臺灣博碩士論文加值系統

本研究以自由基聚合法和鏈轉移劑合成末端帶有胺基的高分子PDMAEMA-NH2，再利用PDMAEMA-NH2的末端胺基與螢光染料Rhodamine B(RhB)的羧酸基進行醯胺化反應，得到末端帶有RhB螢光基團的PDMAEMA-RhB高分子。另外，也利用原子轉移自由基聚合法(ATRP)聚合出雙端官能化的Br-PDMAEMA-Br，再將末端轉換成胺基而得到高分子NH2-PDMAEMA-NH2。同樣地，NH2-PDMAEMA-NH2與Rhodamine B(RhB)的羧酸基進行反應，得到兩末端帶有RhB螢光基團的RhB-PDMAEMA-RhB高分子。此研究以凝膠滲透儀(GPC)、傅立葉轉換紅外線光譜儀(FTIR)及核磁共振光譜(1H NMR)鑑定高分子的分子量和化學結構；以紫外光/可見光光譜儀(UV-vis)和光激螢光光譜儀(PL)量測高分子的光學性質，並由穿透式電子顯微鏡(TEM)觀察高分子在溶液中的自組裝行為。
PDMAEMA高分子具溫敏性和pH應答特性，而RhB分子具有親水性，當RhB接在PDMAEMA高分子鏈上，會提高其低臨界溶解溫度(LCST)，而改變pH值時也會改變PDMAEMA的親疏水性。將所製備的高分子配製成不同pH值的水溶液，並置於氯仿上方，觀察高分子由水相轉移至有機相的現象。以激發光波長為365 nm的紫外光照射，溶液會有近似白光的放射光，而在穿透式電子顯微鏡(TEM)的觀察下，則發現高分子鏈自組裝形成奈米環狀構造。將螢光高分子配製成不同pH值的水溶液，再加入Fe3+離子，則可以觀察到其螢光強度隨著鐵離子濃度變化的現象，可以應用於鐵離子的偵測。

Amine-terminated poly(2-(dimethylamino)ethyl methacrylate) (PDMAEMA-NH2) is prepared by chain transfer radical polymerization. Then PDMAEMA-NH2 reacts with Rhodamine B to result in PDMAEMA-RhB polymer. The other telechelic amine-terminated poly(2-(dimethylamino)ethyl methacrylate) (NH2-PDMAEMA-NH2) is prepared through atom transfer radical polymerization (ATRP). The precursor Br-PDMAEMA-Br is prepared through ATRP of DMAEMA. The bromine groups of the polymer has been transformed into amine groups to result in NH2-PDMAEMA-NH2 polymer. The Rhodamine B end-capped poly(2-(dimethylamino)ethyl methacrylate) (RhB-PDMAEMA-RhB) telechelic polymer is then obtained with the same manner of reacting NH2-PDMAEMA-NH2 with RhB through amidation reaction. The molecular weight and chemical structures of the prepared polymer are determined by GPC, FTIR, and 1H NMR. The emissive properties of fluorescent polymer are characterized by fluorescence spectroscopy. The polymer self-assembly behavior in solution morphologies is observed by TEM.
PDMAEMA polymer is thermo- and pH-resposnive, and RhB is a hydrophilic molecule. The effect of RhB groups on the lower critical solution temperature (LCST) of the PDMAEMA polymers has been observed and discussed. The phase transferring behavior of the polymers from aqueous to organic phase has been observed. The polymers show self-assembly into toroidal structure in chloroform and near-white light fluorescent emission under an excitation at 365 nm. The change in the fluorescent behavior ahs been attributed to the self-assembled nanostructures of the polymers. Moreover, the fluorescence intensities of the PDMAEMA-RhB and RhB-PDMAEMA-RhB polymers changes with the concentrations of Fe3+ ions, indicating the potential application of the polymers as sensors for iron ions.

