近年來高分子化學領域發展出許多方式來設計新材料，其中超分子化學這門領域，因其具有分子識別、自組裝等性質，並且可用較為低廉的成本來開發出新特性的材料，因此被廣泛使用。本實驗第一部分以咔唑(carbazole)為主體以3,6號位連接的方式聚合成的共軛高分子帶上Thymine官能基與利用自由基聚合和點擊化學所製備出的PS衍生物(PVBA);而在實驗的第二部分同樣以自由基聚合和點擊化學製備出嵌段共聚物PS-b-PVBA和PS-b-PVBT，並將具有互補氫鍵官能基的小分子、高分子進行混摻，探討多點式氫鍵官能基(Thymine和Adenine)對材料性質的影響，藉由氫核磁共振光譜(1H NMR)、傅立葉轉換紅外光光譜儀(FT-IR)來進行結構鑑定，並對其混摻物進行熱分析如；微差掃描熱卡計(DSC)來探討混摻均勻性，若在兩相混摻系統的組成範圍內僅有單一Tg值，表示系統呈現勻相的狀態，也可由原子力顯微鏡(AFM)觀察是否為勻相並結合掃描式電子顯微鏡(SEM)探討試片表面，由穿透式電子顯微鏡(TEM)探討高分子混摻前後的微結構改變，最後再由紫外線與可見光譜儀(UV)和螢光光譜儀(PL)探討混摻後具氫鍵作用力對材料性質的改變並分析。

Supramolecular chemistry is a powerful strategy for molecular design due to simple molecular recognition, self-assembly behaviors, a relatively low cost to develop new features of the material. In this study, we prepared the carbazole as the main structure, and polymerized conjugated polymer at 3,6 position, the other is PS-derivatives. After post-functionalization with CuAAC “click” reaction, nucleobase-contained polymers PTC-T、PVBA、PS-b-PVBA and PS-b-PVBT. The supramolecular complexes through Hetero-complementary hydrogen bonding between Adenine and Thymine were investigated. FT-IR, 1H NMR confirmed the chemical structure of polymer. We demonstrate thermal stability of polymer which has hydrogen bonding by DSC, and explore the homogeneous phase. 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. We also observe the ordered morphology of polymer through transmission electron microscopy(TEM). Finally, we investigated by UV-Vis spectroscopy and fluorescence spectroscopy (PL) which the effects of hydrogen bonding on the properties of materials.

目錄
摘要 i
Abstract ii
目錄 iii
圖目錄 v
示意圖目錄 vii
表目錄 vii
第一章 緒論 8
1.1前言 8
1.2研究動機 9
第二章 文獻回顧 10
2.1超分子化學(Supramolecular chemistry) 10
2.2仿DNA多重氫鍵作用力 10
2.3摻合原理 11
2.4氫鍵(Hydrogen bond) 12
2.5分子識別(Molecular recognition) 13
第三章 實驗方法與步驟 15
3.1實驗藥品 15
3.1.2 溶劑與處理過程 15
3.2合成方法 16
3.2.1製備PTC-T 16
3.2.2製備Poly(4-vinylbenzyl triazolylmethyl methyladenine) 16
3.2.3製備Poly(styrene-b-4-vinylbenzyl triazolylmethyl methyladenine) (PS-b-PVBA) 17
3.2.4製備Poly(styrene-b-4-vinylbenzyl triazolylmethyl methylthymine) (PS-b-PVBT) 18
3.3實驗儀器 21
3.3.1 傅立葉轉換紅外光光譜儀(Fourier Transform Infrared Spectrometer，FT-IR) 型號 : Bruker Tensor-27 21
3.3.2核磁共振分析儀(Nuclear Magnetic Resonance，NMR) 型號：Varian Unityinova-500 22
3.3.3薄膜色層分析(Thin Layer Chromatography，TLC) 22
3.3.4管柱色層分析(Column chromatography) 23
3.3.5微差掃描熱卡儀(Differential Scanning Calorimeter，DSC) 型號：TA Q-20 23
3.3.6熱重分析儀(Thermal Gravimetric Analyzer，TGA) 型號：TA Q-50 23
3.3.7凝膠滲透層析儀(Gel Permeation Chromatography，GPC) 型號：Jasco PU-980 23
3.3.8紫外線與可見光譜儀(UV-Vis Spectrophotometer) 型號：JASCO V-770 24
