本實驗利用氮氧基聚合合成poly(styrene-b-4-vinylbenzyl azide) (PS-b-PVBN3)
，接著與propargyl-thymine (PT) 經點擊化學反應後即可得帶有Thymine官能基之嵌段共聚物，其為poly(styrene-b-4-vinylbenzyl triazolylmethyl methylthymine) (PS-b-PVBT)。然後將帶有Thymine官能基之嵌段共聚物 (PS-b-PVBT) 和帶有Adenine官能基之奈米粒子 (OBA-POSS) 進行混摻即可得具自組裝結構之奈米複合材料，而這奈米複合物可藉由A-T間之多重氫間作用力來穩定其結構。當增加奈米粒子OBA-POSS之添加量於雙嵌段共聚物PS-b-PVBT中，則會從一規則結構轉變成另一規則結構，這種藉由添加物誘導而產生規則相轉，是因其具有效的作用力參數和微相分離兩相間之體積分率改變。
另外，本實驗也利用簡單之混摻方法來製備出雙股螺旋結構，將雙嵌段共聚物(PS-b-PVBT)帶有不同聚合度Thymine單元，分別為PS67-b-PVBT16及 PS67-b-PVBT29，並和帶有Adenine官能基之Pyrene (A-Py)及單壁奈米碳管(SWCNTs)進行三相混摻，由於主鏈PS為achiral高分子鏈且PS鏈段上具有A-T多重氫鍵作用力，而Pyrene和SWCNTs有π–π Stacking作用力，故使其可以沿著SWCNT堆疊，進而產生螺旋結構。
最後，再將任意改質過之Thymine或甚至未改質之Thymine小分子與帶有Adenine官能基之Pyrene (A-Py)及單壁奈米碳管(SWCNTs)進行三相混摻，也發現有雙股螺旋結構產生，因其具有A-T多重氫鍵作用力，且 Pyrene 和 SWCNTs 有π–π Stacking作用力存在，因而產生螺旋結構。

In this study we used nitroxide-mediated radical polymerization to synthesize poly(styrene-b-4-vinylbenzyl azide) (PS-b-PVBN3) and then used click chemistry to react it with propargyl-thymine (PT) to obtain a series of (T)-containing BCP [poly(styrene-b-4-vinylbenzyl triazolylmethyl methylthymine), PS-b-PVBT]. Then well-defined self-assembled structures are obtained in the form of block copolymer nanocomposites, prepared by blending octuply (A)-functionalized POSS [(octakis(vinylbenzyladenine-siloxy)silsesquioxane, OBA-POSS] nanoparticles with a (T)-containing BCP PS-b-PVBT; these NPs are stabilized through complementary multiple hydrogen bonding interactions between the A and T units. A transition from one ordered morphology to another occurred upon increasing the content of OBA-POSS NPs in the PS-b-PVBT. The morphologies revealed with concomitant variations in the effective interaction parameter and the overall volume fractions of the two microphase-separated domains.
We report a simple method for the preparation of double helical structures through a series of block copolymers. Then double helical structures are prepared by blending Adeninemethylpyrene (A-Py) with PS-b-PVBT and single-walled carbon nanotubes (SWCNTs). This double helical structure was observed from achiral random-coil polystyrene (PS) main chains, stabilized through the combination of multiple A–T hydrogen bonds and π–π stacking between pyrene units and SWCNTs. Double helical structures are also prepared by blending A-Py with a (T)-containing molecules and SWCNTs.

