以綠色化學概念檢測生物檢體中人工合成麝香與烷基酚類流佈之研究

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吳銘緯(Ming-wei Wu) 查詢紙本館藏

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化學學系

論文名稱

以綠色化學概念檢測生物檢體中人工合成麝香與烷基酚類流佈之研究
(Analysis of synthetic musks and occurence of alkylphenols in biota samples with green chemistry techniques)

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摘要(中)

人工合成麝香在19世紀就已經拿來取代天然麝香，從起源最早的硝基麝香，到後來的多環、巨環與酯環麝香都被廣為使用，因價錢便宜及香味宜人，因此硝基麝香與多環麝香經常添加在個人護理產品中。隨著製造以及使用過程中的排放，導致這些人工合成麝香累積在水、底泥與魚體中，因此必須開發一套快速及便利方法來檢測魚體中麝香的殘留。
　　本研究第一部分是，利用一步完成的微波輔助頂空固相微萃取裝置搭配氣相層析質譜儀分析魚類樣品，方法不僅快速且只需少量溶劑便能使用。將魚肉與4 mL的甲醇混和並攪拌10分鐘，再添加13 mL的去離子水，以PDMS/DVB的塗覆纖維置樣品頂空後，使用80 W微波，萃取5分鐘。此方法的偵測極限為0.08 ng/g – 0.5 ng/g，定量極限為0.3 ng/g – 2 ng/g。
　　對於這些魚肉樣品的初步檢測結果顯示，大部分的樣品都能檢測到人工合成麝香，利用標準添加法進行定量分析，待測物的總濃度介於1.0至14.0 ng/g，而再現性的標準偏差範圍為0.4 %至9.8 %。本研究開發的微波輔助頂空固相微萃取搭配氣相層析質譜儀，是具有快速檢測，步驟簡便及穩定性佳的優點，克服傳統萃取法中耗時且需使用大量溶劑的缺點，可用來偵測環境中魚體內的人工合成麝香。

　　烷基酚為烷基酚聚乙氧基醇類非離子型界面活性劑在環境中所降解的產物，已被證實會干擾生物體的內分泌機制，被稱之為環境賀爾蒙。此化學物質有親酯性質，因此會累積於生物體中，本研究第二部分為檢測馬公、台西、布袋、東石、七股與箔子寮所採樣的螺種，以達到監測烷基酚在生物體中流佈研究。
　　本研究中，利用蒸氣蒸餾法搭配氣相層析質譜儀來檢測螺肉樣品，將螺肉樣品放入圓底瓶中，並且加入100 mL的去離子水混和，與含4 mL正己烷的蒸氣蒸餾管連接，萃取一個小時再使用1 μL衍生化試劑做線上衍生。定量極限皆於20 ng/g以下，每個待測物的回收率介於80.3 % - 114.9 %，而相對標準偏差範圍為2.4 % - 12.7 %。
　　環境中不同的4螺種(細紋玉螺、扁玉螺、蚵岩螺、象牙鳳螺)皆無檢測出4-t-OP，但都可以檢測出4-NPs，其濃度範圍為23 ng/g - 3370 ng/g，在本研究中，不同螺種、不同地區與不同時間所採集的螺種其4-NPs濃度皆有顯著差異性。

摘要(英)

The use of musk flavor has a long history dating back to ancient times. Until the end of the nineteenth century the popular fragrance was obtained from natural sources. Nowadays synthetic compounds are almost exclusively used. They can be divided into four major classes: aromatic nitro musks, polycyclic musks, macrocyclic musks, and alicycloc musks. Due to their flavor odor and lower price, synthetic musks use to be added to personal care products, and release by the waste sludge and sewage. Musks also can easily accumulate in water, sludge, and biota, therefore a simple and effective method is required.
　　The first part of this study, one-step in situ microwave-assisted headspace solid-phase microextraction (MA-HS-SPME) coupled with gas chromato- graphy-mass spectrometry (GC-MS) analysis was presented as a fast and eco-friendly technique to determine synthetic musks in fish samples. The fish sample mixed with 5 mL MeOH and 13 ml deionized water was efficiently extracted by a polymehtylsiloxane- divinylbenzene (PDMS/DVB) fiber place in the headspace when extraction was microwave irradiated at 80 W for 5 min. The limits of detection (LODs) ranged from 0.08 ng/g to 0.5 ng/g and the limits of quantification (LOQs) ranged from 0.3 ng/g to 2 ng/g.
　　A preliminary analysis of fish samples revealed that all sample can be detected the synthetic musks, using a standard addition method, musks concentration were determined to range from 1.0 to 14.0 ng/g with relative standard deviation (RSD) ranging from 0.4 % to 9.8 %.
　　The results show that this MA-HS-SPME and GC-SIM-MS are reliable, sensitive, and stable analytical technique for a trace determination of synthetic musks in fish.
　　4-tert-octylphenol (4-t-OP) and 4-nonylphenol isomers (4-NPs) are two persistent degradation products form widely used nonionic surfactants alkylphenol polyethoxylates (APEOs). They have been demonstrated to exhibit the ability to mimic natural hormones. The second part of this study is analysis and monitors the hydrophobic alkylphenol compounds in snail in Taiwan.
　　In this study, one-step steam-distillation extraction followed by a gas chromatography-mass spectrometry is presented as a simple technique to determine alkylphenols in snail samples. The snail sample mixed with 100 ml deionized water into 250 mL round bottle, and connected with steam distillation tube which contained 4 mL hexane, then extraction for one hour. The recovery for each samples range from 80.3 % to 114.9 % with RSD ranged from 2.4% to 12.7%.
　　The 4-NPs concentrations ranged from 23 ng/g to 3370 ng/g in 4 different species (Natica lineata, NL, Neverita didyma, Nd, Thais clavigera, TC, Babylonia areolata, BA), but 4-t-OP was not detected in snail samples. The results showed that the concentration of 4-NPs in snails were significant different among sampling locations, species, and years.

