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研究生: 舒明威
Shu, Ming-Wei
論文名稱: 手搖輔助超音波增強乳化液液微萃取分析水樣中的內分泌干擾酚類
Analysis of endocrine-disrupting phenols in water samples by shake-assisted ultrasound-enhanced emulsification liquid-liquid microextraction
指導教授: 黃賢達
Huang, Shang-Da
口試委員: 凌永健
傅明仁
學位類別: 碩士
Master
系所名稱: 理學院 - 化學系
Department of Chemistry
論文出版年: 2011
畢業學年度: 99
語文別: 中文
論文頁數: 52
中文關鍵詞: 液相微萃取樣品前濃縮極致效能液相層析儀內分泌干擾酚類4-第三丁基苯酚4-肉桂苯酚4-第三辛基苯酚2,4-雙丁基苯酚壬基苯酚烷基苯酚環境荷爾蒙
外文關鍵詞: Liquid phase mictoextraction, Sample preconcentration, Ultra performance liquid chromatography (UPLC), Endocrine-disrupting phenols, 4-tert-butylphenol, 4-cumylphenol, 4-tert-octylphenol, 2,4-di-tert-butylphenol, 4-nonylphenol, Alkylphenol, Environmental hormone
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  • 本文發展了簡單且快速平衡的液相微萃取技術,以手搖輔助超音波增強乳化液液微萃取(SAUELLME)結合極致效能液相層析儀(UPLC)搭配UV偵測器,前濃縮及分析在海水與清潔劑中的五種內分泌干擾酚類(EDPs)。
    五種研究的內分泌干擾酚類為4-第三丁基苯酚(4-t-BP)、4-肉桂苯酚(4-CP)、4-第三辛基苯酚(4-t-OP)、2,4-雙丁基苯酚(2,4-di-t-BP)與壬基苯酚(4-NP)。
    在手搖輔助超音波增強乳化液液微萃取法(SAUELLME)中,藉由初步的手搖輔助使低密度的有機萃取溶劑形成細小的液滴且乳化分散於水樣中,呈現霧狀。接著超音波震盪使溶液中的細小液滴形成更微小的液滴,藉此增加接觸表面積,以達到提升萃取效果並且更快地萃取分析物達到平衡。
    探討了不同的最佳化參數,最佳化後的條件為:有機萃取溶劑為25 μL的一溴十六碳,5 mL的水樣,1分鐘的超音波萃取時間,10秒鐘的手搖輔助時間,離心3分鐘5000 rpm,鹽類的添加為1 g的氯化鈉,沒有pH值的改變,玻璃離心管平躺放置在超音波震盪器正中央。
    線性濃度範圍的相關係數皆大於0.995。此方法對於海水的偵測極限是0.5 到2.8 ngmL-1,定量極限是1.8 到9.3 ngmL-1,相對標準偏差的範圍介於4.2 % 到 10.3 %。此方法對於清潔劑的偵測極限是0.4 到2.4 μgmL-1,定量極限是1.6到 8.2 μgmL-1,相對標準偏差的範圍介於4.7 % 到 10.0 %。
    在海水水樣與清潔劑水樣中添加分析物測試本實驗的方法是否會受到基質干擾。對於海水的相對回收率為96到109 %,對於清潔劑水樣的相對回收率為81到106 %。


    A simple and fast equilibrium liquid-phase microextraction method based on shake-assisted ultrasound-enhanced emulsification liquid-liquid microextraction (SAUELLME) technique combined with ultra performance liquid chromatography (UPLC) with UV detection was developed for the preconcentration and determination of five endocrine-disrupting phenols (EDPs) in seawater samples and detergent samples. The EDPs studied were 4-tert-butylphenol (4-t-BP), 4-cumylphenol (4-CP), 4-tert-octylphenol (4-t-OP), 2,4-di-tert-butylphenol (2,4-di-t-BP) and 4-nonylphenol (4-NP). For SAUELLME, dispersion of the fine droplets of a low density organic extraction solvent into the aqueous sample is formed by use of the first step shake- assisted for mixing, and then the fine droplets could extract target analytes toward equilibrium faster because of the shorter diffusion distance and larger surface area by ultrasound-enhanced emulsification.
    Different experimental parameters were controlled and the optimum conditions found were: 25 μL of 1-bromohexadecane as the extraction solvent, 5 ml water samples, 1 minute ultrasound extraction time, 10 seconds shake-assisted time, centrifugation for 3 min at 5000 rpm, 1g NaCl for ionic strength, no pH adjustment, centrifugation tube was lying on the center of ultrasonic bath system.
    The correlation coefficient (γ2 ) greater than 0.995 for calibration curve range. The limit of detection (LOD) was 0.5 to 2.8 ngmL-1, the limit of quantitation (LOQ) was 1.8 to 9.3 ngmL-1 and the relative standard deviation (RSD) ranged from 4.2 % to 10.3 % for seawater samples. The limit of detection (LOD) was 0.4 to 2.4 μgmL-1, the limit of quantitation (LOQ) was 1.6 to 8.2 μgmL-1 and the relative standard deviation (RSD) ranged from 4.7 % to 10.0 % for detergent samples.
    Applying proposed method to spiked seawater samples and detergent samples in order to determine matrix effects. The relative recovery was 96 % to 109 % for seawater samples and 81 % to 106 % for detergent samples.

