以超音波輔助分散式液液微萃取法萃取水樣中的多環麝香化合物之方法開發

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楊清雅(Ching-ya Yang) 查詢紙本館藏

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化學學系

論文名稱

以超音波輔助分散式液液微萃取法萃取水樣中的多環麝香化合物之方法開發
(Ultrasound-assisted dispersive liquid-liquid microextraction for the rapid determination of synthetic polycyclic musks in aqueous samples)

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摘要(中)

近年來一群合成麝香香料於市面上廣泛的被使用，其中多環類麝香化合物在環境大氣、淡水、海洋及底泥中已陸續被檢出，此外這類化合物由於親脂性強，因而容易聚集在水中生物的體內，及肌肉細胞中，甚至在人體的脂肪組織及母乳中均檢測出有這類化合物的存在。這類化合物已被證實具有雌激素活性存在，易導致雌化現象產生，此外這類化合物隨著女性血液中所測得的濃度增加而增加女性導致小產的機率。
　　本研究將使用目前新開發的一項簡單，且以少量有機溶劑，即可同時搭配氣相層析質譜儀鑑定六種多環類麝香化合物的前處理方法，此方法為，超音波輔助分散式液液微萃取法(Ultrasound-assisted Dispersive Liquid-Liquid Microextraction，簡稱UA-DLLME)，研究中將探討幾個影響萃取的因素(如分散劑及有機萃取溶劑的選擇、添加鹽類的量等)並做最佳化。萃取的最佳條件為以比例1000 μL / 10 μL 的IPA（分散劑）/CCl4（萃取劑）做為萃取溶劑，將其打入10 mL水樣(含0.5 g NaCl)的尖底玻璃離心管中，接著經由超音波震盪1分鐘後，以5000 rpm離心10分鐘，抽取底部1 μL的液滴進入GC-MS中進樣。
此方法的定量極限(Limit of Quantification，簡稱LOQ)則低於0.5 ng/L。精密度所產生的相對標準偏差範圍均小於13%，回收率所表示的準確度可達到62-104%之間。在環境水樣中，搭配標準添加法，所得定量結果介於8.3至63.9 ng/L之間。
　　本研究所發展的方法，提供了迅速、簡便、節省、環境汙染小及靈敏度與再現佳等優點。是一項可廣泛應用的前處理方式。

摘要(英)

Currently, a group of widely used synthetic musk fragrances, synthetic polycyclic musks have been detected in air, freshwater, seawater and sediment samples. Because of their highly lipophilic properties, polycyclic musks have been also found in aquatic biota, such as mussels and fish, and even in human adipose tissue and breast milk. These compounds have demonstrated estrogenic activity, even higher concentrations of synthetic polycyclic musks in women’’s bloods have been correlated to higher rate of miscarriage.
　　In this study, a simple and solvent-less procedure was developed for the determination of six commonly found synthetic polycyclic musks in aqueous samples using ultrasound-assisted dispersive liquid-liquid microextraction (UA-DLLME) coupled gas chromatography-mass spectrometry (GC-MS). The parameters affecting the extraction efficiency of analytes from water samples were systematically investigated and the conditions optimized. The best extraction conditions involved the rapid injection of a mixture of 1.0 mL of isopropyl alcohol (as a dispersant) and 10 μL of carbon tetrachloride (as an extractant) into 10 mL of water containing 0.5 g of sodium chloride in a conical bottom glass tube. After ultrasonication for 1.0 min and centrifugation at 5000 rpm (10 min), the sedimented phase 1.0 μL was directly injected into the GC-MS system. The limits of quantitation (LOQs) were less than 0.5 ng/L. The precision for these analytes, as indicated by relative standard deviations (RSDs), were less than 13% for both intra- and inter-day analysis. Accuracy, expressed as the mean extraction recovery, was between 62 and 104%. Using a standard addition method, their total concentrations were determined to be in the range from 8.3 to 63.9 ng/L in various environmental samples.
　　The developed technique appears to be a good alternative extraction method for the determination of organic compounds in environmental water samples in that it is a simple, low cost, effective, and eco-friendly analytical method.

關鍵字(中)

★ 合成麝香
★ 超音波輔助分散式液液微萃取

關鍵字(英)

★ Ultrasound-assisted dispersive liquid-liquid mic
★ synthetic polycyclic musks

論文目次

中文摘要 I
Abstract III
謝誌 V
目錄 VI
圖目錄 IX
表目錄 XI
第一章　前言 1
1-1　　研究緣起 1
1-2　　研究目標 3
2-1　　藥物與個人護理產品 4
2-1-1　藥物與個人護理產品的來源 5
2-1-2　合成麝香 6
2-1-3　多環麝香 11
2-1-4　多環類麝香化合物於生物體中的汙染狀況 13
2-1-5　多環麝香化合物的毒性探討 20
2-1-6　相關研究文獻 25
2-2　　超音波輔助萃取法(Ultrasound-assisted extraction) 34
2-3　　分散式液液微萃取 35
2-3-1　引言 35
2-3-2　原理 36
2-3-3　分散式液液微萃萃取效率的影響因素 38
2-3-4　分散式液液微萃的應用 39
2-3-5　總結 42
2-4　　氣相層析質譜儀 48
2-4-1　質譜儀(Mass Spectrometry) 49
2-4-2　電子游離法(Electron ionization) 50
2-4-3　四極矩質譜儀(Quadrupole mass analyzer) 51
第三章　實驗步驟與樣品分析 53
3-1　　實驗藥品與設備 53
3-1-1　實驗藥品 53
3-1-2　儀器設備 54
3-2　　實驗步驟 56
3-2-1　標準品的配製 56
3-2-2　氣相層析質譜儀的參數設定 57
3-2-3　操作流程 59
3-2-4　實驗條件探討 60
3-3　　水樣採集 61
第四章　結果與討論 62
4-1　　氣相層析質譜儀對多環類麝香化合物的測定 62
4-1-1　多環類麝香化合物的分析 62
4-1-2　儀器的偵測極限 67
4-2　　超音波輔助分散式液液微萃取萃取 69
4-2-1　計算萃取濃縮倍率及萃取回收率 70
4-2-2　萃取劑的選擇 71
4-2-3　分散劑的選擇 75
4-2-4　萃取劑體積量的選擇 78
4-2-5　分散劑量的選擇 80
4-2-6　超音波震盪時間選擇 82
4-2-7　鹽的添加對萃取的影響 85
4-2-8　pH的影響 87
第五章　結論 103
第六章　參考文獻 105

參考文獻

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指導教授

丁望賢(Wang-hsien Ding)

審核日期

2011-6-22

推文