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博碩士論文 etd-0616115-152958 詳細資訊
Title page for etd-0616115-152958
論文名稱
Title
以大氣質譜法大規模篩檢環境中塑化劑之物品
Large Scale Screening of Plasticizers by Ambient Mass Spectrometry
系所名稱
Department
畢業學年期
Year, semester
語文別
Language
學位類別
Degree
頁數
Number of pages
112
研究生
Author
指導教授
Advisor
召集委員
Convenor
口試委員
Advisory Committee
口試日期
Date of Exam
2015-07-10
繳交日期
Date of Submission
2015-07-24
關鍵字
Keywords
熱脫附、塑化劑、大氣壓力質譜法、動物用藥、液相微萃取
Veterinary drug, Phthalates, Liquid Phase Microextraction (LPME), Ambient Mass Spectrometry (AMS), Thermal Desorption (TD)
統計
Statistics
本論文已被瀏覽 5717 次,被下載 54
The thesis/dissertation has been browsed 5717 times, has been downloaded 54 times.
中文摘要
大氣質譜法(Ambient Mass Spectrometry, AMS)是一種可以在大氣壓力下進行樣品分析的質譜技術,具有分析時間短、不需要或是只需簡單樣品前處理及可以提升更換樣品的速度等優勢,因此,近年來有許多新式的大氣壓力游離技術陸續被研發出來。本研究結合熱脫附法(Thermal Desorption, TD)及電噴灑游離法(Electrospray ionization, ESI)開發出可快速分析不同樣品之熱脫附電噴灑游離質譜法(Thermal Desorption Electrospray Ionization Mass spectrometry, TD-ESI/MS),其操作流程是先利用探針進行取樣,再將取樣探針置入高溫的熱脫附裝置中,進而脫附產生中性氣相分子,這些氣化的分析物經由熱氣流的帶動,傳送到電噴灑離子雲中進行後游離,經由離子-分子反應(Ion-molecule Reaction, IMR)產生分析物離子,最後經由後端質量分析器進行偵測。

由於大氣質譜法具有快速分析的特色,因此相當適合在短時間內進行大量樣品分析。因此,在第一部分的研究中以熱脫附電噴灑游離質譜法(TD-ESI/MS)針對幼稚園內,所有幼童會接觸到塑膠製品,進行塑化劑的大規模篩檢分析。其做法相當簡單,只需以取樣探針刮取固定面積的樣品表面,再將沾附分析物的探針以TD-ESI/MS進行檢測,並於15秒內得到分析結果。研究中選定高雄市兩所幼兒園,針對內園區內所有塑膠物件,進行八種塑化劑快篩分析,包括有Dibutyl Phthalate(DBP)、Dimethyl Phthalate(DMP)、Di-octyl Phthalate(DOP)、Di(2-ethylhexyl)Phthalate (DEHP)、Di-iso-nonyl Phthalate (DINP)、Benzyl Butyl Phthalate (BBP)、Di-isodecyl Phthalate (DIDP)及Diethyl Phthalate (DEP)。經由TD-ESI/MS快篩分析結果指出,利用探針刮取2cmx 200 µm面積內含有DEHP且檢測值高於2 ng以上的樣品占全部樣品的13.7%,其次則是DINP占了7.7%。就樣品種類而言,含塑膠材質的袋子類和大型玩具類在高含量DEHP的檢出率中分別高達14.3%與13.4%。本次研究於兩所幼稚園現場採集近千件樣品、樣品進行二重複分析、整理質譜數據至撰寫報告,僅需短短2天的時間,證明此技術相當適合應用在即時大規模篩檢分析上。

在第二部分的研究主要是開發簡單的液液萃(Liquid Liquid Extraction, LLE)取作為TD-ESI/MS取樣的前處理步驟,以降低複雜樣品中基質干擾。研究中以液相微萃取法(Liquid Phase Microextraction, LPME)為基礎,開發一簡單萃取探針進行取樣,其作法是在環型探針上方鑲上一片矽膠片(silicon pads),在其保護下可使有機溶劑(約5 µL)在樣品溶液中進行有效萃取,最後結合TD-ESI/MS技術分析萃取後的有機溶劑內之分析物。此方法以簡單的分析流程、造價便宜及低有機溶劑消耗,就在短時間內(約10分鐘)達到高靈敏度及低偵測極限的分析。LPME/TD-ESI/MS的初步結果顯示,在分析100 µg/mL磺胺類藥物(Sulfamethazine, Sulfamethoxazole)和乙型受體素類藥物(Clenbuterol, Salbutamol, Terbutaline),其再現性(n = 5)分別小於8.3%和6.8%。接著,將此動物藥物以添加方式混於牛奶、蜂蜜水和豬血等含水樣品,以LPME/TD-ESI/MS/MS來進行定量分析的測試,其R2分別為0.9979、0.9981和0.9981,均可得到良好的線性範圍。
Abstract
Ambient mass spectrometry (AMS) is known for its unique feature to perform analysis without sample pretreatment, and has been used for direct, rapid, and real-time detection of chemical compounds. Techniques such as DESI, DART, and ELDI have been demonstrated to be useful for rapidly characterizing chemical and biological compounds. In this study, we have developed an ambient mass spectrometric technique known as thermal desorption electrospray ionization mass spectrometry (TD-ESI/MS). A direct metallic sampling probe was used to collect analytes from sample surfaces regardless of sample size or shape. Analytes were thermally desorbed, post-ionized by reacting with charged solvent species in an electrospray plume, and the ions were subsequently detected by the mass analyzer attached to the ion source. .The residual sample on the metallic probe is rapidly removed by burning the probe with a flame from a torch. The time required to complete an analysis was less than 15 seconds.