    目錄 中文摘要.........................................................i Abstract..................................................ii 目錄......................................................iv 圖目錄........................................................vi 表(附錄)目錄............................................viii 第一章、緒論 1-1 前言..................................................1 1-2 環境荷爾蒙.............................................2 1-3 環境荷爾蒙之種類.......................................3 1-4 界面活性劑.............................................5 1-5 烷基苯酚...............................................6 1-6 烷基苯酚的國外文獻探討.................................7 1-7 烷基苯酚的國內文獻探討.................................8 1-8 烷基苯酚的各國相關管制規範.............................9 1-9 萃取原理..............................................11 1-10 傳統萃取方法之介紹...................................11 1-11 較新萃取方法之介紹...................................12 1-12 研究目的.............................................17 二、實驗部份 2-1 試藥與樣品............................................25 2-2 標準溶液和環境樣品溶液................................26 2-3 實驗儀器裝置..........................................26 2-4 萃取步驟..............................................27 2-5 濃縮係數及相對回收率..................................28 第三章、結果與討論 3-1 有機萃取溶劑的選擇....................................29 3-2 超音波水槽擺放與位置選擇..............................29 3-3 萃取溶劑體積的影響....................................30 3-4 超音波時間的影響......................................31 3-5 鹽類的添加............................................31 3-6 操作的模式............................................32 3-7 手搖時間的影響........................................33 3-8 手搖輔助超音波增強乳化液液微萃取法與手搖輔助votex增強乳化液液微萃取法的比較......................................34 3-9 分析方法的確效........................................34 3-10 分析方法於環境樣品的測試.............................35 第四張、結論..............................................36 第五章、參考文獻..........................................50 圖目錄 圖一:環境荷爾蒙與天然荷爾蒙關係圖.........................3 圖二:烷基酚聚乙氧基醇類非離子型界面活性劑之結構...........5 圖三:壬基苯酚聚乙基醇類被水中微生物分解的降解途徑.........6 圖四:壬基苯酚(NP)與雌二醇(Estradiol)有相似的化學結構......7 圖五:美國環保署(USEPA)內分泌干擾物質清單.................10 圖六:固相微萃取裝置圖....................................18 圖七:固相微萃取操作流程..................................18 圖八:單滴微萃取系統......................................19 圖九:單滴微萃取系統......................................19 圖十:針筒的內壁形成有機相薄膜示意圖......................20 圖十一:單滴微萃取系統....................................20 圖十二:頂空單滴微萃取系統................................21 圖十三:中空纖維薄膜微萃取................................21 圖十四:中空纖維薄膜微萃取法之兩相與三相系統..............22 圖十五:Lee Hian-Kee提出中空纖維液相微萃取之裝置..........22 圖十六:溶劑棒微萃取裝置..................................23 圖十七:分散式液液微萃取法................................23 圖十八:冷凝分散液液微萃取法..............................24 圖十九:本實驗的操作過程示意圖............................37 圖二十:有機萃取溶劑的選擇................................37 圖二十一:超音波水槽擺放選擇..............................38 圖二十二:超音波水槽位置選擇..............................38 圖二十三:萃取溶劑體積的影響..............................39 圖二十四:超音波時間的影響................................39 圖二十五:鹽類的添加......................................40 圖二十六:操作的模式......................................40 圖二十七:手搖時間的影響..................................41 圖二十八:手搖輔助vortex增強乳化液液微萃取法..............41 圖二十九:環境樣品海水水樣所得的UPLC層析圖譜..............42 圖三十:環境樣品清潔劑水樣所得的UPLC層析圖譜..............43 表(附錄)目錄 表一:UPLC動相沖提梯度....................................44 表二:分析方法的確效......................................44 表三:對於環境樣品添加不同濃度標準品的相對標準偏差(RSD)...45 附錄一:最佳化萃取條件....................................45 附錄二:各分析物的特性吸收波長............................45 附錄三:本實驗分析的五種分析物分子態的UV吸收..............46 附錄四:本實驗分析的五種分析物結構與資料..................47 附錄五:文獻比較..........................................48

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