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研究生: 劉芳媛
Liou, Fang-Yuan
論文名稱: 含Rhodamine衍生物之螢光共聚高分子合成及其金屬離子感測性質分析
Synthesis of Rhodamine-based Fluorescent Copolymers for Application in Metal-ion Sensing
指導教授: 吳文中
Wu, Wen-Chung
學位類別: 碩士
Master
系所名稱: 工學院 - 化學工程學系
Department of Chemical Engineering
論文出版年: 2020
畢業學年度: 108
語文別: 中文
論文頁數: 132
中文關鍵詞: 螢光感測器汞離子聚集誘導發光跨鍵能量轉移
外文關鍵詞: fluorescent sensor, mercury ion, aggregation-induced emission, through-bond energy transfer
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  • 本研究合成出二rhodamine衍生物4-(3-(3',6'-bis(diethylamino)- 3-oxospiro[isoindoline-1,9'-xanthen]-2-yl)thioureido)phenyl methacrylate (RB)與4-(3-(3',6'-bis(diethylamino)-3-oxo-5-(4-(1,2,2-triphenylvinyl)phenyl)spiro[isoindoline-1,9'-xanthen]-2-yl)thioureido)phenyl methacrylate (TR)分別作為turn-on與TBET汞離子螢光感測器,並以自由基聚合法(free radical polymerization)與親水性單體N-isopropylacrylamide (NIPAAm)及N-hydroxymethylacrylamide (NMA)合成出不同螢光單體比例之共聚高分子poly(NIPAAm-co-NMA-co-RB)與poly(NIPAAm-co-NMA-co-TR),改善螢光單體的親水性,使其更容易與水溶液中的離子作用。
    本研究所合成之感測器對於Hg2+具有感測性,能夠誘導硫代胺基脲(thiosemicarbazide)形成噁二唑(oxadiazole),為不可逆的脫硫環化反應,使螺內醯胺(spirolactam)開環,促使rhodamine螢光強度增加,溶液由無色變為粉紅色,並且具有快速響應性。TR為結合兩螢光基團之分子,以tetraphenylethene作為能量供體,rhodamine作為能量受體,其中tetraphenylethene結構具有聚集誘導發光(aggregation-induced emission, AIE)特性,在弱親和力溶劑中聚集,使分子內旋轉受到限制而放出螢光,添加Hg2+能夠藉由跨鍵能量轉移(trough-bond energy transfer, TBET)的產生觀察到螢光波長的消長與位移,並且具有較大的stokes shift。

    In this study, random copolymers poly(NIPAAm-co-NMA-co-RB) and poly(NIPAAm-co-NMA-co-TR) were synthesized by free radical polymerization. Rhodamine derivatives RB and TR were used as the turn-on and TBET fluorescent sensor for the recognition of mercury ions, respectively. NIPAAm and NMA segments were designed to increase hydrophilicity to facilitate the sensing ability of mercury ions in aqueous solution. The system utilized the irreversible Hg2+-promoted reaction of thiosemicarbazides to form 1,3,4-oxadiazoles, which possess the advantage of quick response time. The interaction with mercury ions could trigger the transformation process from ring-closed spirolactam form to ring-opened amide for rhodamine moieties, which can enhance the fluorescence intensity of rhodamine moieties and the color of the solution was changed from colorless to pink. TR is constructed by coupling a tetraphenylethene donor with a rhodamine acceptor. The tetraphenylethene group of TR with aggregation-induced emission phenomenon showed strong emission in a poor solvent is attributed to the restriction of intramolecular rotation. Upon the addition of mercury ions in the poor solvent, the change of the fluorescent wavelength and intensity could be observed due to through-bond energy transfer, and possessed a large pseudo-stokes shift.

