臺灣博碩士論文加值系統

本篇論文主要分為三個部份，第一部分為了瞭解初期核內體如何形成後期核內體，利用萘甲酸與環氧樹酯進行開環反應，可得兩種異構物分子，接著加入過硫酸銨誘發化合物分子進行3,2-單醯甘油酯基的轉換，可得四種異構物分子且大部分開外產物轉換為開內產物，以利我們了解細胞間內吞作用。利用2D-NMR及FT-IR光譜鑑定結構，螢光光譜儀觀察其放光性質。其中值得注意的是，在一定的濃度下，螢光的光致發光光譜具有激發波長相依放光(EWDP)的性質。第二部分為，在偶然的情況下發現NASR3在DMSO-H2O混和溶劑下具有乳液的性質，且於不同比例下，可以得到不同尺寸的乳液。第三部分則是尋找此有機發光奈米粒子實際應用，發現NASR3具有感測特定金屬之能力。

This study is divided into three parts, The first part is the reactions of bisphenol A diglycidyl ether in different reaction conditions with naphthoic acid and epoxy resin , and add ammonium persulfate to induce compound molecules. Conversion of 3,2-mono-glycolyl ester groups, two isomer molecules are available to facilitate understanding of intercellular endocytosis. We identified structures by 2D-NMR and FT-IR spectroscopy. We observed very different light-emitting properties in the fluorescence spectrometer. It is worth noting that at a certain concentration, the photoluminescence spectrum of the fluorescence has the property of excitation wavelength-dependent emission(EWDP) , and the second part is that we occasionally It was found that NASR3 has the properties of emulsion in DMSO-H2O mixed solvent. We can get emulsions of different sizes at different ratios. The third part is the practical application of organic light-emitting nano particles that we hope to find ourselves in our laboratory. NASR3 was found to have applications for sensing specific metals.

謝詞 I
摘要 II
Abstract III
目錄 IV
圖目錄 VII
表目錄 XI
符號說明 XII
第一章 緒論 1
1-1超分子化學1,2 1
1-2 分子自組裝 2
1-2.1 分子自組裝行為7,8,9,10 2
1-2.2 溶劑對自組裝影響 3
1-3 激發波長相依放光 (Excitation-Wavelength Dependent Photoluminescence, EWDP) 3
1-3.1 尺寸效應 3
1-3.2 濃度效應 5
1-3.3 溶劑效應 6
1-3.4 EWDP之應用 7
1-4 螢光發光原理16 7
1-5 聚集誘導放光17 10
1-6 環氧樹脂簡介18,19,20 11
1-7 微乳液 12
1-7.1 微乳液的結構 13
1-8 界面活性劑26 13
1-8.1 HLB值 Hydrophile -Lipophilic Balance 14
1-8.2 乳液三相圖 15
1-9 DMSO-H2O 混和溶劑29,30 15
1-10 金屬與生物分子感測器31,32 16
1-11 研究動機 18
第二章 實驗方法與步驟 21
2-1 合成文獻 21
2-2 實驗流程 27
2-2.1 NASR3之合成 27
2-2.2 NASR3-s之合成 28
第三章 結果與討論 29
3-1 化合物之結構鑑定與NMR光譜鑑定 29
3-1.1.1 化合物NASR3之結構鑑定 29
3-1.1.2 化合物NASR3之元素分析鑑定 35
3-1.2 化合物NASR3-s之結構鑑定 37
3-2 化合物NASR3系列之FT-IR光譜鑑定 44
3-3 化合物NASR3系列之光學性質 45
3-3.1 化合物NASR3系列的螢光光譜鑑定 45
3-3.2 化合物 NASR3-s系列的螢光光譜鑑定 46
3-3.6 化合物NASR3系列之紫外光/可見光光譜鑑定(UV-Vis) 48
3-4 化合物NASR3之形貌分析 48
3-4.1動態光散射儀量測(Dynamic light scattering, DLS) 48
3-4.2 掃描式電子顯微鏡（Scanning Electro Microscope, SEM） 49
3-5 非傳統乳化劑形成乳液性質 51
3-5.1 不同溶劑是否能形成乳液 55
3-5.2 控制NASR3濃度改變DMSO-H2O比例 57
3-5.3 控制DMSO-H2O莫爾比為1:1改變NASR3濃度 59
3-5.4 控制DMSO-H2O莫爾比1:2改變NASR3濃度 60
3-5.5 控制DMSO-H2O莫爾比1:3改變NASR3濃度 61
3-5.6 掃描式電子顯微鏡（Scanning Electro Microscope, SEM） 61
3-5.7多光子共軛焦顯微鏡(MCMS) 63
3-6 金屬離子偵測器 64
3-6.1 NASR3在DMSO-H2O莫爾比1:1下偵測金屬離子 64
第五章 實驗藥品與儀器 67
5-1 藥品 67
5-2 溶劑 68
5-3 儀器 68
5-3.1核磁共振儀 (Nuclear Magnetic Resonance Spectroscopy, NMR) 68
5-3.2 元素分析儀（Elemental analyzer, EA） 68
5-3.3 螢光光譜儀 (Fluorescence Spectrophotometer，FL) 69
5-3.4 傅立葉轉換紅外光光譜儀(Fourier-transform infrared spectroscopy，FT-IR) 69
5-3.5 紫外光/可見光光譜儀(UV-vis) 69
5-3.6 動態光散射儀(Dynamic light scattering, DLS) 69
5-3.7 掃描式電子顯微鏡(Scanning Electron Microscope, SEM) 70
5-3.8 多光子共軛焦顯微鏡(Multiphoton and Confocal Microscope System) 70
第六章 參考文獻 72

