陸天堯臺灣大學：高分子科學與工程學研究所楊慧君Yang, Hui-ChunHui-ChunYang2007-11-292018-06-292007-11-292018-06-292006http://ntur.lib.ntu.edu.tw//handle/246246/62905利用Grubbs-I催化的開環歧化反應，含二茂鐵之雙二環〔2.2.1〕庚烯骨架的衍生物可以合成一系列的雙股螺旋高分子。藉由單體的精心設計，雙股高分子具有一定的剛性，架橋於雙股之連接基團中的二茂鐵又使雙股高分子有一些柔軟性。另外，利用鹼基促進高分子的水解可得到相對高產率的二條單股高分子和連接基團，二羰酸二茂鐵。STM（Scanning Tunneling Microscopy）觀察雙股高分子得到螺旋狀（helical structure），超螺旋（supercoil）和梯狀（ladder）三種結構和理論計算的結果相符。雙股高分子和DNA的結構相似，它們有相似的寬度，每一段有相似的重覆單元的數量，雙股高分子的五環垂直於連接基團而且相鄰二個單體間也具有相似的距離，這些結果暗示著我們所合成的高分子是類似DNA 結構的雙股螺旋高分子。 另一方面，我們合成出一系列具手性的雙股高分子，由吸收光譜的藍位移證明高分子中存在發色團間的相互作用，由圓二色性光譜 (circular dichroism) 測量，各別單體和高分子的鏡向異構物的圓二色性性質，發現手性中心 (chiral center) 的取代基是主要影響手性單體和手性雙股高分子的圓二性光譜性質的主要因素，在一些例子當中，雙股高分子的圓二色性光譜強度大於手性單體，這些結果暗示著手性雙股高分子的螺旋性增加。The synthesis of a series of helical double strand polymers containing ferrocene moiety by ring opening metathesis polymerization (ROMP) of a bisnorbornene derivative is described.　Ferrocene moiety was incorporated as part of the linker since it has certain rigidity but is somewhat flexible. Base-promoted hydrolysis of this polymer affords the corresponding single stranded polymer and the linker, ferrocene-1,1’-dicarboxylic acid, in excellent yield. Three forms (helical, supercoil and ladder) of the polymer have been observed by STM and simulated by molecular mechanical and dynamical calculations. The polymer thus obtained resembles structurally to DNA by having similar width, number of monomeric units per pitch, five-membered rings in the polymeric frame, perpendicular linkers to the backbones, and similar spacing between neighboring monomeric units. These results suggest that the polymers may adopt our proposed DNA-like double stranded structures. On the other hand, A series of chiral double stranded polymers were designed and synthesized. Between chromophores interaction may occur as evidenced by the blue shift of the absortion maximum. A pair of enantiomeric double stranded monomers and polymers was subjected to CD measurements. Substitute of chiral center may appear to be the pivotal factor to dictate the CD properties of chiral double stranded monomers and polymers. The CD intensity of chiral double stranded polymers is enhancement than monomers. These results suggest that the helixty of chiral double stranded polymers may increased.謝誌…………………………………………………………………………………….I 中文摘要……………………………………………………………………………....II 英文摘要……………………………………………………………………………...III 章節目錄…………………………………………………………...............................IV 表目錄………………………………………………………………………………...VI 圖目錄………………………………………………………………………………..VII縮寫對照表…………………………………………………………………………....X 化合物縮寫對照表.......................................................................................................XI 發表在Angew. Chem. Int. Ed. 2006, 45, 726.的插畫……………………………….XII 第一章 緒論………………………………………………………………………....1 1-1前言……………………………………………………………………………..1 1-2形成雙股高分子的策略與方法………………………………………………10 1-3雙股高分子的初探…………………………………………………………....20 第二章 結果與討論………………………………………………………………..26 2-1二茂鐵連接基團之雙股螺旋高分子…………………………………………26 2-2二茂鐵酯類連接基團之雙股螺旋高分子的合成策略………………………26 2-2-1具雙二環[2.2.1]庚烯骨架二茂鐵（Ferrocene）雙酯類衍生物之雙股螺旋高分子Fc1P的合成與鑑定………………………………………..29 2-2-2具雙二環[2.2.1]庚烯骨架二茂鐵（Ferrocene）雙酯類衍生物之雙股螺旋高分子Fc1P的物理性質的探討…………………………………..47 2-3二茂鐵亞甲基酯類連接基團之雙股螺旋高分子……………………………49 2-3-1具雙二環[2.2.1]庚烯骨架二茂鐵（Ferrocene）亞甲基酯類衍生物之雙股螺旋高分子Fc2P的合成與鑑定…………………………………..50 2-3-2具雙二環[2.2.1]庚烯骨架二茂鐵（Ferrocene）亞甲基酯類衍生物之雙股螺旋高分子Fc2P的物理性質的探討……………………………..59 2-4具手性（Chiral）二茂鐵亞甲基酯類聯結基團之雙股螺旋高分子………..60 2-4-1具雙二環[2.2.1]庚烯骨架二茂鐵（Ferrocene）亞甲基酯類衍生物手性雙股螺旋高分子的合成........................................................................62 2-4-2具雙二環[2.2.1]庚烯骨架二茂鐵（Ferrocene）亞甲基酯類衍生物手性雙股螺旋高分子的鑑定……………………………………………....68 第三章 結論………………………………………………………………………..86 第四章 實驗部分…………………………………………………………………..88 4-1測試儀器………………………………………………………………………88 4-2實驗步驟………………………………………………………………………90 第五章　參考文獻…………………………………………………………………130 附錄A………………………………………………………………………………135 化合物之1H NMR 光譜 附錄B………………………………………………………………………………171 部分化合物之VT-1H NMR 光譜5981401 bytesapplication/pdfen-US螺旋結構雙股高分子掃描式穿隧電子顯微鏡Helical structuerDouble stranded polymerSTMthesishttp://ntur.lib.ntu.edu.tw/bitstream/246246/62905/1/ntu-95-D92549007-1.pdf