臺灣博碩士論文加值系統

在過去十年中，螢光共軛高分子由於具有容易測量和高靈敏度等特性，當其與分析物鍵解在一起時，可以將化學訊號轉換成電子訊號，所以在不同的環境應用當中，此螢光感測材料，引起非常廣大的研究興趣。
在本研究中，主要利用Suzuki和Heck coupling聚合法合成含有三苯胺基團(PFTPA系列)和側鏈三吡啶基團(CPFTPY系列)之聚芴共軛高分子，探討對於光學性質和離子辨識行為的影響。PFTPA系列和CPFTPY系列高分子的重量平均分子量範圍分別為4392~5270和4725~6110，所有高分子的熱裂解溫度Td皆大於353.5 oC，且當溫度高達800 oC時，高分子的殘餘量還有53.2 %以上，顯示所合成的共軛高分子熱穩定性良好。在螢光光譜中發現，PFTPA50和CPFTPY50在不同的溶劑中隨著溶劑的極性增強，螢光光譜有紅移的情形發生。CPFTPY50有明顯紅移的現象，是由於導入三吡啶基團(TPY)使其有電荷轉移的產生。電化學方面PF、PFTPA系列和CPFTPY系列高分子，HOMO值分別為–5.62 eV、–5.63 ~ –5.16 eV、–5.63 ~ –5.10 eV，顯示含有TPA基團有效提高HOMO能階，而LUMO值分別為–2.64 eV、–2.65 ~ –2.21 eV和–2.65 ~ –2.23 eV，發現導入TPY基團亦可降低LUMO能階，藉此降低高分子的能障。在螢光化學感測器的測試，發現僅有TPY含量較高的CPFTPY50具有明顯的辨識效果，其對於Zn2+、Mn2+及Ni2+皆有明顯發生螢光強度驟減的現象，特別對於Ni2+幾乎發生完全螢光萃熄。以Zn2+、Mn2+及Ni2+做濃度滴定實驗，Ksv值分別為3.67 × 104 M-1、4.23 × 104 M-1及1.08 × 105 M-1。此研究證明含有TPY的高分子CPFTPY50適合作離子辨識基團的電子接受體，可應用於螢光化學感測器上。另外使用離子辨識效果最明顯的高分子CPFTPY50，對其做不同酸鹼值下的螢光測試，發現其在pH值為13的環境時，螢光強度並沒有明顯的變化，而在pH值為1時，螢光產生驟減的現象，且再加入等量的OH-後，可以使螢光回復至原本的0.7倍。此外，所有高分子皆具有高螢光量子效率(0.39~0.56)，有利於應用在化學感測器中。

Fluorescent conjugated polymers used as versatile sensory materials are particularly attractive for various environmental applications during the past decade, because of their ease of measurement and high sensitivity in transforming chemical signals into electronic signals when binding with analyte.
This report describes two well-defined conjugated polyfluorenes, incorporating triphenylamine (PFTPA series) and terpyridyl units (CPFTPY series), using Suzuki and Heck coupling polymerization, respectively. The structural effect on optical properties and the effect of the terpyridyl unit on sensory characteristics of fluorescent chemosensors were investigated. The weight-average molecular weight of PFTPA and CPFTPY series were in the range 4392-5270 and 4725-6110 g/mol, respectively. All synthesized polymers revealed highly thermal stable with decomposition temperatures (Td) greater than 353.5 oC and beyond 53.2 % weight loss occurred at 800 oC. Increasing the polarity of organic solvents produced bathochromic shifts in the PL spectra of PFTPA50 and CPFTPY50. Compared to other polymers, CPFTPY50 showed significant bathochromic shift, originating from charge transfer formation through triphenylamine-terpyridine interactions. The estimated HOMO/LUMO energy levels for PF, PFTPA series and CPFTPY series are –5.65/–2.64 eV, –5.63 to –5.16 eV/–2.65 to –2.21 eV, and –5.63 to –5.10 eV /–2.65 to –2.23 eV, respectively. Incorporating electron-donating triphenylamine groups into these polymers raised the HOMO levels, while substituting the polymers with a terpyridine pendent group lowered the LUMO levels. CPFTPY50 with pendant terpyridyl unit showed higher sensitivities toward Zn2+, Mn2+ and Ni2+ as compared with other metal ions. Especially, nearly complete fluorescence quenching of CPFTPY50 was induced when Ni2+ was added. The Ksv values for Zn2+, Mn2+ and Ni2+ were 3.67 × 104 M-1, 4.23 × 104 M-1 and 1.08 × 105 M-1, respectively. CPFTPY50 showed complete fluorescence quenching when the pH value of aqueous solution at 1, however; the pH value at 13 showed little effect on the fluorescence intensity. Adding an equivalent of OH– recovered the fluorescence intensity to approximately 70 % of original intensity. All polymers revealed higher fluorescence quantum yields (ΦPL = 0.39−0.56), suggesting that they are promising materials for chemosensor applications.

目錄
摘要 I
Abstract III
誌謝 V
目錄 VI
流程目錄 IX
表目錄 IX
圖目錄 X
第一章 緒論 1
1-1 前言 1
1-2 研究動機與目的 2
第二章 原理與文獻回顧 5
2-1 共軛高分子介紹與應用 5
2-2 螢光介紹 8
2-2-1 螢光原理 8
2-2-2 影響螢光之因素 11
2-2-3 溶劑效應(solvent effect) 14
2-3 螢光能量轉移 15
2-4 螢光感測器原理與應用 17
2-4-1 感測器的組成與原理 17
2-4-2 常見的分子辨識基團 18
2-4-3 螢光感測器的訊號變化與傳遞機制 26
2-4-4 共軛高分子在螢光感測器上的應用 31
2-4-5 螢光感測器的可逆性 33
2-5 螢光萃熄常數 37
2-5-1 動態淬熄 37
2-5-2 靜態淬熄 39
2-6 以Donor-acceptor型分子作為螢光感測器之發展 39
第三章 實驗內容 43
3-1 實驗儀器與裝置 43
3-2 儀器鑑定 44
3-3 物性測量儀器 46
3-4 實驗藥品與材料 50
3-5 實驗步驟 53
3-5-1 單體合成 53
3-5-2 共軛高分子合成 55
3-6 合成反應機制 59
3-7 高分子光學性質探討 62
3-8 螢光感測現象的量測 63
3-8-1 陽離子對螢光發光的影響 63
3-8-2 pH值對螢光發光的影響 64
3-9 量子效率測量 64
3-10 藉由循環伏安法探討高分子的電化學性質 66
第四章 結果與討論 68
4-1 結構鑑定 69
4-1-1 單體結構之鑑定 69
4-1-2 高分子結構之鑑定 70
4-2 高分子分子量的量測 71
4-3 高分子熱性質分析 72
4-3-1 熱重分析 73
4-3-2 微差式掃描熱卡計分析 73
4-4 高分子光學性質 75
4-4-1 高分子在溶液態中及薄膜態的光學性質 75
4-4-2 高分子在不同溶劑中的光學性質 78
4-4-3 高分子在溶液態的金屬離子感測效應 80
4-4-4 高分子在溶液態的陰離子感測效應 83
4-4-5 高分子在不同酸鹼性環境中的發光特性 84
4-5 相對量子效率 85
4-6 高分子電化學性質分析 86
第五章 結論 116
參考文獻 119
自述 123

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