圖目錄
圖 1- 1巨環化學之化合物(a)crown ether (Pedersen) (b)cryptand (Lehn) (c)spherands (Cram)............................................................................... 1
圖 1- 2 分子自組裝的一級、二級和三級結構 .......................................... 2
圖 1- 3 多孔矽薄膜不同放光顏色 .............................................................. 4
圖 1- 4 多孔矽奈米薄膜之激發波長相依光致發光之螢光光譜圖 .......... 4
圖 1- 5 Pyromellitic diimide (PMDI)之結構 ............................................... 5
圖 1- 6 PMDI奈米線之(a)SEM圖和(b)TEM圖 ........................................ 5
圖 1- 7 Pyromellitic diimide (PMDI)網狀奈米線之光致發光圖 ................ 5
圖 1- 8 B-CDs和Y-CDs之不同激發波長相依光致發光現象 ................. 6
圖 1- 9 活性球狀物質之界面經由矽修飾物質之放光光譜圖 .................. 6
圖 1- 10 電子能階狀態的躍遷情形 ............................................................ 8
圖 1- 11 分子激發能階示意圖 .................................................................... 9
圖 1- 12 n-EDFONP之放光光譜計算和氫鍵示意圖 ............................... 11
圖 1- 13 環氧樹脂之化學結構以及構造機能 .......................................... 11
圖 1- 14 微乳液微胞型態(左圖)O/W微乳液(右圖)W/O微乳液 ........... 13
圖 1- 15 界面活性劑組成結構 .................................................................. 14
圖 1- 16水、油和表面活性劑的比例，各種微胞結構的三相圖 ........... 15
圖 1- 17 DMSO電荷分離 .......................................................................... 15
圖 1- 18 DMSO與H2O混和後可能形成結構 ......................................... 16
圖 1- 19 DMSO與H2O作用力示意圖 .................................................... 16
圖 1- 20 化學感測器之作用機制 .............................................................. 17
圖 1- 21 化學感測分子應用於Fe3+之辨識作用圖 .................................. 18
圖 1- 22 化學感測分子應用於細胞間Fe3+之辨識應用 .......................... 18
圖 1- 23 傳統有機發光奈米粒子的延伸π共軛系統圖 .......................... 19
圖 1- 24 細胞內吞作用簡易圖 .................................................................. 20
圖 2- 1 Shechter等人提出合成路徑 .......................................................... 22
圖 2- 2 環氧化物與羧酸等當量的非催化反應 ........................................ 22
圖 2- 3 鹼催化合成路徑 ............................................................................ 23
圖 2- 4 不同鹼催化劑催化速率 ................................................................ 23
圖 2- 5 羧酸與胺鹽和氫氧化鉀可逆平衡 ................................................ 24
圖 2- 6苯甲酸與環氧化開環反應機制 ..................................................... 25
圖 2- 7 BisphenolA-bis-((2-hydroxypropyl)-3-naphthoic)之開環反應機制.............................................................................................................. 26
圖 2- 8 NASR3之合成流程 ....................................................................... 27
圖 2- 9 NASR3-s之合成流程 .................................................................... 28
圖 3- 1 NASR3之異構物之主產物和副產物 ........................................... 29
圖 3- 2 NASR3之1H-NMR與13C-NMR之光譜圖(CDCl3) ................... 30
圖 3- 3 NASR3之13C-DEPT之光譜圖(CDCl3) ....................................... 31
圖 3- 4 NASR3之1H- 13C-NMR HSQC之光譜圖(CDCl3) ...................... 31
圖 3- 5 NASR3之1H- 13C-NMR HMBC之光譜圖(CDCl3) ..................... 32
圖 3- 6 NASR3之1H- 13C-NMR HSQC之A區光譜圖(CDCl3) ............. 33
圖 3- 7 NASR3之1H- 13C-NMR HMBC之B、C區光譜圖(CDCl3) ..... 34
圖 3- 8 為NASR3之元素分析數據圖 ..................................................... 36
圖 3- 9 NASR3-s之主產物與副產物比例圖 ............................................ 37
圖 3- 10 NASR3-s之1H、13C與DEPT光譜圖(CDCl3) ......................... 38
圖 3- 11 NASR3-s之1H-13C-NMR HSQC光譜(CDCl3) .......................... 39
圖 3- 12 NASR3-s之1H-13C-NMR HMBC光譜(CDCl3) ......................... 39