3.3.9原子力顯微鏡(Atomic Force Microscope，AFM) 型號:NanoMan NS4+D3100 24
3.3.10螢光光譜儀(Fluorescence Spectrofluorometer) 型號:LabGuide X350 25
3.3.11 穿透式電子顯微鏡(Transmission Electron Microscope，TEM) 型號:JEOL-2100 25
3.3.12 小角度X光散射儀(Small Angle X-ray Scattering，SAXS) 型號:NSRRC BL23A 25
3.3.13 動態光散射儀(Dynamic Light Scattering，DLS) 型號: BT-90 25
3.3.14 掃描式電子顯微鏡(Scanning Electron Microscopy, SEM) 型號: JSM6380 26
第四章 結果與討論 26
Part Ⅰ: PTC-T/PVBA研究及討論 26
4.1 PTC-T/PVBA之性質變化探討 26
4.1.1 PVBA合成鑑定分析 26
4.1.2 PTC-T合成鑑定分析 27
4.1.3 PTC-T熱性質分析 34
4.1.4 PTC-T和PVBA分子量分析 35
4.2 PTC-T/ PVBA混摻性質分析 36
4.2.1 PTC-T/PVBA混摻之A-T氫鍵作用力探討 36
4.2.2 PTC-T/PVBA混摻之熱分析與氫鍵作用力的探討 38
4.2.3 PTC-T/PVBA混摻之UV/Vis吸收光譜與氫鍵作用力探討 39
4.2.4 PTC-T/PVBA混摻之PL放光光譜與氫鍵作用力探討 40
4.2.5 PTC-T/PVBA混摻之原子力顯微鏡(AFM)與氫鍵作用力探討 42
Part Ⅱ: PS-b-PVBA/PS-b-PVBT研究及討論 43
4.3 PS-b-PVBA/PS-b-PVBT之性質變化探討 43
4.3.1 PS-b-PVBA合成鑑定分析 43
4.3.2 PS-b-PVBT合成鑑定分析 45
4.4 PS-b-PVBA/ PS-b-PVBT混摻性質分析 47
4.4.1 PS-b-PVBA/PS-b-PVBT混摻之A-T氫鍵作用力探討 47
4.4.2 PS-b-PVBA/PS-b-PVBT混摻之熱分析與氫鍵作用力的探討 48
4.4.3 PS-b-PVBA/PS-b-PVBT混摻之原子力顯微鏡(AFM)與氫鍵作用力探討 49
4.4.4 PS-b-PVBA/PS-b-PVBT混摻之動態光散射儀(DLS)與氫鍵作用力探討 50
4.4.5 PS-b-PVBA/PS-b-PVBT錯合物的結構與形態探討 51
第五章 結論 55
第六章 參考文獻 57

1. Huang, C. W.; Chang, F. C.; Chu, Y. L.; Lai, C. C.; Lin, T. E.; Zhu, C. Y.; Kuo, S. W. J. Mater. Chem. C 2015, 3, 8142.
2. John, G.; Masuda, M.; Okada, Y.; Yase, K.; Shimizu, T.Adv. Mater. 2001, 13, 715.
3. Kim, H.J.;Zin, W. C.; Lee, M. S. J. Am. Chem. Soc. 2004, 126, 7009.
4. Hirschberg, J. H. K.; Brunsveld, L.; Ramzi, A.; Vekemans, J. A. J. M.; Sijbesma, R. P.; Meijer,E. W. Nature 2000, 407, 161.
5. Kuo, S. W.; Cheng, R. S. Polymer 2009, 50,177.
6. Kuo, S. W.; Tsai, H. T. Macromolecules 2009, 42, 4701.
7. Kuo, S. W.; Hsu, C. H. Polym. Inter. 2010, 59, 998.
8. Kuo, S. W.; Tsai, H. T. J. Appl. Polym. Sci. 2012, 123, 3275.
9. Park, P.; Zimmerman, S. C. J. Am. Chem. Soc. 2006, 128, 11582.
10. Coleman, M. M.; Painter, Prog. Polym. Sci. 1995, 20, 1.
11. He, Y.; Zhu, B.; Inoue Y. Prog. Polym. Sci. 2004, 29, 1021.
12. Kuo, S. W. J. Polym. Res. 2008, 15, 459.
13. Goshe, A. J.; Steele, I. M.; Ceccarelli, C.; Rheingold, A. L.; Bosnich, B. Proc. Natl. Acad. Sc. 2002, 99,4823.
14. (a) Anwar, N.; Willms, T.; Grimme, B.; Kuehne, A. J. C. ACS Macro Letters 2013, 2, 766; (b) Pedresen, J. S.; Svaneborg, C. Current opinion in colloid ＆ interface science 2002, 7, 158; (c) Shen, H.; Eisenberg, A. Angew. Chem. Int. Ed. Engl. 2000, 39, 3310; (d) Zhulina, E. B.; Borisov, O. V. Macromolecules 2002, 35, 9191; (e) Kataoka, K.; Harada, A.; Nagasaki, Y. Advanced drug delivery reviews 2001, 47, 113; (f) Eisenberg, A.; Moffitt, M.; Vali, H. Chem. Mater. 1998, 10, 1021.