摘要 I
Abstract II
誌謝 IV
目錄 V
圖目錄 VII
表目錄 XVI
第一章 緒論 1
1-1 有機發光染料 1
1-2 刺激型高分子 5
1-3 原子轉移自由基聚合法(ATRP) 8
1-4 光致發光原理 11
1-5 研究動機 13
第二章 文獻回顧 14
2-1 pH應答型高分子 14
2-1-1 含有DMAEMA之特性 17
2-1-2 高分子自組裝行為 22
2-2 螢光奈米粒子 35
2-2-1 無機物接枝螢光基團 35
2-2-2 螢光基團在高分子之應用 39
第三章 實驗部分 58
3-1 藥品 58
3-2 儀器設備 60
3-3 名詞對照 61
3-4 螢光高分子合成 62
3-4-1 PDMAEMA-NH2之合成45 62
3-4-2 PDMAEMA-RhB之合成 63
3-5 Br-PDMAEMA-Br之合成 64
3-6 N3-PDMAEMA-N3之合成31 65
3-7 NH2-PDMAEMA-NH2之合成46 66
3-8 RhB-PDMAEMA-RhB之合成 67
第四章 結果與討論 68
4-1 PDMEMA-RhB結構鑑定 68
4-1-1 PDMAEMA-NH2結構鑑定 68
4-1-2 PDMAEMA-RhB結構鑑定與螢光性質分析 71
4-2 RhB-PDMAEMA-RhB 結構鑑定 91
4-2-1 NH2-PDMAEMA-NH2結構鑑定 91
4-2-2 RhB-PDMAEMA-RhB結構鑑定與螢光性質分析 94
第五章 結論 112
第六章 引用文獻 113
圖1-1 Xanthene(A) 和 Rhodamine(B) 染料之分子結構3 2
圖1-2 Rhodamine B在三種平衡狀態下的分子結構4 3
圖1-3 RhB (L形式) 在不同溶劑下的放射光譜：(1) benzene (2) chlorobenzene (3) methylene chloride (4) methanol (5) dimethylsulfoxide 4
圖1-4 刺激應答型聚合物分類6 5
圖1-5 熱感應型高分子之LCST行為示意圖11 6
圖1-6 原子轉移自由基加成反應示意圖20 8
圖1-7 原子轉移自由基聚合反應通用機制示意圖22 9
圖1-8 利用ATRP法聚合出的高分子組成以及功能性分子材料22 10
圖1-9 光致發光能階圖23 11
圖2-1 (A)酸基聚合物在酸性溶液中酸基未被解離 (B)酸基聚合物在中性或鹼性溶液中酸基被離子化產生膨潤24,25 15
圖2-2 (A) 聚胺基聚合物在中性或鹼性溶液中胺基未被離子化 (B) 胺基聚合物在酸性溶液中胺基被質子化產生膨潤24,25 16
圖2-3 P(DMAEMA-stat-PEGMA)在不同pH值水溶液的LCST 27 19
圖2-4 PDMAEMA不同分子量和不同pH值的LCST(□, PDMAEMA108; ▲, (PDMAEMA100)3.1;★, (PDMAEMA170)18) 28 20
圖2-5 PDMAMEA-b-P(PEGMA) DLS與pH值關係圖 29 21
圖2-6 不同構型的刺激型奈米粒子30 22
圖2-7 (a) PDMAEMA-N3 (b) PNIPAM-N3 (c) CS(-g-PDMAEMA)-g-PNIPAM之FTIR圖31 24
圖2-8 CS(-g-PDMAEMA)-g-PNIPAM 之1H NMR圖在D2O (a) pH值4的水溶液和25℃下 (b) pH值4的水溶液和40℃下 (c) pH值6.8的水溶液和25℃下 (d) pH值9.6的水溶液和25℃下 31 25
圖2-9 CS(-g-PDMAEMA)-g-PNIPAM (a) pH值4的水溶液和40℃下 26
