臺灣博碩士論文加值系統

本研究主要包含兩個主題。第一個主題是利用2-vinyl-4,6- diamino-1,3,5-triazine(VDAT)與vinyl benzyl thymine(VBT)和甲基丙烯酸甲酯(MMA)自由基聚合製備一系列的聚甲基丙烯酸甲酯－鹼基共聚物。在檢測方面，利用1H核磁共振分析儀(1H NMR)、傅立葉轉換光譜儀(FTIR)、凝膠滲透層析儀(GPC)、微差式掃描熱卡儀(DSC)對共聚物poly(2-vinyl-4,6-diamino-1,3,5- triazine -co-methyl methacrylate) (PVDAT-co-PMMA)與共聚物poly(vinylbenzylthymine-co-methyl methacrylate) (PVBT-co-PMMA)做基本的結構鑑定與熱性質的分析。藉由DSC所測量不同比例混摻的玻璃轉移溫度代入Kwei方程式中所繪出的圖表發現有很明顯的正相關可證明在兩共聚物間存在著多重的氫鍵作用力。從變溫、二維的FTIR和固態13C核磁共振分析的結果可得有利證據，證明在PVDAT上的diamino-1,3,5-triazine官能基和PVBT上的thymine官能基間存在著三個氫鍵的作用。
第二個主題是以開環聚合方式利用γ-Benzyl L-glutamate N-carboxyanhydride的NCA單體聚合成一系列帶有三鍵的poly(γ-Benzyl L-glutamate) (alkyne-PBLG)。隨後以點擊反應(click reaction)的方式將alkyne-PBLG接在帶有八個官能基分子的多面體倍半矽氧烷寡聚體(POSS)而形成具α-螺旋和β-板狀之聚胜肽嵌段共聚物。在檢測上則是利用1H核磁共振分析儀(1H NMR)、傅立葉轉換光譜儀(FTIR)、凝膠滲透層析儀(GPC)、微差式掃描熱卡儀(DSC)對聚胜肽嵌段共聚物 POSS-b-PBLG (Polyhedral oligomeric silsesquioxanes -Poly(γ-benzyl -L-glutamate)) 做基本的結構鑑定與熱性質的分析。藉由傅立葉紅外線光譜儀(FTIR)和固態13C核磁共振分析的結果可得在POSS末端上的聚胜肽端會因彼此的作用力和聚胜肽端的長度的影響使β-板狀的結構受到破壞。

This research includes two topics. The first topic is prepared a series of poly(methyl methacrylate) (PMMA)-based copolymers through free radical copolymerizations of methyl methacrylate in the presence of the either 2 - vinyl - 4,6 -diamino - 1, 3, 5triazine(VDAT) or vinylbenzyl -thymine (VBT). Using 1H nuclear magnetic resonance (NMR) spectroscopy, Fourier transform infrared (FTIR) spectroscopy, differential scanning calorimetry (DSC), we investigated the thermal properties and hydrogen-bonding interactions within blends of the two copolymers poly(2-vinyl-4,6-diamino-1,3,5-triazine-co-methyl methacrylate) (PVD AT-co-PMMA) and poly(vinylbenzylthymine-co-methyl methacrylate) (PVBT-co-PMMA). A large positive deviation in the behavior of the glass transition temperature determined by using the Kwei equation and DSC analyses indicated that strong multiple hydrogen-bonding interactions existed between the two copolymers. The FTIR and solid-state NMR spectroscopic analyses provided positive evidence for the presence of three hydrogen bonds between the diamino-1,3,5-triazine groups of PVDAT and thymine groups of PVBT.
The second topic is synthesized a series of alkyne end-terminated poly(γ-Benzyl L-glutamate) (alkyne-PBLG), which was prepared by the ring-opening polymerization of the N-carboxyanhydride monomer of γ-Benzyl L-glutamate-carboxyanhydride. Then combination of the alkyne-PBLG with polyhedral oligomeric silsesquioxanes (POSS) with eight function groups are prepared through the click reation and formed a peptide-based block polymer with α-helice and β-sheet conformations. The thermal properties and structure of these polypeptides were characterized by using 1H NMR and FTIR. The FTIR, solid-state NMR and WXRD spectroscopic analyses provided evidence for the change of secondary structure between POSS and terminated peptide group, so that the conformation of β-sheets and α-helices would be influenced by the incorporation of POSS nanoparticle.