15. Mather, B. D.;Lizotte, J. R.; Long, T. E. Macromolecules 2004, 37, 9331.
16. Yamauchi, K.; Kanomata, A.; Inoue, T.; Long, T. E. Macromolecules 2004, 37, 3519.
17. Kaur, G.; Chang, S. L. Y.; Bell, T. D. M.; Hearn, T. W.; Saito, K. J. Polym. Sci. Part A Polym. Chem. 2011, 49, 4121.
18. Wang, Y. S.; Cheng, C. C.; Ye, Y. S.; Yen, Y. C.; Chang, F. C. ACS Macro Lett. 2012, 1, 159.
19. Watson, J. P.; Crick, F. H. Nature. 1953, 171, 964.
20. Tanaka,H.; Nakagawa, T.; Kawai, T. Surface Science 1996, 364, 575.
21. Furukawa, M.; Tanaka, H.; Kawai, T. Surface Science 2000, 445, 1.
22. Chen, Q.; Frankel, Daniel J.; Richardson, Neville V. Langmuir 2002, 18, 3219.
23. Mamdouh, W.; Dong, M.; Xu, S.; Rauls, E.; Besenbacher, F. J. Am. Chem. Soc. 2006, 128, 13305.
24. Furukawa, M.; Tanaka, H.; Kawai, T. J. Chem. Phys. 2001, 115, 3419.
25. Iwaura, R.; Yoshida, K.; Masuda, M.; Kameyama, M. O.; Yoshida, M.; Shimizu, T. Angew. Chem. 2003, 115, 9.
26. Mulet, X.; Thomas, K.; Conn, C. E.; Waddington Lynne J. Kennedy; Danielle, F.; Weerawardena, A.; Drummond, Calum J. Langmuir 2010, 26, 18415.
27. Wang, D.; Su, Y.; Jin, C.; Zhu, B.; Pang, Y.; Zhu, L.; Liu, J.; Tu, C.; Yan, D.; Zhu, X. Biomacromolecules 2011, 12, 1370.
28. Lin, I. H.; Cheng, C. C.; Yen, Y. C.; Cheng, F. C. Macromolecules 2010, 43, 1245.
29. He, Y.; Zhu, B.; Inoue Y. Prog. Polym. Sci. 2004, 29, 1021.
30. Jeon, H. K.; Kim, J. K. Macromolecules 2000, 33, 8200.
31. Kuo, S. W.; Chang, F. C. Macromolecules 2001, 34, 5224.
32. Kuo, S. W.; Chang, F. C. Macromolecules 2001, 34, 4089.
33. Kuo, S. W.; Huang, W. J.; Huang, C. F.; Chan, S. C.; Chang, F. C. Macromolecules 2004, 37, 4164.
34. Chen, D.; Jiang, M. Acc. Chem. Res. 2005, 38, 494.
35. Wilson, A. J. Soft Matter 2007, 3, 409.
36. De Jesús, O. L. P.; Ihre, H. R.; Gagne, L.; Fréchet, J. M. J.; Szoka, F. C., Jr. Bioconjugate Chem. 2002, 13, 453.
37. Goshe, A. J.; Steele, I. M.; Ceccarelli, C.; Rheingold, A. L.; Bosnich, B. Proc. Natl. Acad. Sc. 2002, 99, 4823.
38. Kim, S. H.; Park, Y. C.; Jung, G. H.; Cho, C. G. Macromolecular Research 2007, 15, 587.
39. Kyogoku, Y.; Lord, R. C.; Rich, A. J. Am. Chem. Soc. 1967, 89, 496.
40. Mater, B. D.; Baker, M. B.; Beyer, F. L.; Berg, M. A. G.; Green, M. D.; Long, T. E. Macromolecules 2007, 40, 6834.
41. Wu, Y. C.; Kuo, S. W. J. Mater. Chem. 2012, 22, 2982.
42. Cheng, C. C.; Wang, Y. S.; Chang, F. C.; Lee, D. J.; Yang, L. C.; Chen, J. K. Chem. Commun. 2015, 51, 672.
43. Wu, Y. C.; Kuo, S. W. Polym. Chem. 2012, 3, 3100.
44. Chen, S. C.; Kuo, S. W.; Jeng, U. S.; Su, C. J.; Chang, F. C. Macromolecules 2010, 43, 1083.
45. Wu, Y. S.; Wu, Y. C.; Kuo, S. W. Polymers 2014, 6, 1827.