臺灣博碩士論文加值系統

本研究開發一種靈敏、簡單、快速、方便、消耗較少量吸附材料、不須離心機械力輔助，且對環境友善的檢驗方法，用於檢測環境水樣中五種benzophenones (BPs)汙染物之殘留。
環境水樣中以磁性金屬有機骨架當作吸附材料。金屬有機骨架中加入Fe3O4透過簡單的靜置組裝合成磁性金屬有機骨架(Fe3O4@ZIF-8)，磁性吸附劑的優勢為簡單、高效和節省離心時間。本研究以磁性固相萃取法(Magnetic Solid Phase Extraction，MSPE)進行樣品前處理，以超高效液相層析儀串聯電灑游離法(+)四極桿飛行時間式質譜儀(UHPLC-ESI(+)-QTOF-MS)分析。
前處理實驗中，先以單因子對實驗條件進行選擇及優化，再以實驗設計探討多因子間的交互關係，實驗設計只須較少的實驗次數，即可得到最優化的實驗條件，以此降低實驗時間和耗材成本。先以Multilevel categoric design (MLCD)實驗設計進行非數值因子的最佳化。再以Box-Behnkne Design (BBD) 實驗設計進行數值因子的最優化。
本研究開發的方法之偵測極限（LOD）及定量極限（LOQ）分別介於 0.05-0.3 ng/mL 及 LOQ : 0.2-2 ng/mL。再以 Intra day & Inter day 檢測其精密度和再現性，相對標準偏差（RSD）皆小於8%，表示此方法有良好的再現性，且在環境水樣中檢測到benzophenones (BPs) 的殘留。研究結果得知本研究開發的方法是一種簡單、快速且相對環境友善的檢測方法。

This research developed a simple, efficient, and environmentally friendly analytical method for the determination of five frequently found benzophenones (BPs) residues in our aquatic environment, and no need for time-consuming centrifugal mechanical force assistance.
A magnetic zeolitic imidazolate framework‑8 (Fe3O4@ZIF-8) was synthesized by a static self-assembled method and applied as an adsorbent for the magnetic solid phase extraction (MSPE) technique. MSPE was then coupled with ultra-high performance liquid chromatography electrospray ionization (+)-quadrupole time-of-flight mass spectrometry (UHPLC-ESI (+)-QTOF-MS) to determine five target BPs residues in water samples. Comparison with traditional dispersive micro solid-phase extraction, the magnetic adsorbent of MSPE is the key factor affecting the adsorption effect during a sample pretreatment due to the magnetic adsorbent is quickly separated from the sample solution by applying an external magnetic field (no centrifugation), allowing the simple and convenient isolation of analytes.
One-factor-at-a-time approaches were conducted initially to select experimental conditions, and then experimental designs approaches were applied to explore the interaction between multiple experimental factors. Application of experimental designs minimized the number of experimental runs requiring to obtain the optimal conditions, thus reducing experimental time and the costs. In this study, multilevel categoric design (MLCD) was firstly used for the screening of non-numeric factors, and followed by Box-Behnken Design (BBD) for optimization of numeric factors. After optimization, the limits of detection (LOD) and limits of quantification (LOQ) of the method ranged between 0.050.3 ng/mL and 0.22 ng/mL, respectively. Precision was evaluated using intra-day and inter-day analyses, with relative standard deviations (RSD) of all below 8%, indicating good repeatability of the method. A preliminary analysis of the surface water revealed that 2- hydroxy-4-methoxybenzophenone (BP-3) was the most common BPs present in our aquatic environment, likely due to its widespread applications and slow rate of degradation.

目錄
摘要...................................................... i
Abstract.................................................iii
謝誌 ..................................................... v
目錄 ................................................... vii
圖目錄 ................................................... x
表目錄 ................................................... x
第一章 前言 .............................................. 1
1-1研究緣起 .............................................. 1
1-2研究目的 .............................................. 2
第二章 文獻回顧 ........................................... 3
2-1金屬有機骨架 ........................................... 3
2-1-1金屬有機骨架簡介...................................... 3
2-1-2金屬有機骨架發展及應用................................. 4
2-1-3磁性金屬有機骨架材料.................................. 5
2-1-4金屬有機骨架ＺＩＦs系列 ............................... 8
2-2磁性固相萃取法（Magnetic Solid Phase Extraction簡稱MSPE） ...... 11
2-2-1前言................................................ 11
2-2-2原理................................................ 12
2-3二苯甲酮類化合物（BPs） ............................... 13
2-3-1介紹................................................ 13
2-3-2對環境及人體的影響................................... 15
2-3-3相關法規............................................ 15
第三章 實驗步驟及樣品分析 ................................. 17
3-1實驗藥品和設備 ........................................ 17
3-1-1實驗藥品............................................ 17
3-1-2儀器設備............................................ 18
3-2實驗步驟 ............................................. 19
3-2-1標準品配置.......................................... 19
3-2-2超超高效液相層析串聯四極桿飛行時間式質譜儀參數設定...... 20
3-2-3質量校正............................................ 21
3-2-4磁性金屬有機骨架(MOF)合成 ........................... 22
3-2-4-1 Fe3O4合成........................................ 22
3-2-4-2 Fe3O4@ZIF-8合成 ................................. 23
3-2-4-3 Fe3O4@ZIF67-8合成 ............................... 23
3-2-5磁性金屬有機骨架Fe3O4@ZIF-8鑑定及性質探討 ............ 24
3-2-5-1 SEM圖 ........................................... 24
3-2-5-2 EDX圖 ........................................... 25
3-2-5-3紅外光譜圖 ....................................... 26
3-2-5-4 X射線繞射圖譜 .................................... 27
3-2-5-5熱重分析圖 ....................................... 29
3-2-5-6氮氣等溫吸脫附圖 .................................. 30
3-2-5-7超導量子干涉磁化圖 ................................ 31
3-2-6磁性固相萃取(micro-solid phase extraction，簡稱MSPE). 32
第四章 結果與討論 ........................................ 33
4-1 UPLC-QTOF-MS 對待測物的測定 .......................... 33
4-1-1待測物層析圖譜....................................... 33
4-1-2待測物的質譜圖....................................... 34
4-2磁性固相萃取法條件優化探討 ............................. 35
4-2-1單因子優化探討....................................... 35
4-2-1-1磁性金屬有機骨架吸附材料的選擇 ..................... 35
4-2-1-2磁性金屬有機骨架吸附材料的用量 ..................... 36
4-2-1-3萃取過程的機械力選擇 .............................. 37
4-2-1-4吸附過程的時間 .................................... 38
4-2-1-5脫附過程的時間 .................................... 39
4-2-1-6脫附溶劑的選擇 .................................... 40
4-2-1-7脫附溶劑的用量 .................................... 41
4-2-2實驗設計(Design of Experiments) .................... 42
4-2-2-1 Multilevel categoric design(MLCD) ............... 43
4-2-2-2 Box-Behnkne Design(BBD) ......................... 52
4-3 檢量線與檢測極限 ..................................... 63
4-4 方法準確度與精密度 ................................... 64
4-5 真實樣品檢測 ......................................... 65
第五章 結論 ............................................. 69
參考文獻 ................................................ 71
附錄 .................................................... 77

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