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研究生: 黃邦瑜
Huang, Pang-Yu
論文名稱: Naphthoquinone-Rhodamine based衍生物螢光感測分子之合成與靜電紡絲奈米纖維態製備並應用於鐵離子感測
Naphthoquinone-Rhodamine based Fluorescent Sensing Probe: Synthesis, Electrospinning NanoFibers Fabrication and Application in Fe3+ Detection
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: 2024
畢業學年度: 112
語文別: 中文
論文頁數: 117
中文關鍵詞: 螢光感測器 、鐵離子 、靜電紡絲奈米纖維 、跨鍵能量轉移
外文關鍵詞: fluorescent sensor, iron ion, electrospun nanofibers, through-bond energy transfer
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  • 本研究利用自由基聚合法(free radical polymerization)合成出三種含有不同單體比例之螢光高分子poly(NIPAAm-co-NMA-co-RN), PNNRN。

    共聚高分子PNNRN分別由Naphthoquinone-Rhodamine based 螢光單體、親水性高分子NIPAAM、可交聯高分子NMA所組成 : NIPAAM鏈段使高分子具有收縮-膨潤的特性;經化學熱交聯後之NMA鏈段使高分子具有溶劑耐受性,不會回溶於溶劑;本研究設計的naphthoquinone-rhodamine based 螢光單體,對Fe3+具有感測性質,結構中的rhodamine 可與 Fe3+螯合而開環,產生rhodamine之吸收峰。能量可透過跨鍵能量轉移(through-bond energy transfer , TBET)的機制,由 naphthoquinone 轉移到rhodamine,產生螢光放射,可視作為一 off-on 之感測器。並透過靜電紡絲技術(electrospinning technique)將高分子加工成奈米纖維,做為固態螢光感測器應用於環境的感測。

    螢光高分子PNNRN對Fe3+顯示出良好的選擇性,並在其餘金屬陽離子的干擾下具備優秀的競爭性。由job plot之結果推論PNNRN與Fe3+是以1:2的當量形成錯合物,螢光滴定曲線結果可觀察到高分子溶液態與纖維態在各自區間的感測上表現出高度線性,也具備低偵測極限,可達到1.21 µM,並由pH值測試證實PNNRN能應用於常見之酸鹼環境之中(pH 值6-10),且具備短時間感測 Fe3+之能力。雖然數據顯示高分子纖維態的感測性相較溶液態顯得略為遜色,然而高分子纖維態為固態介質,具有便於攜帶、操作簡單等優點,具有應用於固態螢光感測器之優秀潛力。

    This study is to synthesize three types of fluorescent polymers, poly(NIPAAm-co-NMA-co-RN) (PNNRN) via free radical polymerization with varying monomer ratios. PNNRN is composed of a naphthoquinone-rhodamine based fluorescent monomer, hydrophilic NIPAAM, and cross-linkable NMA. The NIPAAM segments provide the polymer with shrink-swell properties, while the NMA segments, after chemical and thermal cross-linking, confer solvent resistance. The designed fluorescent monomer is sensitive to Fe3+. After chelation with Fe3+, cause the spirolactam ring in rhodamine unit to open and exhibit an absorption peak. Energy transfer from naphthoquinone to rhodamine results in fluorescence emission, functioning as an off-on sensor.

    The polymer is processed into nanofibers via electrospinning for solid-state fluorescent sensor applications. PNNRN demonstrates high selectivity and competitiveness in detecting Fe3+ amidst other metal ions. Job plot results indicate to form chelation complex with 1:2 stoichiometry between PNNRN and Fe3+. Fluorescence titration curves show high sensitivity with Fe3+, and a low detection limit of 1.49 µM. The pH tests confirm its effectiveness in common acidic and basic environments (pH 6-10), with rapid Fe3+ sensing capability. Despite the solid-state sensor's slightly lower sensitivity compared to its solution state, it offers advantages such as portability and ease of use, highlighting its potential as a solid state fluorescent sensor.

