以離子配對高效液相層析儀檢測螢光增白劑在不同基質中之研究

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許瑋娟(Wei-Chuan Shu) 查詢紙本館藏

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化學學系

論文名稱

以離子配對高效液相層析儀檢測螢光增白劑在不同基質中之研究
(Determination of Fluorescent Whitening Agents in different matrixs by Ion-Pair High-Performance Liquid Chromatography)

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摘要(中)

摘要
本研究是針對四個二苯乙烯C.I.28、C.I.205、C.I.134和DAS1及一個二苯乙烯聯苯的DSBP螢光增白劑(Fluorescent Whitening Agents, FWAs)，發展出一套穩定、可靠的微量檢測技術，以測定這些物質在不同基質－洗衣用清潔劑、紙類、嬰幼兒衣物及環境中水樣中之含量。這個方法包括了在樣品前處理中－洗衣用清潔劑是以溶解、振盪及過濾三步驟完成;紙類和嬰幼兒衣物以hot-water extraction/SPE進行;水樣則是採用碳-18固相萃取法，以達到同時分離、萃取及去除干擾物質的目的，並藉由離子配對-高效液相層析儀搭配螢光偵測器(Ion-Pair HPLC/FLD)來加以定性及定量。
HPLC以C18當作層析管柱，藉由等速流析離子配對液相層析法可達到良好的分離，線性範圍為0.5 ~ 5?103 ng/L，線性相關係數0.999以上，定量偵測極限為0.1~0.01 µg/L。
本研究針對市面上常見之19種洗衣用清潔劑進行分析，結果顯示DSBP和DAS1是比較普遍使用添加於洗衣清潔劑中的FWAs。而hot-water extractiont成功地應用於紙類及嬰幼兒服飾的處理，利用碳-18萃取回收率分別為76~91%及81~92%，相對標準偏差分別在2.0~3.8%及3.1~4.0%之間。環境水樣實驗結果顯示，在添加FWAs於不同水樣時，其碳-18萃取回收率為72.6~89.4%，相對標準偏差在2.4~8.9%之間，而各個測點所偵測到的FWAs其相對標準也皆在3.0~5.8%之內，此說明了本套分析技術的穩定性及對複雜環境樣品中微量污染物檢測之可行性。

摘要(英)

Abstract
The purpose of this study is to develop a method for the analysis of four stilbene-type disulfonate and one distyrylbiphenyl-type fluorescent whitening agents (FWAs) in different matrixes: laundry detergents, papers and infant clothes, as well as river waters. The sample pretreatment methods involve: the laundry detergent using dissolved, filter and oscillation; the paper and infant cloth samples using a hot-water extraction with SPE; the water sample using the C18 SPE cartridge. The contents of FWAs were then determined by an isocratic ion-pair chromatography with C18 reversed- phase column, applying TBA as the ion-pair reagent, and equipped with fluorescent detection. No further sample cleanup procedures were necessary due to the sensitive and selective fluorescence detection. The accuracy and precision of the method was validated and was successfully applied to determine the contents of FWAs in laundry detergents, papers, infant clothes and surface waters.
The quantitation limits were 0.1 to 0.01 ?g/L. The linear response was performed in the concentration covering the range from 0.05 to 500 ng/mL for DSBP, and 0.5 to 5000 ng/mL (in five-level) for other four FWAs. The calibration curve was linear with coefficients of determination r2 > 0.999. The precisions of the curves as indicated by R.S.D. of calibration factors (CF = peak area/amount) were 4.5 ~ 8.7%.
For laundry detergents, the results show that the DSBP (0.5 to 2700 ?g/g) and DAS1 (29 to 980 ?g/g) are the two most added FWAs in detergents. For paper and infant cloth, recovery of FWAs in spiked paper and infant cloth samples was between 76 to 92% and precision (RSD) ranging from 2.0 to 4.0%. Analysis of six paper materials and three infant clothes found concentrations of FWAs ranging between 0.01 to 3.8 ?g/g and n.d. to 24 ?g/g, respectively. For river water, recovery of FWAs in spiked water samples was between 73 to 89% and precision (RSD) ranging from 2.4 to 8.9%. Analysis of for water samples found concentrations of FWAs ranging between 0.02 to 3.5 ?g/L. The results demonstrated that the developed method is reliable, and offering a convenient analytical technique for trace-level determination of FWAs in complex environmental samples.

關鍵字(中)

★ 螢光增白劑
★ 固相萃取法
★ 清潔劑
★ 高效液相層析儀

關鍵字(英)

★ fluorescent whitening agent
★ solid-phase extraction
★ high performance liquid chromatography