關鍵字(中)

★ 綠色化學
★ 麝香
★ 烷基酚

關鍵字(英)

★ green chemistry
★ musks
★ alkylphenols

論文目次

中文摘要 I
英文摘要 III
謝誌 V
目錄 VI
圖目錄 X
表目錄 XIII
第一章　前言 1
1-1　研究緣起 1
1-2　研究目標 4
第二章　文獻回顧 5
2-1　麝香 5
2-1-1　麝香簡介 5
2-1-1-1　硝基麝香 7
2-1-1-2　多環麝香 10
2-1-1-3　巨環麝香 12
2-1-1-4　酯環麝香 15
2-1-2　合成麝香之危害性 17
2-1-3　文獻回顧 26
2-2　烷基酚類化合物 28
2-2-1-1　烷基酚類化合物簡介 28
2-2-2　烷基酚類化合物之危害性 32
2-2-3　文獻回顧 34
2-3　微波 36
2-3-1　微波介紹 36
2-2-2　加熱原理 37
2-2-3　微波優點 39
2-3　固相微萃取法 40
2-5　蒸氣蒸餾法 46
2-6　衍生化技術 48
2-6-1　矽烷化衍生法 48
2-7　品質保證與品質管制(quality assurance and quality control) 51
2-7-1　Mandel test 52
2-7-2　缺適性實驗(Lack-of-Fit test) 55
第三章　實驗步驟與樣品分析 57
3-1　實驗藥品與設備 57
3-1-1　實驗藥品 57
3-1-2　儀器設備 59
3-2　實驗步驟 61
3-2-1　標準品的配製 61
3-2-2　氣相層析質譜儀( 離子井 )的參數設定 63
3-2-2　氣相層析質譜儀( 四極柱 )的參數設定 65
3-2-4　MA-HS-SPME裝置 67
3-2-4　操作流程(固相微萃取法) 67
3-2-6　蒸氣蒸餾法裝置圖 69
3-2-7　操作流程(蒸氣蒸餾法) 69
3-3　生物檢體採集 71
第四章　結果與討論 72
4-1　人工合成麝香化合物之測定 72
4-1-1　氣相層析質譜儀對人工合成麝香的分析 72
4-1-1　人工合成麝香標準品的儀器偵測極限與線性範圍 76
4-1-3　固相微萃取法的塗覆纖維的最佳化 77
4-1-4　微波瓦數與時間的最佳化 79
4-1-5　萃取溶劑體積的最佳化 83
4-1-6　鹽類添加量的最佳化 85
4-1-7　pH的最佳化 87
4-1-8　微波輔助頂空固相微萃取的最佳化結果 89
4-1-8-1　微波輔助頂空固相微萃取之最佳化條件 89
4-1-8-2　微波輔助頂空固相微萃取之檢量線 90
4-1-9　Mandel測試與缺適性測試 92
4-1-10　魚類樣品中人工合成麝香的測定 94
4-2　烷基酚類化合物之測定 107
4-2-1　氣相層析質譜儀對烷基酚類化合物的分析 107
4-2-2　採樣地點與收集 109
4-2-3　萃取方法與回收率 111
4-2-4　螺種在地區上的差異 114
4-2-5　螺種在時間上的差異 116
4-2-6　不同螺種的差異 118
4-2-7　台灣本島與外島的差異性 120
4-2-8　萃取回收率 112
第五章　結論與建議 121
5-1　結論 121
5-2　建議 123
第六章　參考文獻 124

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指導教授

丁望賢(Wang-hsein Ding)

審核日期

2012-6-19

推文