圖2-10 雙親水性CS(-g-PDMAEMA)-g-PNIPAM在水溶液中行為示 意圖31 26
圖2-11 PDMAEMA-b-PBLG (DMSO-d6) (上)和PDMAEMA-b-PGA (D2O)(下)的1H NMR 32 27
圖2-12 (a) PDMAEMA85-b-PGA186在pH值 6.2水溶液之TEM圖 (b) 高倍率的TEM圖 (c) 靜電囊泡示意圖 32 28
圖2-13 PDMAEMA85-b-PGA77 在水溶液pH值為 4 (a) 5 (b) 6 (c) 之TEM圖32 29
圖2-14 具溫度和pH應答網狀接枝的PDMAEMA-g-PNIPAM 凝膠製備示意圖33 30
圖2-15 P(DMAEMA-co-ProA) 含有5%莫耳ProA(a) 10%莫耳ProA(b) 15%莫耳ProA(c) SEM圖33 30
圖2-16 PDMAEMA-g-PNIPAM凝膠膨潤/去膨潤可逆循環33 31
圖2-17 不同比例的PNIPAM-g-PDMAEMA在不同溫度不同pH值的水溶液下藥物釋放比率 左-PDMAEMA-g-PNIPAM-5 32
圖2-18 表面改質後的超順磁性Fe3O4粒子34 33
圖2-19 Fe3O4-D2.0-b-PDMAEMA-b-PPEGMA 33
圖2-20 Dox裝載的Fe3O4-D2.0-b-PDMAEMA-b-PPEGMA 34
圖2-21 RhB 和SIA-PGMA-RhB在THF溶液中螢光放射光譜 (a) 激發光 λex=365 nm (b) 激發光 λex=532 nm 35 36
圖2-22 (a) RhB (b) SIA-PGMA-RhB以激發光波長為365 nm和532 nm照射的發光行為 35 36
圖2-23 製備物理吸附(PA-RhB/SNP)和化學吸附(CB-RhB/SNP)之螢光二氧化矽粒子示意圖36 37
圖2-24 CB-RhB/SNP和PA-RhB/SNP在THF中的螢光放射圖譜(a) 激發光 λex=532 nm螢光光譜 (b) 激發光 λex=365 nm螢光光譜 (c) 實際照光發光行為 36 38
圖2-25 poly(NIPAM-co-RD)在酸性溶液中不同溫度下的螢光強度37 40
圖2-26 poly(NIPAM-co-RD)不同溫度下的結構示意圖37 40
圖2-27 poly(NIPAM-co-RD)溶於不同pH值的水溶液中觀察其螢光放射強度 41
圖2-28 製備R1和R2的示意圖38 42
圖2-29 (a) R1 (b) R2 在不同pH值水溶液中的吸收光譜38 42
圖2-30 利用R2染色的HeLa細胞38 43
圖2-31 以RAFT法合成poly(1x-co-DMAEMAy) 39 43
圖2-32 (a) poly(1x-co-DMAEMAy) 不同比例的吸收光譜 (b) poly(1x-co-DMAEMAy)不同比例及不同溫度下的螢光光譜39 44
圖2-33 (a) poly(11.4-co-DMAEMA98.6) 轉換室溫和50℃的螢光強度(b) 螢光激發poly(11.4-co-DMAEMA98.6) 轉換室溫和50℃實照圖(c) UV照射的實照圖 39 45
圖2-34 多色轉換系統之兩性溫敏嵌段共聚物40 P(St-co-NBDAE-co-SPMA)-b-P(NIPAM-co-RhBAM) 示意圖 46
圖2-35 多色轉換共聚物(a) 螢光放射圖譜(激發光470 nm) (b) 以UV燈波長365 nm照射的實物照 (c) 水溶液pH值3-9的螢光放射圖譜40 47
圖2-36 NBD-P(OEGMA-co-DEGMA)-RhB2改變溫度和水溶液pH值之FRET on-off的示意圖41 48