圖 3- 13 NASR3-s之1H-13C-NMR HSQC A區域放大圖(CDCl3) .......... 40
圖 3- 14 NASR3-s之1H-13C-NMR HMBC光譜B、C區域放大圖-1(CDCl3) ............................................................................................. 41
圖 3- 15 NASR3-s之1H-13C-NMR HMBC光譜B、C區域放大圖-2(CDCl3) ............................................................................................. 42
圖 3- 16 NASR3-s之1H-13C-NMR HMBC光譜B、C區域放大圖-3(CDCl3) ............................................................................................. 43
圖 3- 17 NASR3之FT-IR光譜圖 ............................................................. 44
圖 3- 18 NASR3-s之FT-IR光譜圖 .......................................................... 45
圖 3- 19 NASR3在0.1Mm、1Mm、10Mm、50Mm下的激發光譜圖 45
圖 3- 20 NASR3在0.1Mm、1Mm、10Mm、50Mm下的光致發光譜圖.............................................................................................................. 46
圖 3- 21 NASR3-s在0.1Mm、1Mm、10Mm、50Mm下的激發光譜圖.............................................................................................................. 47
圖 3- 22 NASR3-s在0.1Mm、1Mm、10Mm、50Mm下的光致發光譜圖.............................................................................................................. 47
圖 3- 23為SR3、NA、NASR3之UV光譜圖 ........................................ 48
圖 3- 24 10mM NASR3在SEM下所觀測之粒徑大小 ........................... 50
圖 3- 25 NASR3預測之構型圖 ................................................................. 51
圖 3- 26 NASR3與DMSO相互排列之預測圖 ....................................... 51
圖 3- 27 NASR3與DMSO相互排列之示意圖 ....................................... 52
圖 3- 28 NASR3、DMSO與H2O形成微胞之示意圖 ............................ 52
圖 3- 29 NASR3、DMSO與H2O形成多層囊泡之示意圖 .................... 52
圖 3- 30 DMSO訊號位移之1H-NMR光譜圖(DMSO-d6) ...................... 53
圖 3- 31 加入三滴DMSO樣品之NMR-DOSY光譜圖(DMSO-d6) ..... 54
圖 3- 32 形成微乳液態之NMR-DOSY光譜圖(DMSO-d6) ................... 55
圖 3- 33為不同混和溶液剛配好時 ........................................................... 56
圖 3- 34為不同混和溶液經一夜放置後 ................................................... 56
圖 3- 35 固定NASR3濃度但改變混和溶劑比例 ................................... 57
圖 3- 36 固定NASR3濃度但改變混和溶劑比例之三相圖 ................... 59
圖 3- 37 固定溶劑DMSO-H2O改變濃度NASR3之外觀 ..................... 59
圖 3- 38 固定溶劑DMSO-H2O改變濃度NASR3之外觀 ..................... 60
圖 3- 39 固定溶劑DMSO-H2O改變濃度NASR3之外觀 ..................... 61
圖 3- 40 固定DMSO-H2O莫爾比1:1改變NASR3濃度(a)10mM(b)30mM(c)40mM(d)42mM(e)45mM(f)50mM之SEM圖 62
圖 3- 41 NASR3乳液狀態之MCMS圖 ................................................... 63
圖 3- 42 NASR3金屬偵測螢光光譜圖 ..................................................... 65
圖 3- 43 各種金屬陽離子之消光率 .......................................................... 65
圖 3- 44 NASR3在DMSO-H2O莫爾比1:1下加入金屬離子外觀 ........ 65
圖 3- 45 NASR3在DMSO-H2O莫爾比1:1下加入金屬離子照射紫光雷射筆...................................................................................................... 65

表目錄
表 1- 1 乳液與微乳液的差異 .................................................................... 13
表 2- 1 各種溶劑對於反應的影響 .......................................................... 24
表 3- 1 標準品Acetanilide 元素分析 ...................................................... 35
表 3- 2 標準品NASR3 元素分析 ............................................................ 35
表 3- 3 固定NASR3濃度改變DMSO-H2O比例之平均粒徑 ............... 58
表 3- 4 固定NASR3濃度改變DMSO-H2O比例之有效粒徑 ............... 58
表 3- 5 固定NASR3濃度改變DMSO-H2O比例之各組成分 ............... 58
表 3- 6 固定DMSO-H2O比例改變NASR3濃度之有效粒徑 ............... 60

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