發(fā)布時(shí)間：2019-05-28 08:14

【摘要】：含有離子液體(咪唑、吡啶等基團(tuán))的聚合物(PILs)是一類具有導(dǎo)電性以及較低的玻璃化轉(zhuǎn)變溫度性質(zhì)的聚電解質(zhì)。此類基于離子液體性質(zhì)的聚電解質(zhì)在很多應(yīng)用領(lǐng)域例如能源、催化和生物醫(yī)藥科學(xué)等已經(jīng)顯示出了良好的應(yīng)用前景。近年來,具有溫敏型的PILs由于其特定的帶電基團(tuán)以及聚合物與溶劑之間相互作用,相對(duì)于非離子型聚合物或弱帶電側(cè)基的聚合物,具有溫敏型的PILs受到了越來越多的關(guān)注。我們?cè)O(shè)計(jì)了一系列側(cè)基含各種吡啶BF4-基團(tuán)的聚(γ-4-氯甲基芐基-L-谷氨酸),旨在豐富含有IL側(cè)基的溫敏型多肽的數(shù)目,并研究其結(jié)構(gòu)與性能之間關(guān)系,并探討該類聚合物在水溶液以及有機(jī)溶劑中的聚合物和溶劑之間的相互作用。1、利用開環(huán)聚合、季銨鹽化反應(yīng)和離子交換反應(yīng)等合成了一系列側(cè)基含有各種吡啶鹽基團(tuán)(即吡啶鹽、2-甲基吡啶鹽、3-甲基吡啶鹽和4-甲基吡啶鹽)和氟硼酸根反離子的聚(4-甲基芐基-L-谷氨酸酯)。通過核磁共振氫譜(1H NMR)和傅里葉變換紅外光譜(FTIR)驗(yàn)證了中間體和目標(biāo)產(chǎn)物的分子結(jié)構(gòu)。1 H NMR分析表明,吡啶鹽基團(tuán)的接枝效率達(dá)到93-97%。通過變溫紫外-可見光譜研究目標(biāo)產(chǎn)物在醇和水溶液中的高臨界溶液溫度(UCST)類型的溫敏性質(zhì)及其相轉(zhuǎn)變溫度(Tpt)。結(jié)果表明,所得聚合物在甲醇(3 mg/mL)和水溶液(10 mg/mL)的相轉(zhuǎn)變溫度范圍分別為24.9 37.2℃及24.9 37.2℃,Tpt的高低與吡啶鹽基團(tuán)取代基位置相關(guān)。此外,Tpt隨著聚合物濃度的減小而顯著降低。2、設(shè)計(jì)并合成了一系列含吡啶鹽基團(tuán)和氟硼酸根反離子(PyBF4)和低聚乙二醇(OEG)的無規(guī)共聚多肽(PPLG-PyBF4-r-OEG)。該類聚合物的制備包括多步后聚合反應(yīng):聚(γ-3-氯丙基-L-谷氨酸酯)與疊氮化鈉之間的親核取代反應(yīng)、銅催化的1,3-偶極環(huán)加成反應(yīng)接枝OEG側(cè)基,季銨鹽化反應(yīng)接枝吡啶鹽側(cè)基、離子交換反應(yīng)等。PyBF4的摩爾含量小于0.4的PPLG-PyBF4-r-OEG樣品在常溫下具有水溶性及低臨界溶解溫度(LCST)類型的溫敏性質(zhì)。FTIR和圓二色譜(CD)分析顯示,水溶性聚合物在本體以及水溶液中具有α-螺旋構(gòu)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 (緯-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，

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