臺灣博碩士論文加值系統

石墨烯量子點具有量子限制侷限（quantum confinement）和邊緣效應（edge effect），其特殊性質近年來受到高度重視，因此得以在螢光應用上蓬勃發展。石墨烯量子點具有低毒性、溶解度高、化學惰性和穩定的發光性質，主要用於感測器和生物成像。
　　本研究分兩部分，第一部分研發由下向上法合成石墨烯量子點，利用檸檬酸與兩個不同的胺基酸(甘胺酸、半胱胺酸)在一鍋脫水反應後，合成出兩種摻雜氮原子的石墨烯量子點(N-doped Graphene Quantum Dots, N-GQDs)，胺基酸在此反應中同時扮演碳源和氮源的雙重角色，以甘胺酸合成的量子產率約為14%，半胱胺酸合成的量子產率約為58%，相較於其他一鍋法合成的GQD，具有較高螢光產率之優點。合成出的產物，利用FTIR、PL、TEM、UV、AFM與XPS等儀器進行表徵分析，結果顯示我們成功的以快速、簡易的一鍋法方式合成摻雜氮原子的石墨烯量子點。
第二部分利用N-GQDs的優點，運用在蜂蜜中四環素（tetracycline）的感測，發展快速篩選方法，達到零有機溶劑、簡便、快速的目的。感測機制基於操控N-GQDs螢光的開閉、N-GQDs和四環素間的π-π堆疊作用力、和猝滅N-GQD的螢光。利用標準添加法測定蜂蜜中的四環素，偵測極限為4 ppb，回收率為77-112%，相對標準偏差為14.5%。應用於21件市售蜂蜜樣品的快篩，篩選結果顯示4件有四環素殘留量。

Graphene quantum dots (GQDs) are nano-sized materials having unique properties like the quantum confinement effect and edge effect which has led to its emergence in fluorescence-based applications. The low toxicity, high solubility, chemically inertness, and stable luminescent properties of GQDs must be explored further for its application in sensors and bio imaging studies.
A one-pot synthesis of GQDs based on the bottom-up approach has been developed in this study with citric acid and amino acids（glycine、cysteine） precursors to successfully achieve two N-doped Graphene Quantum Dots (N-GQD). In this reaction, amino acid plays dual role of donating both carbon and nitrogen atom. These as-prepared N-GQDs have a high quantum yield of 14（glycine） and 58%（cysteine） as compared to previously reported GQDs. The final product has been characterized using FT-IR, PL, TEM, UV-Vis, XPS, and AFM, which shows successful nitrogen doping as GQDs.
These highly fluorescent N-GQDs have been used for faster sensing of tetracycline in honey, making this, a green method as it does not involve the use of any toxic reagent. The detection is based on the on-off mechanism and fluorescent control of N-GQDs. The sensing is primarily based on a π-π stacking interaction between N-GQD and tetracycline by quenching the fluorescence of N-GQDs. Detection of honey has been carried out using a standard addition method. A detection limit of 4 μg·L−1, recovery of 77-112%, and a relative standard deviation of 14.5% is a proof to a highly sensitive detection. Further, rapid detection of 21 commercial honey samples has been carried out, of which, four samples have been found with the presence of tetracyclin.

目錄
第一章 緒論 1
1.1 研究背景 1
1.2 四環素檢驗方法 5
1.3 石墨烯量子點 9
1.4 雜化石墨烯量子點 12
1.5 石墨烯量子點的應用 13
1.6 研究動機與目標 16
第二章 工作原理 17
2.1 螢光原理 17
2.2 量子產率 18
2.3 pH對螢光的影響 19
2.4 螢光消光(Quench) 19
2.5 π-π堆疊作用力(π-π stacking interaction)…………………..19
2.6 雜化石墨烯量子點與四環素間的作用力 21
第三章 實驗方法 22
3.1 N-GQDs樣品製備 22
3.2 S、N-GQDs樣品製備 23
3.3 從下而上製備GQDs之機制 25
3.3 N-GQDs和S、N-GQDs的量子產率 26
3.4 儀器設備 28
3.4.1 可見光紫外光分光光譜儀 29
3.4.2 螢光光譜儀 29
3.4.3 高解析X射線光電子能譜儀 30
3.4.4 傅立葉轉換紅外光譜儀 30
3.4.5 穿透式電子顯微鏡 31
3.4.6 原子力顯微鏡 31
3.5實驗設備 32
3.6實驗藥品 32
第四章 結果與討論 33
4.1 N-GQDs之特性分析 33
4.1.1 N-GQDs的TEM圖像 33
4.1.2 N-GQDs的AFM圖像 35
4.1.3 N-GQDs的高解析X射線光電子能譜分析 36
4.1.4 N-GQDs的FTIR光譜圖 38
4.1.5 N-GQDs的紫外光吸收光譜圖 39
4.1.6 N-GQDs在不同激發波長下的螢光放射光譜 41
4.1.7 N-GQDs的螢光放射光譜 42
4.2 S、N-GQDs之特性分析 43
4.2.1 S、N-GQDs的TEM圖像 43
4.2.2 S、N-GQDs的AFM圖像 45
4.2.3 S、N-GQDs的高解析X射線光電子能譜分析 46
4.2.4 S、N-GQDs的FTIR光譜圖 48
4.2.5 S、N-GQDs的紫外光吸收光譜圖 49
4.2.6 S、N-GQDs在不同激發波長下的熒光放射光譜 51
4.2.7 S、N-GQDs的螢光放射光譜 52
4.3兩種含氮石墨烯量子點的比較 53
4.4 N-GQDs的干擾物測定 57
4.5 不同pH下N-GQDs的螢光強度 58
4.6 不同濃度的四環素對N-GQDs的影響 59
4.7 N-GQDs應用在分析蜂蜜中的四環素 63
4.8 回收率測定 66
4.9 N-GQDs應用在分析蜂蜜中的四環素 67
第五章 結論 69
第六章 參考文獻 70

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