    摘要 i Abstract ii 目錄 xvi 圖目錄 xx 表目錄 xxix 第一章、 緒論 1 1.1 前言 1 1.2 研究動機與目的 2 第二章、 文獻回顧 3 2.1 重金屬對環境與人體的危害 3 2.2.2 螢光原理 5 2.3.1 光致發光 (photoluminescence) 5 2.2.2 激發態分子之去激發機制 6 2.2.3 影響螢光之變數 9 2.2.4 螢光淬滅機制 13 2.3 感測器 15 2.3.1 螢光感測器 16 2.4 聚集誘導發光機制(Aggregation-Induced Emission, AIE) 30 2.5 rhodamine-based感測器在檢測金屬離子上之應用 35 2.6 環境應答型高分子 39 2.7 靜電紡絲技術 43 2.7.1 靜電紡絲簡介 43 2.7.2 靜電紡絲原理與裝置 43 2.7.3 影響靜電紡絲之參數 44 第三章、 實驗 51 3.1 實驗藥品 51 3.2 實驗方法 53 3.2.1 螢光單體 4-(3-(3',6'-bis(diethylamino)-3-oxospiro [isoindoline-1,9'- xanthen]-2-yl)thioureido)phenyl methacrylate (RB)合成 53 3.2.2 螢光單體 4-(3-(3',6'-bis(diethylamino)-3-oxo-5-(4-(1,2,2- triphenylvinyl)phenyl)spiro[isoindoline-1,9'-xanthen]-2-yl)thioureido) phenyl methacrylate (TR)合成 55 3.2.3 Poly(NIPAAm-co-NMA-co-RB)合成 57 3.2.4 Poly(NIPAAm-co-NMA-co-TR)合成 58 3.2.5 靜電紡絲奈米纖維(electrospinning of nanofibers)製備 59 3.2.6 吸收與螢光光譜之量測 60 3.2.7 Lower critical solution temperature (LCST)量測 60 3.3 儀器鑑定 61 3.3.1 Nuclear Magnetic Resonance (NMR) 61 3.3.2 Gel permeation chromatography (GPC) 61 3.3.3 Ultraviolet-visible spectra (UV-vis. spectra) 62 3.3.4 Fluorescence spectrophotometer (FL) 62 3.3.5 High resolutionfield emission scanning electron microscope (HR FE-SEM) 62 第四章、結果與討論 63 4.1 單體合成與高分子聚合之鑑定 63 4.1.1 PITC-OH鑑定 63 4.1.2 PITC鑑定 64 4.1.3 RB hydradize 鑑定 65 4.1.4 RB 鑑定 66 4.1.5 TPE-Br鑑定 67 4.1.6 TPE-B(OH)2鑑定 68 4.1.7 RB-Br鑑定 69 4.1.8 TRNH2鑑定 70 4.1.9 TR鑑定 71 4.1.10 Poly(NIPAAm-co-NMA-co-RB)共聚高分子鑑定 72 4.1.11 Poly(NIPAAm-co-NMA-co-TR)共聚高分子鑑定 76 4.2 螢光感測器之光學性質探討 80 4.3 .小分子溶液之感測性探討 81 4.3.1 螢光單體TR對溶劑組成之影響 81 4.3.2 螢光單體TR之TBET效應探討 84 4.3.3 螢光單體RB與TR對金屬離子之選擇性 85 4.3.4 螢光單體RB與TR對汞離子與銅離子之響應時間 90 4.3.5 螢光單體RB與TR對汞離子之感測性 93 4.4 高分子溶液之感測性探討 96 4.4.1 高分子PTR溶液對溶劑組成之影響 96 4.4.2 高分子PR與PTR溶液對金屬離子之選擇性 99 4.4.3 高分子PR與PTR溶液對汞離子、銅離子之響應時間 102 4.4.4 高分子PR與PTR溶液之金屬離子競爭性 104 4.4.5 高分子PR與PTR溶液對酸鹼值環境之影響 105 4.4.6 高分子PR與PTR溶液對汞離子之感測性 107 4.4.7 溫敏性高分子之LCST探討 116 4.5 靜電紡絲纖維探討 117 4.5.1 靜電紡絲纖維結構鑑定 117 4.5.2 靜電紡絲纖維之感測性探討 119 4.5.3 靜電紡絲纖維之溫度應答探討 120 第五章、結論 121 參考文獻 123

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