含吡啶盐聚多肽的制备及其在醇或水中的UCST型温敏性质研究
发布时间：2019-05-28 08:14
【摘要】：含有离子液体(咪唑、吡啶等基团)的聚合物(PILs)是一类具有导电性以及较低的玻璃化转变温度性质的聚电解质。此类基于离子液体性质的聚电解质在很多应用领域例如能源、催化和生物医药科学等已经显示出了良好的应用前景。近年来,具有温敏型的PILs由于其特定的带电基团以及聚合物与溶剂之间相互作用,相对于非离子型聚合物或弱带电侧基的聚合物,具有温敏型的PILs受到了越来越多的关注。我们设计了一系列侧基含各种吡啶BF4-基团的聚(γ-4-氯甲基苄基-L-谷氨酸),旨在丰富含有IL侧基的温敏型多肽的数目,并研究其结构与性能之间关系,并探讨该类聚合物在水溶液以及有机溶剂中的聚合物和溶剂之间的相互作用。1、利用开环聚合、季铵盐化反应和离子交换反应等合成了一系列侧基含有各种吡啶盐基团(即吡啶盐、2-甲基吡啶盐、3-甲基吡啶盐和4-甲基吡啶盐)和氟硼酸根反离子的聚(4-甲基苄基-L-谷氨酸酯)。通过核磁共振氢谱(1H NMR)和傅里叶变换红外光谱(FTIR)验证了中间体和目标产物的分子结构。1 H NMR分析表明,吡啶盐基团的接枝效率达到93-97%。通过变温紫外-可见光谱研究目标产物在醇和水溶液中的高临界溶液温度(UCST)类型的温敏性质及其相转变温度(Tpt)。结果表明,所得聚合物在甲醇(3 mg/mL)和水溶液(10 mg/mL)的相转变温度范围分别为24.9 37.2℃及24.9 37.2℃,Tpt的高低与吡啶盐基团取代基位置相关。此外,Tpt随着聚合物浓度的减小而显著降低。2、设计并合成了一系列含吡啶盐基团和氟硼酸根反离子(PyBF4)和低聚乙二醇(OEG)的无规共聚多肽(PPLG-PyBF4-r-OEG)。该类聚合物的制备包括多步后聚合反应:聚(γ-3-氯丙基-L-谷氨酸酯)与叠氮化钠之间的亲核取代反应、铜催化的1,3-偶极环加成反应接枝OEG侧基,季铵盐化反应接枝吡啶盐侧基、离子交换反应等。PyBF4的摩尔含量小于0.4的PPLG-PyBF4-r-OEG样品在常温下具有水溶性及低临界溶解温度(LCST)类型的温敏性质。FTIR和圆二色谱(CD)分析显示,水溶性聚合物在本体以及水溶液中具有α-螺旋构象。
[Abstract]:Polymer (PILs) containing ionic liquids (imidazole, pyridine, etc.) is a kind of polyelectrolytes with conductivity and low glass transition temperature. This kind of polyelectrolytes based on the properties of ionic liquids have shown good application prospects in many application fields such as energy, catalysis and biomedical science. In recent years, temperature-sensitive PILs has attracted more and more attention due to its specific charged groups and the interaction between polymer and solvent. Compared with Nonionic polymer or weakly charged side group polymer, temperature-sensitive PILs has attracted more and more attention. We designed a series of side groups containing various pyridine BF4- groups (纬-4-chloromethylbenzyl-L-glutamic acid) in order to enrich the number of temperature-sensitive peptides containing IL side groups and to study the relationship between their structure and properties. The interaction between polymers and solvents in aqueous solution and organic solvent was also discussed. 1, by ring-opening polymerization, A series of side groups containing various pyridine salt groups (pyridine salt, 2-methylpyridine salt) were synthesized by quartile ammonium salinization and ion exchange reaction. Poly (4-methylbenzyl-L-glutamic acid) of 3-methyl pyridine salt and 4-methyl pyridine salt) and fluoroborate counterion. The molecular structure of the intermediate and the target product was verified by 1H NMR and Fourier transform infrared spectroscopy (FTIR). 1H NMR analysis showed that the grafting efficiency of pyridine group was 93 鈮，
本文编号：2486892
[Abstract]:Polymer (PILs) containing ionic liquids (imidazole, pyridine, etc.) is a kind of polyelectrolytes with conductivity and low glass transition temperature. This kind of polyelectrolytes based on the properties of ionic liquids have shown good application prospects in many application fields such as energy, catalysis and biomedical science. In recent years, temperature-sensitive PILs has attracted more and more attention due to its specific charged groups and the interaction between polymer and solvent. Compared with Nonionic polymer or weakly charged side group polymer, temperature-sensitive PILs has attracted more and more attention. We designed a series of side groups containing various pyridine BF4- groups (纬-4-chloromethylbenzyl-L-glutamic acid) in order to enrich the number of temperature-sensitive peptides containing IL side groups and to study the relationship between their structure and properties. The interaction between polymers and solvents in aqueous solution and organic solvent was also discussed. 1, by ring-opening polymerization, A series of side groups containing various pyridine salt groups (pyridine salt, 2-methylpyridine salt) were synthesized by quartile ammonium salinization and ion exchange reaction. Poly (4-methylbenzyl-L-glutamic acid) of 3-methyl pyridine salt and 4-methyl pyridine salt) and fluoroborate counterion. The molecular structure of the intermediate and the target product was verified by 1H NMR and Fourier transform infrared spectroscopy (FTIR). 1H NMR analysis showed that the grafting efficiency of pyridine group was 93 鈮，
本文编号：2486892
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