利用深共熔溶劑結合超音波輔助液液微萃取法檢測茶飲中的BTRs與BTHs殘留

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許哲叡(Che-Jui Hsu) 查詢紙本館藏

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化學學系

論文名稱

利用深共熔溶劑結合超音波輔助液液微萃取法檢測茶飲中的BTRs與BTHs殘留

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摘要(中)

本研究開發一種靈敏、簡單且對環境友善的方法檢測不同茶湯中的八種 Benzotriazoles (BTRs) 和 Benzothiazoles (BTHs)。茶湯樣品的前處理以深共熔溶劑結合超音波震盪進行液液微萃取。深共熔溶劑為一個合成快速，對環境友善、低揮發性的萃取劑，其中的氯化膽鹼具生物相容性。氯化膽鹼和 4−氯酚以莫耳數比 1 : 3 形成疏水性的深共熔溶劑萃取茶湯中的待測物，再以超高效液相層析高解析度串聯式質譜儀 (UHPLC−QTOF−MS) 進行分析。
再最佳化時，以 Design expert 軟體進行最佳化模擬，首先以 Multilevel categoric design 進行種類實驗的最佳化，結果以深共熔溶劑比例1 : 3、萃取的機械力為超音波震盪、不冰浴直接離心，得到最佳回收率。接著，利用 Face-centered Central Composite Design 的多因子實驗設計和反應曲面法及多變量分析 (ANOVA) 進行各項變因的最佳化，結果以萃取劑的體積 800 μL、超音波溫度 55℃、超音波震盪的時間 5 分鐘為最佳回收率。接著離心之後利用甲醇定量至 1 毫升，最後取其中 2 μL 的樣品注入至 UHPLC−QTOF−MS。
將本研究將開發的方法進行偵測極限 (LOD) 及定量極限 (LOQ) 的分析，得到的濃度分別介於 0.1 ~ 7.5 ng/mL 及 0.15 ~ 20 ng/mL 之間，再藉由 Inter−day 和 Intra−day 的測試精密度，相對標準偏差 (RSD) 皆小於16 %，說明此方法有良好的再現性。最後在茶湯中也成功測出茶中含 BTHs 的存在。

摘要(英)

In this study, a sensitive, simple and environmental−friendly method for the determination of eight Benzotriazoles (BTRs) and Benzothiazoles (BTHs) derivatives in tea beverages was developed. The target analytes were extracted from tea beverages using deep eutectic solvent−based ultrasound−assisted liquid−liquid microextraction (DES−USALLME). DESs are a group of novel “green” solvents, and the benefits of DESs include: starting materials are affordable, can be easily prepared at room temperature, have low or negligible toxicity, and can be tuned for hydrophobic or hydrophilic organic analytes. A hydrophobic DES was used in this study, which based on the mixture of choline chloride (as a hydrogen bond acceptor) and 4−chlorophenol (as a hydrogen bond donor) at molar ratio of 1 : 3. The determination of target analytes was performed by the combination of ultrahigh− performance liquid chromatography quadrupole time−of−flight mass spectrometry (UHPLC−QTOF−MS).
The parameters of DES−USALLME were screened and optimized by multivariate experimental design base on Multilevel categoric design and Face-centered Central Composite Design plus with response surface design and analysis of variance (ANOVA), respectively. For Multilevel categoric design screening, the optimal selections were: molar ratio of DES was 1 : 3, the extraction mechanical force was ultrasonication, and no required ice bath after ultrasonication. Then, the optimal conditions for Face-centered Central Composite Design were: 800 μL of DES, and sonicated for 5 mins in ultrasonic bath at 55 ℃. After optimization, the method was validated and shown to possess low limits of quantification (LOQs) ranging from 0.15 to 20 ng/mL, high precisions (less than 16%) for both inter-day and intra-day analysis. The developed method was then successfully applied for the analysis of some selected BTRs and BTHs in tea beverages.

關鍵字(中)

★ 深共熔溶劑
★ 苯並三唑
★ 苯並噻唑
★ 液液微萃取
★ 茶湯樣品

關鍵字(英)

★ Deep eutectic solvent
★ Benzotriazoles
★ Benzothiazoles
★ microextraction
★ tea samples

論文目次

目錄
第一章前言 1
1−1 研究源起 1
1−2 研究目標 2
第二章文獻回顧 3
2−1 綠色化學溶劑 3
2−1−1 離子液體的介紹 3
2−1−1−1 離子液體的起源 4
2−1−1−2 離子液體的性質 4
2−1−2 深共熔溶劑 5
2−2 分散液液微萃取 7
2−2−1 液液萃取的發展 7
2−2−2 分散液液微萃取 8
2−2−3 分散液液微萃取影響因素 9
2−2−4 分散液液微萃取法發展 10
2−2−5 深共熔溶劑結合超音波輔助液液微萃取法 12
2−3 超高效液相層析串聯質譜儀 13
2−4 待測物介紹 14
2−4−1 Benzotriazoles and Benzothiazoles 介紹 14
2−4−2 BTRs 及 BTHs 來源及生物影響 16
2−4−3 毒性研究 17
2−4−4 每日暴露量 18
2−4−5 相關規範 19
2−4−6 相關檢測文獻 19
第三章實驗藥品、儀器與流程 23
3−1 實驗藥品與儀器 23
3−1−1 實驗藥品 23
3−1−2 實驗儀器與設備 24
3−2 實驗流程 25
3−2−1標準品配製 25
3−2−2 超高效液相層析串聯質譜儀參數設定 26
3−2−3 質量校正 28
3−2−4 真實樣品製備 29
3−2−5 深共熔溶劑的製備 30
3−2−6 萃取方法 31
第四章結果與討論 33
4−1 待測物 UHPLC−QTOF−MS 的測定結果 33
4−1−1 層析圖圖譜 33
4−1−2 質譜圖圖譜 35
4−2 深共熔溶劑的探討 37
4−2−1 深共熔溶劑的選擇 37
4−2−2 深共熔溶劑的密度與黏度 37
4−2−3 深共熔溶劑FT−IR 圖譜 39
4−2−4 深共熔溶劑在 NMR 圖譜 40
4−3 單因子最佳化探討 42
4−3−1 深共熔溶劑的比例 42
4−3−2 深共熔溶劑的體積 43
4−3−3 鹽類對萃取的影響 44
4−3−4 萃取機械力對萃取的影響 45
4−3−5 超音波震盪水浴溫度對萃取的影響 46
4−3−6 超音波震盪時間對萃取的影響 47
4−4 實驗設計探討 48
4−4−1 Multilevel categoric design 48
4−4−2 半常態描點圖 50
4−4−3 ANOVA 分析 51
4−4−4 顯著變因探討 52
4−4−5 殘差分布圖 54
4−5 Face-centered Central Composite Design (FCCCD) 55
4−5−1 FCCCD 因子階層與因子模型結果 55
4−5−2 ANOVA 分析與因子交互作用探討 58
4−5−3 殘差分布圖 60
4−5−4 FCCCD最佳化結果 61
4−6 待測物偵測極限與檢量線 62
4−7 真實樣品的檢測 64
4−8 方法的精密度與準確度 65
4−9 文獻比較 66
4−10 Analytical Eco−Scale 68
第五章結論 71
第六章參考文獻 73

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指導教授

丁望賢(Wang-Hsien Ding)

審核日期

2021-7-7

推文