利用綠色溶劑結合超音波輔助液液微萃取法檢測水體中防腐劑parabens的含量

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研究生：	劉冠宜 Kuan-Yi Liu
論文名稱：	利用綠色溶劑結合超音波輔助液液微萃取法檢測水體中防腐劑parabens的含量
指導教授：	丁望賢 Wang-Hsien Ding
口試委員:
學位類別：	碩士 Master
系所名稱：	理學院 - 化學學系 Department of Chemistry
論文出版年：	2020
畢業學年度：	108
語文別：	中文
論文頁數：	140
中文關鍵詞：	疏水性深共熔溶劑、超音波輔助疏水性深共熔溶劑乳化微萃取法、對-羥基苯甲酸酯
外文關鍵詞：	deep eutectic solvent, DES-USAEME, parabens
相關次數：	點閱：13 下載：0
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本研究開發了一種簡單、靈敏且對環境友好的方法以檢測水樣中
九種 parabens 防腐劑的殘留。此方法是以超音波輔助疏水性深共熔溶
劑乳化微萃取法 ( Deep eutectic solvent-based ultrasound- assisted emulsification microextraction , DES-USAEME ) 從水樣中萃取待測物，再透過超高效液相層析串聯電灑游離（-）-四極桿飛行時間質譜儀（UHPLC-ESI（-）-QTOF-MS）進行測定。選擇莫耳比為 2:1 的薄荷醇（作為氫受體）和十二烷酸（作為氫供體）的疏水性深共熔溶劑作為萃取劑，因其較便宜、容易在室溫下合成且對環境友善。本研究透過 Box-Behnken Design 實驗設計法（BBD）的多變量實驗設計及反應曲面法和多變量分析（ANOVA）進行各項因子的最佳化。
所得出的最佳條件為：在離心管中將 5 mL 水樣與 500 µL DES 混合。經過充分混和後加入 50 mg NaCl，並在 65°C 的超音波水浴中震盪 20 分鐘。再以 3000 rpm 離心 10 分鐘後，取出上層並用甲醇定溶至 500 µL，最後將 2 µL 提取物直接注入 UHPLC-QTOF-MS 中進行檢測。所開發方法的定量極限（LOQ）為 1 至 3.2 ng / mL。在 Intra-day及 Inter-day 的測試中，相對標準偏差 (RSD) 皆小於 10%，且回收率為82％至 99％，顯示此方法有良好的穩定性和再現性。最佳化後的 DES-USAEME 結合高選擇性和高靈敏度的 UHPLC-ESI（-）-QTOF-MS 已成功用於檢測水樣中的 parabens 防腐劑的微量殘留。

In this study, a simple, sensitive, and environmental-friendly method for determining the presence of nine paraben preservatives in water samples was developed. The target analytes were efficiently extracted from water samples using a deep eutectic solvent-based ultrasound- assisted emulsification microextraction (DES-USAEME), and their determination were then performed by the combination of ultrahigh- performance liquid chromatography and electrospray ionization (-)- quadrupole time-of-flight mass spectrometry (UHPLC-ESI(-)-QTOF-MS). Due to the cost and easy synthesis at room temperature, the hydrophobic DES of choice in this study was based on the mixture of menthol (as a hydrogen bond acceptor) and dodecanoic acid (as a corresponding hydrogen bond donor) at molar ratio of
2:1. The parameters of DES-USAEME were optimized by multivariate experimental design based on Box-Behnken design (BBD) plus with response surface design and analysis of variance (ANOVA). The optimal conditions were: 5 mL of water sample mixed with 500 µL of DES in a centrifuge tube. After vortex, 50 mg of NaCl were added and sonicated for 20 min in ultrasonic bath at 65 °C. After centrifugation at 3000 rpm for 10 min, the supernatant was collected and reconstituted with
methanol to 500 μL, and then 2 μL of the extract was directly injected into UHPLC-QTOF-MS for detection. The limits of quantification (LOQs) of the developed method ranged from 1 to 3.2 ng/mL. High precisions were
obtained for both intra- and inter-day analysis, and ranged from 1 to 10%.Satisfactory average spiked recovery ranged from 82 to 99%. Optimal DES-
iv USAEME combined with highly selective and sensitive UHPLC-ESI(-)-QTOF-MS was successfully applied for the determination of selected parabens presenatives in various water samples at trace-level.

摘要    i
Abstract    iii
謝誌    v
目錄    vii
圖目錄    xii
表目錄    xv
第一章    前言    1
1-1    研究緣起    1
1-2    研究目標    3
第二章    文獻回顧    5
2-1-1 離子液體    5
2-1-2 深共熔溶劑 Deep Eutectic Solvents(DES)    6
2-1-2-1 深共熔溶劑製備    9
2-1-2-2 深共熔溶劑應用    9
2-2 超高效液相層析高解析串聯質譜儀    10
2-3 分散式液液微萃取法    13
2-3-1前言    13
2-3-2 原理    13
2-3-3 DLLME流程    14
2-3-4影響因素    15
2-3-5 DLLME的後續發展    17
2-4 超音波輔助深共熔溶劑液液微萃取法    18
2-5 同位素稀釋定量法    20
2-6 防腐劑(Preservative)    21
2-6-1對-羥基苯甲酸酯簡介    23
2-6-2 對環境及人體的影響    25
2-6-3 毒性研究    26
2-6-3-1 毒性探討    26
2-6-3-2 每日暴露量    28
2-6-4 相關規範    29
2-6-5 相關檢測文獻    30
第三章    實驗步驟與樣品分析    35
3-1 實驗藥品與設備    35
3-1-1實驗藥品    35
3-1-2儀器設備    37
3-2實驗步驟    39
3-2-1標準品配製    39
3-2-2 超高效液相層析串聯質譜儀參數設定    40
3-2-3 質量校正    42
3-2-4 深共熔溶劑(DES)合成    42
3-2-5超音波輔助深共熔溶劑液液微萃取法    43
3-3 樣品採集    45
第四章    結果與討論    47
4-1 UHPLC-QTOF-MS對待測物的測定    47
4-1-1 待測物分析    47
4-1-2 待測物之質譜圖    48
4-2 深共熔溶劑探討    52
4-2-1 深共熔溶劑的選擇    52
4-2-2 深共熔溶劑性質    52
4-2-2-1 物理性質    52
4-2-2-2 Infrared Spectroscopy圖    54
4-2-2-3 NMR圖    55
4-3 超音波輔助深共熔溶劑液液微萃取法最佳化條件探討    57
4-3-1 單因子最佳化探討    57
4-3-1-1 萃取劑的比例    57
4-3-1-2萃取劑的體積    58
4-3-1-3 NaCl的重量    59
4-3-1-4 超音波震盪時間    60
4-3-1-5 超音波震盪溫度    61
4-3-2 Experimental Design    62
4-3-2-1 Box-Behnken design與結果    62
4-3-2-3 因子間交互作用力之探討    66
4-3-2-2 殘差分布圖    68
4-3-2-3 最佳化結果    71
4-4 檢量線與偵測極限    71
4-4-1 Mandel test    73
4-5 真實樣品的檢測    75
4-6 方法精密度與準確度    80
4-7 萃取方法比較    81
4-8 Analytical Eco-Scale    83
第五章 結論    85
第六章 參考文獻    87
附錄A    96
個別parabens的BBD結果    96
MeP    96
EtP    98
iPrP    100
PrP    102
iBuP    104
BuP    106
PeP    108
HxP    110
BzP    112
附錄B    114

                                

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