論文審定書 i
誌謝 ii
摘要 iii
Abstract iv
圖目錄 ix
表目錄 xii
第一章 緒論 1
1-1 前言 1
l-2 研究動機 2
第二章 理論及文獻回顧 3
2-1 嵌段共聚物(Block copolymer) 3
2-2 多面體矽氧烷寡聚物(Polyhedral Oligomeric Silsesquioxanes, POSS)[41] 4
2-3 高分子摻合原理 5
2-4 氫鍵於混摻系統之原理 6
2-5 Adenine與Thymine自組裝行為 9
第三章 實驗方法及步驟 11
3-1 實驗內容及流程 11
3-2 實驗藥品 12
3-3 製備Poly(styrene-b-4-vinylbenzyl triazolylmethyl methylthymine) (PS-b-PVBT)之嵌段共聚物 13
3-3.1 合成Propargyl-Thymine (PT) 13
3-3.2 合成Polystyrene Homopolymers (PS-TEMPO) 13
3-3.3 合成Poly(styrene-b-vinylbenzyl chloride) (PS-b-PVBC) 13
3-3.4 合成Poly(styrene-b-4-vinylbenzyl azide) (PS-b-PVBN3) 14
3-3.5 合成Poly(styrene-b-4-vinylbenzyl triazolylmethyl methylthymine) (PS-b-PVBT)[75] 14
3-4 製備Octakis(vinylbenzyladeninesiloxy)silsesquioxane (OBA-POSS)之奈米粒子[76] 14
3-4.1 合成octakis(vinylbenzyl chloride)silsesquioxane (OVBC-POSS) 14
3-4.2 合成octakis(vinylbenzyladeninesiloxy)silsesquioxane (OBA-POSS) 15
3-5 嵌段共聚物/奈米粒子之混摻製備方法 15
3-5.1 PS-b-PVBT/OBA-POSS之混摻 15
3-5.2 PS-b-PVBT/OBA-POSS之熱處理 15
3-6 製備1-Adeninemethylpyrene (A-Py) 16
3-6.1 合成Propargyl-Adenine (PA) 16
3-6.2 合成1-Azidomethylpyrene (Py-N3) 16
3-6.3 合成1-Adeninemethylpyrene (A-Py) 16
3-7 嵌段共聚物/A-Py/單壁奈米碳管之三相混摻製備方法 17
3-7.1 PS-b-PVBT/A-Py之混摻 17
3-7.2 PS-b-PVBT/A-Py/SWCNT之三相混摻 17
3-8 製備9-hexadecylthymine (TC-16) 17
3-8.1 合成9-hexadecylthymine (TC-16) 17
3-9 製備Octakis(vinylbenzylthyminesiloxy)silsesquioxane (OBT-POSS)之奈米粒子 18
3-9.1合成 1-(4-vinylbenzyl)thymine (VBT) 18
3-9.2 合成Octakis(vinylbenzylthyminesiloxy)silsesquioxane (OBT-POSS) 18
3-10 小分子/A-Py/單壁奈米碳管之三相混摻製備方法 18
3-10.1 TC-16/A-Py之混摻 18
3-10.2 T-C16/A-Py/SWCNT之三相混摻 19
3-10.3 OBT-POSS/A-Py之混摻 19
3-10.4 OBT-POSS/A-Py/SWCNT之三相混摻 19
3-10.5 Thymine/A-Py之混摻 19
3-10.6 Thymine/A-Py/SWCNT之三相混摻 19
3-11 儀器介紹 25
3-11.1 核磁共振光譜儀(Nuclear Magnetic Resonance, NMR)型號: Varian® Unity Inova-500 25
3-11.2 傅利葉轉換紅外線光譜儀(Fourier Transform Infrared Spectrometer, FT-IR)型號﹕Bruker Tensor-27 26
3-11.3 凝膠滲透層析儀(Gel Permeation Chromatography, GPC)型號: Jasco PU-980 27
3-11.4 微差掃瞄卡計(Differential Scanning Calorimeter, DSC)型號：TA Q-20 27
3-11.5 小角度Ｘ光散射儀(Small Angle X-ray Scattering, SAXS)型號：Bruker AXS VANTEC-2000 28
3-11.6 穿透式電子顯微鏡(Transmission Electron Microscope, TEM)型號：JEOL JEM-2100 29
第四章 結果與討論 30
4-1 嵌段共聚物(PS-b-PVBT)與奈米粒子(OBA-POSS)之混摻性質分析研究 30
4-1.1 Poly(styrene-b-4-vinylbenzyl triazolylmethyl methylthymine) (PS-b-PVBT)嵌段共聚物之鑑定分析[77, 78] 31
4-1.2 Octakis(vinylbenzyladeninesiloxy)silsesquioxane (OBA-POSS)奈米粒子之鑑定分析 38
4-1.3 PS-b-PVBT/OBA-POSS混摻之熱分析 43
4-1.4 PS-b-PVBT/OBA-POSS混摻之紅外線光譜分析 46
4-1.5 PS-b-PVBT/OBA-POSS混摻之相轉變分析 48
4-2 嵌段共聚物(PS-b-PVBT)與A-Py之混摻性質分析研究 55
4-2.1 Adeninemethylpyrene (A-Py)之鑑定分析 56
4-2.2 PS-b-PVBT/A-Py混摻之氫鍵作用力分析 61
4-2.3 PS-b-PVBT/A-Py/SWCNT混摻之螺旋結構分析 63
4-3 小分子與A-Py之混摻性質分析研究 69
4-3.1 合成9-hexadecylthymine (TC-16)之鑑定分析 70
4-3.2 Octakis(vinylbenzylthyminesiloxy)silsesquioxane (OBT-POSS)奈米粒子之鑑定分析 74
4-3.3 TC-16/A-Py/SWCNT混摻之螺旋結構分析 79
4-3.4 OBT-POSS/A-Py/SWCNT混摻之螺旋結構分析 79
4-3.5 Thymine/A-Py/SWCNT混摻之螺旋結構分析 80
第五章 結論 85
第六章 參考文獻 86

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