圖2-37 NBD-P(OEGMA-co-DEGMA)-RhB2在水溶液pH值為4溫度25-45℃的螢光圖譜(激發光波長470 nm) 41 48
圖2-38 NBD-P(OEGMA-co-DEGMA)-RhB2固定溫度在45℃改變水溶液pH值2-10的螢光圖譜(激發光波長為470nm) 41 49
圖2-39 製備(PPEGMA-b-PGMA/RhB)流程示意圖42 50
圖2-40 PPEGMA-b-PGMA/RhB的螢光光譜(a) 以激發波長為532 nm激發 (b) 以激發波長365 nm激發 (c) 實際照光圖42 51
圖2-41 PPEGMA-b-PGMA/RhB 靜置一個月後的(a) TEM圖 (b) 螢光光譜42 52
圖2-42 Hela細胞用PPEGMA-b-PGMA/RhB奈米粒子培養用共軛交顯微鏡觀察42 52
圖2-43 製備共聚高分子示意圖43 53
圖2-44 RhB衍生物開還過程示意圖43 53
圖2-45 以(EtOH/H2O 1:1,v/v)在不同pH值的水溶液下加入RhB衍生物和不同金屬離子觀察螢光減少效率43 54
圖2-46 RhB衍生物在pH值為7的溶液下加入Hg(II) (上左)螢光放射圖譜(下左)吸收光譜(下右)實物照43 55
圖2-47 (a) PNIPAAM-RhB和RhB-PNIPAAM-RhB結構式 (b) PNIPAAM-RhB和RhB-PNIPAAM-RhB 溶於25℃移動到40℃的CHCl3中 (c) 在CHCl3自組裝的TEM圖 (d) 在CHCl3自組裝的AFM圖44 57
圖3-1 PDMAEMA-NH2製備 62
圖3-2 PDMAEMA-RhB製備 63
圖3-3 Br-PDMAEMA-Br製備 64
圖3-4 N3-PDMAEMA-N3 製備 65
圖3-5 NH2-PDMAEMA-NH2製備 66
圖3-6 RhB-PDMAEMA-RhB 製備 67
圖4-1 PDMAEMA-NH2之FT-IR光譜圖 69
圖4-2 PDMAEMA-NH2之1H NMR圖譜，溶劑為d-chloroform 70
圖4-3 PDMAEMA-NH2之GPC圖 70
圖4-4 PDMAEMA-NH2、RhB、PDMAEMA-RhB 之FT-IR圖 71
圖4-5 PDMAEMA-RhB之1H NMR圖，溶劑為D2O 72
圖4-6 PDMAEMA-NH2 和 PDMAEMA-RhB濃度為1 mg/ml在不同pH值的水溶液及不同溫度下的穿透度圖，由圖中穿透度變化可決定個別高分子樣品的LCST 74
圖4-7 RhB(濃度0.01 mg/ml)、PDMAEMA和PDMAEMA-RhB 在pH 4、pH 7、pH 10 的水溶液環境下濃度為1 mg/ml之UV-vis 吸收光譜圖 75
圖4-8 RhB、PDMAEMA和PDMAEMA-RhB在pH 4、pH 7、pH 10的水溶液下以 (a) 以波長365 nm的光激發 (b) 以波長532 nm的光激發所得到的放射光譜圖(除了RhB濃度為0.01 mg/ml外，其他濃度均為1 mg/ml) 77
圖4-9 (a) PDMAEMA (b) RhB (c) PDMAEMA-RhB在pH值4(d) pH值7 (e) pH值10的水溶液以不同波長進行激發的實照圖(左：無照光、中：以激發光波長為365 nm照射、右：以激發光波長為532 nm照射) (除了RhB濃度為0.01 mg/ml外，其他均為1 mg/ml) 78
圖4-10 PDMAEMA-RhB溶於pH值10水溶液中(濃度1 mg/ml) / CHCl3加熱前後的螢光放射光譜(a) 以激發光波長為365 nm激發 (b) 以激發光波長為532 nm激發 79
