量表明,这些旋涂薄膜的表面亲水性随着PEG嵌段含量的增加而增加。

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