開發基質固相分散萃取法檢測生物樣品中鹵系阻燃劑

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姓名

陳志明(Jhih-Ming Chen) 查詢紙本館藏

畢業系所

化學學系

論文名稱

開發基質固相分散萃取法檢測生物樣品中鹵系阻燃劑

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摘要(中)

鹵系阻燃劑如：五溴酚 (Pentabromophenol, PeBP)、四溴雙酚A (Tetrabromobisphenol A, TBBPA)、四氯雙酚A (Tetrachlorobisphenol A, TCBPA) 被廣泛添加於民生用品與防火材料中，在生產及使用過程中，容易經由水的途徑而進入環境裡。這類鹵系阻燃劑由於具有較高的親脂性，因此在食物鏈中會累積放大，其殘留濃度也已在水產中被檢測出。
本研究主要是發展一套簡單、有效率，可快速檢測這三種鹵系阻燃劑的樣品前處理法，將其應用於不同種類的生物樣品中。利用基質固相分散萃取法 (Matrix solid-phase dispersion, MSPD) 進行樣品前處理，搭配氣相層析質譜儀結合電子捕捉負離子化學游離法 (GC-ECNI-MS) 進行偵測。
從生物樣品中萃取目標待測物，並將影響萃取效率之實驗參數，利用實驗統計設計 (Statistical experimental design) Box-Behnken design (BBD) 及變異數分析 (Analysis of variance, ANOVA) 來做最佳化探討。最佳化後的萃取條件為，將0.5 g經由冷凍乾燥的生物樣品與1 g矽酸鎂，放入振盪器中快速均勻混合。將混合物轉移到含有1 g C18的玻璃管柱中，再用12 mL乙腈沖提出來，最後將萃取溶液旋濃乾燥。以內標準品含有衍生試劑回溶進行離線矽烷化衍生，取1 μL待測物溶液利用GC-ECNI-MS進行偵測，可得偵測極限 (LOD) 在0.06-0.15 ng/g間。在inter-days及intra-day的測試中，所得之相對標準偏差 (RSD) 小於7 %，顯示此方法穩定且具有良好的再現性。在生物檢體中，三種鹵系阻燃劑的濃度介於0.3至2.2 ng/g。

摘要(英)

Halogenated flame retardants, such as pentabromophenol (PeBP), tetrabromobisphenol A (TBBPA), and tetrachlorobisphenol A (TCBPA), are widely used to add in fire protection materials. After production and use, halogenated flame retardants enter the environment easily through the water way. Because of their high lipophilicity, they can be bio-accumulated and bio-magnificated in the food chain. Currently in various aquatic and terrestrial species have detected containing such substances.
In this study, a simple and effective method for the rapid analysis of these three halogenated flame retardants in various sea food samples was developed. The method involved the use of vortex-homogenization matrix solid-phase dispersion (VHMSPD) extraction for the sample pretreatment, and determination by gas chromatography-electron capture negative ion mass spectrometry (GC-ECNI-MS).
The parameters affecting the extraction efficiency of the target analytes from sea food samples were optimized by Box-Behnken design and analysis of variance. The optimal conditions of VHMSPD involved dispersing of 0.5 g of freeze-dried sea food sample with 1 g of Florisil by a vigorous shaking to obtain a dry homogenous mixture. The mixture was transferred to a glass column containing 1 g of octadecyl bonded silica (C18), as the clean-up co-sorbent. The target analytes were then eluted with 12 mL of acetonitrile. The extract was dried under nitrogen and the residue was redissolved in 50 μL ethyl acetate with internal standard and derivatization regent (BSTFA). Then 1 μL of the derivatized sample was injected to GC-ECNI-MS for analysis. The limits of detection (LODs) were 0.06-0.15 ng/g. Inter-days and intra-day precision (% RSD) for three analytes were less than 7 %. It indicated that the method shows good reproducibility and stability. The total concentrations of these halogenated flame retardants in sea food samples ranged from 0.3-2.2 ng/g.

關鍵字(中)

★ 鹵系阻燃劑
★ 基質固相分散萃取法
★ 電子捕捉負離子化學游離法
★ 生物檢體

關鍵字(英)

★ halogenated flame retardants
★ matrix solid-phase dispersion
★ electron capture negative ion
★ biota sample

論文目次

摘要 I
英文摘要 III
謝誌 V
目錄 VII
圖目錄 XI
表目錄 XIII
第一章前言 1
1-1 研究緣起 1
1-2 研究目標 5
第二章文獻回顧 7
2-1阻燃劑 7
2-1-1阻燃劑簡介與原理 7
2-1-2阻燃劑之分類 9
2-2鹵系阻燃劑 12
2-2-1溴化阻燃劑簡介 12
2-2-2氯化阻燃劑簡介 14
2-2-3鹵系阻燃劑性質 15
2-2-4鹵系阻燃劑毒性 18
2-3國外相關研究 20
2-4基質固相分散萃取法 24
2-4-1基質固相分散萃取法簡介 24
2-4-2基質固相分散萃取法原理 25
2-5衍生化技術 27
2-5-1衍生化技術的種類和條件 27
2-5-2矽烷化反應 28
2-6氣相層析質譜儀 29
2-6-1氣相層析質譜儀簡介 29
2-6-2電子捕捉負離子化學游離法 31
2-6-3四極矩質譜儀 33
2-6-4選擇離子偵測法 34
2-7實驗設計法 35
2-7-1實驗設計簡介 35
2-7-2反應曲面法 36
2-7-3 Box-Behnken Design 37
2-8線性回歸 39
2-8-1 Mandel test 39
2-8-2 The Lack-of-Fit test 41
2-9基質效應 43
第三章實驗步驟與樣品分析 45
3-1實驗藥品與設備 45
3-1-1實驗藥品 45
3-1-2儀器設備 47
3-2實驗步驟 48
3-2-1標準品的製備 48
3-2-2基質固相分散萃取法實驗流程 51
3-2-3索氏萃取法實驗流程 52
3-3生物檢體採集 53
3-4樣品添加步驟 53
第四章結果與討論 55
4-1衍生化反應條件之探討 55
4-1-1衍生化試劑 55
4-1-2衍生化溫度的影響 56
4-1-3衍生化時間的影響 57
4-2鹵系阻燃劑 58
4-2-1矽烷化待測物的分析 58
4-2-2檢量線及偵測極限 61
4-3基質固相分散萃取法最佳化條件探討 63
4-3-1沖提溶劑與分散吸附劑種類選擇 63
4-3-2 Box-Behnken Design基質固相分散萃取法最佳化 65
4-3-3因子間交互作用力的探討 68
4-4 Mandel test與The Lack-of-Fit test 72
4-4-1 Mandel test 72
4-4-2 The Lack-of-Fit test 73
4-5基質效應 74
4-6真實樣品之檢測 76
4-7檢測方法的穩定性 85
4-8方法比較 86
第五章結論 89
第六章參考文獻 91
附錄 101

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指導教授

丁望賢(Wang-Hsien Ding)

審核日期

2016-6-20

推文