本研究將酪胺酸酐以開環聚合的方式聚合成聚酪胺酸，分別在二甲基甲醯胺及甲醇與聚[4-乙烯基吡啶]進行混摻，觀察兩者間之相溶性與聚胜肽二級結構的差異。從傅立葉紅外線光譜儀的檢測中發現，聚酪胺酸上的氫氧基和聚[4-乙烯基吡啶]上的吡啶基產生很強的氫鍵作用力。利用微差式掃描熱卡儀做熱分析，結果指出，不論兩者比例為何，以甲醇作為溶劑的混摻物之玻璃轉移溫度均大於二甲基甲醯胺。根據儀器測定結果:假定兩者高分子鏈段於二甲基甲醯胺下呈現不規則捲曲，致使溶劑抽乾後聚胜肽為不規則捲曲的形貌；然而，由於在甲醇的環境下，兩種高分子間彼此的氫鍵作用力較強，故假設鏈段間彼此以錯合的方式排列，使得聚胜肽以β-層板的形式存在著。這些二級結構的變化，以傅利葉紅外線光譜儀、固態核磁共振儀、廣角繞射儀檢測之。

In this study we synthesized poly(tyrosine) (PTyr) through living ring-opening polymerization of α-amino acid-N-carboxyanhydride and then blended with poly(4-vinyl pyridine) (P4VP) homopolymer in N, N-dimethylformamide (DMF) and methanol solutions to control the miscibility behavior and the secondary structures of poly(tyrosine). Infrared spectrum analysis suggests that the mixture of PTyr/P4VP possesses strong hydrogen-bonding interaction between the hydroxyl group of PTyr and the pyridine group of P4VP. DSC analyses indicate that these PTyr/P4VP complexes from methanol solution always have higher glass transition temperatures than the corresponding PTyr/P4VP miscible blends obtained from DMF solution. We proposed that the polymer chain behavior of PTyr/P4VP blend from DMF solution is the separated random coil and thus the PTyr chain possesses the random coil secondary structure after solvent evaporation. However, by increasing the hydrogen bonding for PTyr/P4VP complex from methanol solution, inter-polymer complex aggregate is proposed and the corresponding chain behavior enhances the intermolecular hydrogen bonding interaction of PTyr with P4VP that results in the β-sheet conformation based on Fourier transforms infrared (FTIR), solid state nuclear magnetic resonance (NMR) spectroscopy, and wide-angle X-ray diffraction analyses.

摘要 1
ABSTRACT 2
目錄 3
表目錄 5
圖目錄 6
第一章 緒論 7
1-1前言 7
1-2動機與文獻回顧 8
1-3簡介 10
1-3-1聚胜肽 (Polypeptides) 10
1-3-2 摻合原理 11
1-3-3氫鍵摻合系統原理 12
第二章 實驗內容 13
2-1 實驗內容及流程 13
2-2實驗藥品 14
2-3 實驗步驟 15
2-3-1 左旋-酪胺酸酐之合成[56] (synthesis of L-tyrosine N-carboxyanhydride, Tyr-NCA) 15
2-3-2 乙炔基聚[左旋-酪胺酸]之合成 (synthesis of Alkyne end-terminated poly(L-tyrosine), alkyne-PTyr) 15
2-3-3 高分子混摻 (polymer blend) 16
2-3-4 高分子錯合物 (polymer complex) 16
2-4 儀器介紹 17
2-4-1核磁共振光譜儀(Nuclear Magnetic Resonance, NMR)型號: VarianR Unity Inova-500。 17
2-4-2 傅利葉轉換紅外線光譜儀(Fourier Transform Infrared Spectrometer, FT-IR) 型號﹕Bruker Tensor-27 18
2-4-3微差掃瞄卡計(Differential Scanning Calorimeter, DSC)型號：TA Q-20 18
2-4-4 凝膠滲透層析儀（Gel Permeation Chromatography , GPC）型號: Jasco PU-980 19
2-4-5 固態核磁共振儀 (Solid State Nuclear Magnetic Resonance Spectrometer, ssNMR) 型號：BRUKER DSX-400WB 20
2-4-6 基質輔助雷射脫附游離飛行時間質譜儀 (Matrix-Assisted Laser Desorption/Ionization Time of Flight Mass Spectrometer, MALDI-TOF MS) 型號： Bruker Autoflex III TOF/TOF 21
2-4-7 廣角X光繞射儀 (Wide Angle X-Ray Diffraction, WAXD) 型號: NSRRC BL17A 21
第三章 結果與討論 22
3-1 化合物鑑定 22
3-2 PTyr/P4VP混摻及錯合的熱分析 26
3-3 PTyr/P4VP混摻及錯合之紅外線光譜分析 29
3-4 PTyr/P4VP混摻及錯合13C固態核磁共振及廣角X光繞射分析 35
第四章 結論 39
第五章 未來展望 40
參考文獻 41
作者自介 46

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