論文目次

目錄
中文摘要 ------------------------------------------------------------------- I
英文摘要 ------------------------------------------------------------------- III
目錄 ------------------------------------------------------------------------- V
表目錄 ---------------------------------------------------------------------- VIII
圖目錄 ---------------------------------------------------------------------- IX
第一章前言 -------------------------------------------------------------- 1
1-1 研究緣起 -------------------------------------------------------- 1
1-2 研究目標 -------------------------------------------------------- 3
第二章文獻回顧 --------------------------------------------------------- 4
2-1 螢光增白劑簡介 -------------------------------------------------- 4
2-2 螢光增白劑的分類 ----------------------------------------------- 7
2-2-1 主要研究之螢光增白劑 ---------------------------------- 8
2-2-2 螢光增白劑的作用 ---------------------------------------- 10
2-2-3 螢光增白劑的增白原理 ---------------------------------- 11
2-3 螢光增白劑的其他相關性質研究 ----------------------------- 13
2-4 國內外檢測方法之相關研究 ----------------------------------- 17
2-5 固相萃取法 -------------------------------------------------------- 19
2-6 高相液相層析儀 ------------------------------------------------- 23
2-6-1 原理 --------------------------------------------------------- 23
2-6-2 離子配對層析法 ------------------------------------------ 25
第三章實驗步驟與樣品分析----------------------------------------- 27
3-1 實驗藥品與儀器設備 ------------------------------------------- 27
3-1-1 實驗藥品 --------------------------------------------------- 27
3-1-2 儀器設備 --------------------------------------------------- 29
3-2 實驗步驟 ---------------------------------------------------------- 30
3-2-1 標準品的製備 --------------------------------------------- 30
3-2-2 固相萃取步驟 --------------------------------------------- 30
3-2-3 樣品前處理步驟 ------------------------------------------ 31
3-2-4 高效能液相層析儀設定參數 --------------------------- 32
3-3 採樣地點及流程 ------------------------------------------------- 33
第四章結果與討論 ----------------------------------------------------- 35
4-1 建立分析方法 ---------------------------------------------------- 35
4-1-1 分析物最大吸收長 --------------------------------------- 35
4-1-2 離子對試劑的選擇 ----------------------------------------- 37
4-1-3 離子對試劑濃度的影響 ----------------------------------- 39
4-2 經HPLC分離的結果與討論 -------------------------------- 41
4-3 定性、定量及偵測極限 -------------------------------------- 42
4-4 檢量線製作 ----------------------------------------------------- 44
4-5 回收率探討 ----------------------------------------------------- 45
4-6 洗衣用清潔劑之檢測 ----------------------------------------- 48
4-7 紙類及嬰兒幼服飾之檢測 ----------------------------------- 53
4-8 環境水樣 -------------------------------------------------------- 58
第五章結論 ------------------------------------------------------------ 61
參考文獻 --------------------------------------------------------------- 63
表目錄
表2-1 螢光增白劑的種類----------------------------------------------- 7
表2-2 Greifensee和Switzerland中螢光增白劑的結果------------ 16
表2-3 SPE方法的結果整理--------------------------------------------- 20
表2-4逆相離子對層析圖的系統--------------------------------------- 26
表4-1 分析物之理論板數 ---------------------------------------------- 41
表4-2 HPLC再線性的探討---------------------------------------------- 43
表4-3市售洗以用清潔產品之檢測結果------------------------------ 49
表4-4 Spiked reproducibility and contents of FWAs found in paper materials and infant clothes-------------------------------------- 54
表4-5 真實水樣分析結果----------------------------------------------- 59
圖目錄
圖1-1 DAS1和DSBP的結構及全名 ------------------------------------ 2
圖2-1 (a) 香豆素 ------------------------------------------------------------- 5
(b)4,4’-三嗪基氨基二苯乙烯-2,2’-二磺酸衍生物體結構----- 5
圖2-2 分析物的結構 -------------------------------------------------------- 9
圖2-3 螢光增白劑的作用 ------------------------------------------------ 10
圖2-4 螢光增白劑之吸收光波波長之作用模式 --------------------- 12
圖2-5 Amsonic acid與Diethylstilbestrol結構圖 ------------------- 14
圖2-6 異構化過程（Reversible isomerization process）------------- 15
圖2-7 二種固相萃取劑的化學構造 ------------------------------------ 22
圖2-8 固相萃取流程圖 -------------------------------------------- 22
圖2-9 HPLC/FLD結構圖 ----------------------------------------------- 24
圖3-1 採樣點地圖----------------------------------------------------------- 34
圖 4-1 分析物之螢光光譜吸收圖譜 ----------------------------------- 36
圖4-2 不同長碳鏈離子對試劑對分析物分離的影響---------------- 38
圖4-3 (I) TBA濃度的影響------------------------------------------------- 39
(II) TBA濃度變化的層析圖-------------------------------------- 40
圖4-4 五個螢光增白劑標準品的層析圖------------------------------- 41
圖4-5檢量線----------------------------------------------------------------- 44
圖4-6 不同條件對固相萃取法之回收率影響------------------------- 46
圖4-7萃取層析圖：(a) spike (b) blank------------------------------- 47
圖4-8 液狀清潔劑層析圖------------------------------------------------ 50
圖4-9 粉狀清潔劑層析圖------------------------------------------------ 51
圖4-10 衣領精層析圖----------------------------------------------------- 52
圖4-11 Tissue代表層析圖------------------------------------------------ 55
圖4-12 Tissue代表層析圖------------------------------------------------ 56
圖4-13 (a) SPE spike (b) Infant cloth-II層析圖----------------------- 57
圖4-14真實水樣層析圖 (a) SPE spike (b) site I
(C) site IV ------------------- 60

參考文獻

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指導教授

丁望賢(Wang-Hsien Ding)

審核日期

2004-6-29

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