圖4-11 PDMAEMA-RhB溶於pH值10水溶液中(濃度1 mg/ml) / CHCl3加熱前後實照圖 (依序為無照光、以激發光波長為365 nm照射、以激發光波長為532 nm照射) 79
圖4-12 將PDMAEMA-RhB溶於pH值為4和10的水溶液為上層液(濃度1 mg/ml)/下層液為chloroform 80
圖4-13 上層液為PDMAEMA-RhB溶於pH值為10的水溶液(濃度1 mg/ml)/下層液為CHCl3觀察PDMAEMA-RhB 螢光光譜的變化 (a) 上層液激發光波長為365 nm激發 (b) 上層液激發光波長為532 nm激發 (c) 下層液激發光波長為365 nm激發 (d) 下層液激發光波長為365 nm激發 82
圖4-14 PDMAEMA-RhB 溶於pH值10水溶液(濃度1 mg/ml) /CHCl3 實照圖(a) 靜置0天 (b) 22天(左：無照光、中：以激發光波長為365 nm激發、右：以激發光波長為532 nm激發) 83
圖4-15 觀察PDMAEMA-RhB高分子從水相進入有機相的自組裝TEM圖 84
圖4-16 PDMAEMA-RhB溶於pH值為4的水溶液中(濃度為1 mg/ml)再加入Fe3+離子後觀察溶液螢光變化 (a) 激發光波長為365 nm (i) 激發光波長為365 nm的440 nm放射螢光強度與溶液中Fe3+離子濃度作圖 (ii) 激發光波長為365 nm的588 nm放射螢光強度與溶液中Fe3+離子濃度作圖 (b) 激發光波長為532 nm (c) 紫外光/可見光吸收光譜圖/加入Fe3+離子前後實照圖放射螢光強度與溶液中Fe3+離子濃度作圖 (iii) 激發光波長為532 nm的588 nm放射螢光強度與溶液中Fe3+離子濃度作圖 86
圖4-17 PDMAEMA-RhB溶於pH值為7的水溶液中(濃度為1 mg/ml)再加入Fe3+觀察溶液的螢光變化 (a) 激發光波長為365 nm (b) 激發光波長為532 nm (c) 紫外光/可見光吸收光譜圖/加入Fe3+離子前後實照圖 88
圖4-18 PDMAEMA-RhB溶於pH值為10的水溶液中(濃度為1 mg/ml)再加入Fe3+離子觀察溶液的螢光變化 (a) 激發光波長為365 nm激發 (i) 激發光波長為365 nm的440 nm放射螢光強度與溶液中Fe3+離子濃度作圖 (ii) 激發光3波長為65 nm的575 nm放射螢光強度與溶液中Fe3+離子濃度作圖 (b) 激發光波長為532 nm激發 (c) 紫外光/可見光吸收光譜圖/加入Fe3+離子前後實照圖 (d) 激發光532 nm放大圖 90
圖4-19 Br-PDMAEMA-Br、N3-PDMAEMA-N3、NH2-PDMAEMA-NH2 之FT-IR光譜圖 92
圖4-20 Br-PDMAEMA-Br之1H NMR圖，溶劑為D2O 93
圖4-21 Br-PDMAEMA-Br之GPC圖 93
圖4-22 NH2-PDMAEMA-NH2、RhB、RhB-PDMAEMA-RhB 之FT-IR光圖譜 94
圖4-23 RhB-PDMAEMA-RhB之1H NMR圖，溶劑為D2O 95
圖4-24 Br-PDMAEMA-Br 和 RhB-PDMAEMA-RhB濃度為1 mg/ml在不同pH值的水溶液及不同溫度下的穿透度圖，由圖中穿透度變化可決定個別高分子樣品的LCST 96
圖4-25 RhB(濃度0.01 mg/ml)、Br-PDMAEMA-Br(濃度為1 mg/ml)和RhB-PDMAEMA-RhB (濃度為1 mg/ml)在pH值4、pH值7、pH值10水溶液的UV-vis 吸收光譜圖 97
圖4-26 RhB、PDMAEMA和RhB-PDMAEMA-RhB在pH值4、pH值7、pH值10水溶液下以 (a) 以激發光波長為365 nm激發 (b) 以激發光波長為532 nm激發的放射光譜 99
