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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姓名

劉冠宜(Kuan-Yi Liu) 查詢紙本館藏

畢業系所

化學學系

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

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摘要(中)

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。

摘要(英)

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.

關鍵字(中)

★ 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

關鍵字(英)

★ deep eutectic solvent
★ DES-USAEME
★ parabens

論文目次

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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指導教授

丁望賢(Wang-Hsien Ding)

審核日期

2020-7-20

推文