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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研究生：	陳志明 Jhih-Ming Chen
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
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：	2016
畢業學年度：	104
語文別：	中文
論文頁數：	126
中文關鍵詞：	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
外文關鍵詞：	halogenated flame retardants, matrix solid-phase dispersion, electron capture negative ion, biota sample
相關次數：	點閱：10 下載：0
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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。

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.

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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