圖4-27 RhB-PDMAEMA-RhB(濃度為1 mg/ml)在pH值4、pH值7、pH 10值的水溶液中以不同波長照射的實照圖(左：無照光、中：以激發光波長為365 nm照射、右：以激發光波長為532 nm照射) 100
圖4-28 RhB-PDMAEMA-RhB 溶於pH值10的水溶液中(濃度為1 mg/ml) / CHCl3加熱前後的螢光放射光譜 (a) 以激發光波長為365 nm激發 (b) 以激發光波長為532 nm激發 101
圖4-29 RhB-PDMAEMA-RhB 溶於pH值10的水溶液中(濃度為1 mg/ml)/ CHCl3加熱前後實照圖 (左：無照光、中：以激發光波長為365 nm照射、右：以激發光波長為532 nm照射) 101
圖4-30 上層液為RhB-PDMAEMA-RhB溶於pH值10溶液(濃度為1 mg/ml)/下層液為CHCl3觀察RhB-PDMAEMA-RhB 螢光光譜的變化 (a) 上層液以激發光波長為365nm激發 (b) 上層液以激發光波長為532 nm激發 (c) 下層液以激發光波長為365 nm激發 (d) 下層液以激發光波長為532 nm激發 103
圖4-31 RhB-PDMAEMA-RhB 溶於pH值10的水溶液中(濃度為1 mg/ml)/CHCl3實照圖靜置0天、23天、84天 (左：無照光、中：以激發光波長為365 nm照射、右：以激發光波長為532 nm照射) 104
圖4-32 觀察從水相進入有機相的RhB-PDMAEMA-RhB高分子自組裝 105
圖4-33 將RhB-PDMAEMA-RhB溶於pH值為4的水溶液中(濃度為1 mg/ml)再加入Fe3+觀察溶液螢光變化 (a) 激發光波長為365 nm激發 (i) 激發光波長為365 nm激發的440 nm放射螢光強度與溶液中Fe3+離子濃度作圖 (ii) 激發光波長為365 nm的588 nm放射螢光強度與溶液中Fe3+離子濃度作圖 (b) 激發光波長為532 nm激發 (c) 紫外光/可見光吸收光譜圖/加入Fe3+離子前後實照圖放射螢光強度與溶液中Fe3+離子濃度作圖 (iii) 激發光波長為532 nm的588 nm放射螢光強度與溶液中Fe3+離子濃度作圖 107
圖4-34 將RhB-PDMAEMA-RhB溶於pH值為7的水溶液中(濃度為1 mg/ml)再加入Fe3+觀察溶液螢光變化(a) 激發光波長為365 nm激發 (b) 激發光波長為532 nm激發 (c) 紫外光/可見光吸收光譜圖/加入Fe3+離子前後實照圖 109
圖4-35 將RhB-PDMAEMA-RhB溶於pH值為10的水溶液中(濃度為1 mg/ml)再加入Fe3+觀察溶液螢光變化(a) 激發光波長為365 nm激發 (i) 激發光波長為365 nm激發的470 nm放射螢光強度與溶液中Fe3+離子濃度作圖 (ii) 激發光波長為365 nm激發的575 nm放射螢光強度與溶液中Fe3+離子濃度作圖 (b) 激發光波長為532 nm激發 (c) 紫外光/可見光吸收光譜圖/加入Fe3+離子前後實照圖 (d) 激發光波長為532 nm放大圖 111
 
表目錄
表2-1 利用ATRP法用不同類型的起始劑和配位劑聚合DMAEMA26 17
表2-2 不同比例的P(DMAEMA-stat-PEGMA)在不同pH值水溶液下的LCST 27 18
表2-3 PDMAEMA在pH= 7、8、9、10 水溶液中的LCST(1.0 g/L；0.1 g/L)28 19
表2-4 不同PDMAEMA-b-PGA分子量以及等電點比較 32 27

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