    摘要 I ABSTRACT II 誌謝 X 目錄 XII 圖目錄 XVI 表目錄 XXI 第一章、 緒論 1 1.1前言 1 1-2研究動機 1 第二章、 文獻回顧 3 2.1 鐵離子對人體的危害[1] 3 2.2螢光原理 3 2.2.1光致發光(photoluminescence) 3 2.2.2激發態分子之去激發途徑 3 2.2.3 影響螢光的變因 6 2.2.4螢光淬滅機制[8, 9] 9 2.3 感測器[10-12] 12 2.3.1 螢光感測器[13] 14 2.3.2 rhodamine-based 感測器應用於金屬離子檢測[28, 29] 24 2.3.3 Schiff base 的應用[30-33] 25 2.4 功能性高分子[34] 26 2.4.1 環境應答高分子[35-38] 26 2.4.2 可交聯高分子[40] 28 2.5 靜電紡絲技術 29 2.5.1 靜電紡絲簡介[41, 42] 29 2.5.2 靜電紡絲裝置與原理[41, 43] 29 2.5.3 影響靜電紡絲之參數 30 第三章、 實驗 38 3.1實驗藥品 38 3.2 實驗方法 40 3.2.1螢光單體 2-(4-((E)-(allylimino)methyl)phenyl)-3-(4-((E)-((3',6'-bis(ethylamino)-2',7'-dimethyl-3-oxospiro[isoindoline-1,9'-xanthen]-2-yl)imino)methyl)phenyl)naphthalene-1,4-dione (RN) 之合成 40 3.2.2 螢光高分子 Poly(NIPAAm-co-NMA-co-RN) (PNNRN)合成 44 3.2.3 靜電紡絲奈米纖維(electrospinning of nanoFiber)之製備 45 3.2.4 吸收光譜與螢光光譜之測量 47 3.3 儀器鑑定 49 3.3.1 Nuclear magnetic resonance spectroscopy (NMR) 49 3.3.2 Ultraviolet-visible spectrophotometer (UV-vis) 50 3.3.3 Gel Permeation Chromatography(GPC) 50 3.3.4 Photoluminescence spectrophotometer (PL) 50 3.3.5 High resolution field emission-scanning electron microscopy (HR FE-SEM) 51 3.3.6 Attenuated Total Reflection-Fourier-transform infrared spectroscopy (ATR-FTIR) 51 第四章、 結果與討論 52 4.1 螢光單體與高分子合成之鑑定 52 4.1.1 R6GNH2 鑑定 52 4.1.2 NaphCHO 鑑定 53 4.1.3 R6GNaph 鑑定 54 4.1.4 RN monomer 鑑定 55 4.1.5 螢光高分子 Poly(NIPAAm-co-NMA-co-RN) 鑑定 56 4.2 靜電紡絲纖維結構之鑑定 61 4.3 螢光分子之光學感測性質探討 66 4.4 螢光小分子溶液之感測性探討 67 4.4.1 螢光單體RN對溶劑組成之影響 67 4.4.2 RN單體對金屬離子之選擇性 68 4.4.3 RN單體對金屬離子之競爭性 69 4.4.4 RN單體以及前驅物R6GNaph與 Fe3+之螯合計量比例 71 4.4.5 RN單體溶液對 Fe3+之感測性 72 4.5 螢光高分子溶液與纖維態之感測性探討 74 4.5.1螢光高分子PNNRN對溶劑組成之影響 74 4.5.2 螢光高分子PNNRN對Fe3+之響應時間 75 4.5.3螢光高分子PNNRN對金屬離子之選擇性 76 4.5.4 螢光高分子PNNRN對金屬離子之競爭性 77 4.5.5螢光高分子PNNRN與 Fe3+之螯合計量比例 78 4.5.6 螢光高分子PNNRN溶液對 Fe3+之感測性 79 4.5.7螢光高分子PNNRN溶液對酸鹼值之影響 82 4.5.8靜電紡絲纖維對 Fe3+之感測性 83 4.6 螢光高分子之溶液態及纖維態的感測性探討 86 第五章、 結論 89 參考文獻 90

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