摘要 .................................................... Ⅰ
英文摘要 ................................................ Ⅲ
目錄 .................................................... Ⅴ
表目錄 .................................................. Ⅹ
圖目錄 ................................................ ⅩⅠ
第一章 緒論 ............................................. 1
1-1 簡介與研究動機 ...................................... 1
第二章 利用多重氫鍵對PMMA熱性質的改良 ................. 5
2-1理論與文獻回顧 ...................................... 5
2-1-1氫鍵作用力概說 .................................. 5
2-1-2 摻合原理 ........................................ 7
2-2實驗方法與步驟 ...................................... 9
2-2-1實驗內容 ........................................ 9
2-2-2 實驗藥品 ....................................... 11
2-2-3 合成方法 ....................................... 12
2-2-3-1 乙烯基苯甲基胸腺嘧啶合成(synthesis of vinyl benzyl thymine, VBT) ........................... 12
2-2-3-2共聚合反應(Copolymerization, T-PMMA & D-PMMA) ..................................... 12
2-2-3-3高分子混摻(Polymer blend) ................ 13
2-2-6 儀器檢測 ....................................... 13
2-2-6-1 氫核磁共振光譜儀(Proton Nuclear Resonance Spectrometer, 1H-NMR) .......................... 13
2-2-6-2 傅利葉轉換紅外線光譜儀(Fourier Transform Infrared, FTIR) ................................. 14
2-2-6-3 微差掃瞄卡計(Differential Scanning Calorimeter, DSC) ......................................... 15
2-2-6-4 熱重量分析儀(Thermogravimetric Analysis, TGA) .............................................................................................. 16
2-2-6-5 凝膠滲透層析儀(Gel Permeation Chromatography, GPC) ......................................... 17
2-2-6-6 固態核磁共振儀(Solid State Nuclear Magnetic Resonance,Solid-State NMR) ...................... 18
2-2-6-7 黏度詴驗(viscosity ) ...................... 19
2-3 結果與討論 ......................................... 20
2-3-1 VBT單體、PVBT-co-PMMA與PVDAT-co-PMMA共聚物
鑑定 ................................................ 20
2-3-2 PVBT-co-PMMA與PVDAT-co-PMMA二共聚物混摻 分析 ................................................ 22
2-3-2-1 DSC分析 ............................... 22
2-3-2-2 FTIR分析 .............................. 23
2-3-2-3 Solid-State NMR與黏度分析 ............... 26
2-4結論 ............................................... 38
2-5補充及未來延伸 ..................................... 38
第三章 POSS對PBLG二級結構的影響 ..................... 41
3-1理論與文獻回顧 ..................................... 41
3-1-1奈米複合材料 ................................... 41
3-1-2多面體矽氧烷寡聚物(Polyhedral Oligomeric Silsesquioxanes , POSS) ............................................... 42
3-1-3 Click reation概說及其應用 ......................... 45
3-2實驗方法與步驟 ..................................... 47
3-2-1實驗內容 ....................................... 47
3-2-2 實驗藥品 ....................................... 51
3-2-3 合成方法 ....................................... 52
3-2-3-1 L-谷氨酸酐-5-苄脂 (synthesis of γ-Benzyl
L-glutamate N-carboxyanhydride, BLG-NCA) ........ 52
3-2-3-2 乙炔基聚[L-谷氨酸-5-苄脂]( synthesis of Alkyne end -terminated poly(γ-Benzyl L-glutamate) ,alkyne-PBLG) ............................................. 52
3-2-3-3 二乙基苯甲基氯多面體矽氧烷寡聚物合成(synthesis of octakis [dimethyl(phenethylchloro)siloxy]silsesquioxane, VBC-POSS) ................................... 53
3-2-3-4 二乙基苯甲基疊氮多面體矽氧烷寡聚物合成(synthesis of octakis [dimethyl(phenethylazidoo)siloxy]silsesquioxane, N3 -POSS) ............................................. 54
3-2-3-5 Click反應(click reaction of alkyne-PBLG and N3 -POSS) ....................................... 54
3-2-4 儀器檢測 ....................................... 55
3-2-4-1 氫核磁共振光譜儀(Proton Nuclear Resonance Spectrometer 1H-NMR) .......................... 55
3-2-4-2 傅利葉轉換紅外線光譜儀(Fourier Transform Infrared, FTIR) ................................. 55
3-2-4-3 微差掃瞄卡計(Differential Scanning Calorimeter, DSC) ......................................... 55
3-2-4-4固態核磁共振儀(Solid State Nuclear Magnetic
Resonance,Solid State NMR) ...................... 55
3-2-4-5 廣角X光繞射儀(wide-angle X-ray diffraction,WAXD) .............................. 55
3-3 結果與討論 ......................................... 56
3-3-1 N3 –POSS合成鑑定 ............................... 56
3-3-2 alkyne-PBLG合成鑑定 ............................ 57
3-3-3 星狀 PBLG-POSS共聚物合成鑑定 ................. 58
3-3-4 星狀 PBLG-POSS共聚物熱分析 ................... 59
3-3-5 PBLG胜肽的二級結構分析 ........................ 60
3-4 結論 ............................................... 78
參考文獻 ................................................ 79

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