近年來透過多重氫鍵作用力用於分子結構上的設計頗為關注，尤其是在超分子結構或嵌段共聚物自組裝形成的奈米結構。因此，本實驗利用一個簡單有效的方法，透過仿效 DNA 相互作用力，使帶有胸腺嘧啶官能基的聚苯乙烯(PVBT)和末端帶有腺嘌呤的聚氧化乙烯(PEO-A)自組裝形成仿生微胞，並對 PVBT 上的 thymine 進行光交聯，製備出穩定的核交聯微胞，在共同溶劑(DMF)下，利用 PEO-A 與 PVBT 鏈間具有的互補多重氫鍵作用力，得到類似接枝的聚合物，然後在選擇性溶劑(H2O或MeCN)的添加下，逐漸形成 PVBT 為核、PEO-A 為殼的穩定微胞。此結構經由染色技術和穿透式電子顯微鏡(TEM)可被清楚觀察到。然而在經過UV光的照射後，對於微胞結構的形狀和大小沒有太大的改變，顯示了此種光核交聯的微胞在尺寸穩定性上的提升；另外，我們結合活性自由基聚合(NMRP)和點擊化學的方式，合成出具有相同聚合度並帶有高含量DNA鹼基對的聚苯乙烯，此 PVBT/PVBA 的錯合系統，因為 A-T 間很強的多點氫鍵作用力，使得兩相混摻系統在所有組成範圍內皆只有單一Tg 值，表示系統呈現勻相的狀態，也因作用力的關係，使得兩高分子鏈段形成物理交聯的超分子結構，這些都可經由 DSC、TEM 和流變儀等分析得到證實；最後，我們進一步合成出帶有DNA 鹼基對的嵌段共聚物 PS67-b-PVBA27，並經由 TEM 觀察到大範圍有序排列的 lamella 層狀結構，然而此結構並沒有因混入具有互補性多重氫鍵作用力的高分子而產生相轉，這與混入的高分子主鏈結構有關，可經由 DSC、SAXS 得到佐證。

Complementary multiple hydrogen bonding interactions in molecular design have recently received significant attention because of the tendency to form new supramolecular structures or the self-assembly of nanostructures from block copolymers. In this study, we mimicked DNA-like interaction, to prepare stable core-crosslinked micelles and subsequent bioinspired photo-crosslinking of the thymine units in PVBT. The micelles featuring PVBT as the core and PEO-A as the shell were formed in the selective solvent pairs. The shapes and sizes of the core/shell micelle structures did not change after exposure to UV light, revealing the enhanced dimensional stability of these photo-core-crosslinked micelles. In addition, We prepare two heteronucleobases homopolymers with the same molecular weight. This binary blend system is able to form a miscible phase and supramolecular network structures due to the strong complementary multiple hydrogen bonding interactions between the A and T units. Finally, we synthesize block copolymer containing DNA base and observe well-defined lamella structure through transmission electron microscopy (TEM). However, this ordered morphology doesn’t have phase transition upon blending with complementary multiple hydrogen bonding homopolymer. This is associated with homopolymer main chain structure.

目錄
摘要 i
Abstract ii
目錄 iii
表目錄 vi
圖目錄 vii
第一章 緒論 1
1.1前言 1
1.2研究動機 2
第二章 文獻回顧 4
2.1微胞的形成 4
2.2仿DNA多重氫鍵作用力 5
2.3氫鍵於高分子混摻系統之原理 6
2.4聚氧化乙烯 (Poly(ethylene oxide), PEO) 7
2.5嵌段共聚物 8
第三章 實驗方法與步驟 9
3.1實驗藥品 9
3.2合成方法 10
3.2.1製備Poly(4-vinylbenzyl triazolylmethyl methylthymine) (PVBT) 10
3.2.2製備Poly(ethylene oxide)-Adenine (PEO-A) 11
3.2.3製備Poly(4-vinylbenzyl triazolylmethyl methyladenine) (PVBA) 11
3.2.4製備Poly(styrene-b-4-vinylbenzyl triazolylmethyl methyladenine) (PS-b-PVBA) 12
3.3實驗儀器 17
3.3.1 核磁共振分析儀(Nuclear Magnetic Resonance, NMR) 型號：Varian® Unity Inova-500 17
3.3.2 傅立葉紅外線光譜(Fourier Transform Infrared Spectrometer, FT-IR) 型號：Bruker Tensor-27 18
3.3.3 微差掃瞄熱卡儀(Differential Scanning Calorimeter, DSC) 型號：TA Q-20 18
3.3.4 小角度Ｘ光散射儀(Small Angle X-ray Scattering, SAXS) 型號：Bruker AXS VANTEC-2000 19
3.3.5 穿透式電子顯微鏡(Transmission Electron Microscope, TEM) 型號：JEOL JEM-2100 19
3.3.6 動態光散射儀(Dynamic Light Scattering, DLS) 型號 : BT-90 19
3.3.7 原子力顯微鏡(Atomic Force Microscope, AFM) 型號 : NanoMan NS4+D3100 20
第四章 結果與討論 21
4.1 PVBT/PEO-A混摻之微胞形態學探討 21
4.1.1 PVBT合成鑑定分析 21
4.1.2 PEO-A合成鑑定分析 22
4.1.3微胞的製備 28
4.2 PVBT/ PVBA混摻性質分析 33
4.2.1 PVBA合成鑑定分析 33
4.2.2 PVBT/PVBA混摻之熱分析 36
4.2.3 PVBT/PVBA混摻之氫鍵作用力探討 38
4.2.4 PVBT/PVBA 錯合物的結構形態研究 40
4.3 PS-b-PVBA/PVBT混摻之自組裝結構分析 44
4.3.1 PS-b-PVBA合成鑑定分析 44
4.3.2 PS-b-PVBA/PVBT混摻之熱分析與氫鍵作用力探討 48
4.3.3 PS-b-PVBA/PVBT混摻之多層次自組裝結構 50
第五章 結論 52
第六章 參考文獻 53

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