In the first study, TD-ESI/MS was used to screen phthalates [ Dibutyl Phthalate (DBP), Dimethyl Phthalate (DMP), Di-octyl Phthalate (DOP), Di(2-ethylhexyl)Phthalate (DEHP), Di-iso-nonyl Phthalate (DINP), Benzyl Butyl Phthalate (BBP), Di-isodecyl Phthalate (DIDP)and Diethyl Phthalate (DEP) ] on the objects in two kindergartens. Approximately one thousand samples were collected, analyzed and the results were reported within two days. Sample collection was completed in approximately 3hrs, TD-ESI/MS analysis was completed in 10 hrs, and data organization and report writing took another 5 hrs. The results indicate that approximately 30% and 20% of the objects in the two kindergartens contain higher level of phthalates. The success in screening phthalates in all the objects found in the two kindergartens suggests that performing large scale screening of phthalates in the living environment is possible.

In the second study, liquid-phase microextraction (LPME) was coupled with an ambient ionization technique, known as thermal desorption electrospray ionization (TD-ESI) for rapid screening of veterinary drug residues in foods. The ambient TD-ESI ion source consisted of (1)a metal loop suspending 5 μL of organic solvent was used for analyte extraction in liquids, (2)after equilibrium among analytes, sample solution, and extraction solvent was reached, a heating oven for desorbing analytes on the LPME probe.Preliminary results of LPME/TD-ESI/MS/ showed that reproducibility tests (n=5) for 10 µg/mL of sulfonamides(sulfamethazine, sulfamethoxazole) and β-agonists (clenbuterol, salbutamol, terbutaline) were less than 7.6 % and 10.2 %, respectively. The sensitivities of sulfamethazine(m/z 279) and clenbuterol(m/z 277)improved,; where detection limits could be decreased as low as 1.0 µg/mL, and 0.1 µg/mL while using the LPME fiber as a sampling probe. Furthermore, the capacity of LPME/TD-ESI/MS for quantitative analysis was evaluated using milk, honey and pork blood spiked with spiked veterinary drugs. Excellent correlations of determination were achieved for analytes with R2values greater than 0.997、0.998 and 0.972, respectively.
目次 Table of Contents
論文審定書………………………………………………………………………………i
謝誌…………………………………………………………………………………….. ii
中文摘要…………...………………………………………………………………….. iv
英文摘要……………………………………………………………………………..... vi
目錄…………...…………………………………………………………………….... viii
圖目錄…………..………………………………………………………………………xi
表目錄…………..………………………………………………………………….....xvii
第一章、緒論……………………………………………………………………………1
第一節、前言 1
第二節、傳統層析方法檢測 2
第三節、大氣壓力游離質譜法(Ambient Ionization Mass Spectrometry) 6
1.直接游離法(Direct Ionization) 6
2.直接脫附游離法(Direct Desorption/Ionization) 7
3.兩階段式游離法(Two- step Ionization) 7
第四節、熱脫附電噴灑游離法(Thermal Desorption Electrospray Ionization, TD-ESI) 9
第五節、液相微萃取法(Liquid Phase Microextraction, LPME) 11
1.液相微萃取之簡介 11
2.單滴微萃取(Single Drop Microextraction, SDME) 12
3.中空纖維液相微萃取法(Hollow-Fiber Liquid Phase Microextraction, HF-LPME) 13
4.分散式液-液微萃取法(Dispersive liquid-liquid microextraction, DLLME) 15
第六節、液相微萃取法結合大氣壓力游離質譜法分析技術 17
1.液相微萃取法結合脫附電噴灑游離質譜法(Desorption electrospray ionization Mass Spectrometry, DESI-MS)17
2.液相微萃取法結合直接分析即時游離質譜法(Direct analysis in real time-Mass Spectrometry, DART-MS) 19
3.液相微萃取法結合大氣壓力雷射輔助脫附遊離法(Atmospheric-PressureMatrix-Assisted Laser-Desorption Ionisation Mass Spectrometry, AP-MALDI-MS) 19
第七節、論文目標 21
第二章、實驗………………………………………………………………………….22
第一節、實驗設計 22
1. TD-ESI/MS操作的分析流程 22
2.大規模樣品採樣流程 23
2-1事前準備工作 23
2-2實際採樣過程 24
2-3樣品存放盒置放流程 25
3.液相微萃取(Liquid Phase Microextraction, LPME)裝置設計 25
4. LPME/TD-ESI/MS之分析流程 26
5. TD-ESI/MS和LPME/TD-ESI/MS參數設定 28
第二節、實驗藥品與試劑 30
1.試劑 30
2.藥品 30
第三節、藥品配製 33
第四節、儀器設備 35
1.三段式四極柱串聯質譜儀 35
第三章、結果與討論……………………………………………………………..…….37
第一節、以TD-ESI/MS大規模篩檢幼稚園塑化劑之物品 37
1.塑化劑的種類介紹 37
2.大規模篩檢塑化劑之參數探討 39
3.大規模篩檢塑化劑之TD-ESI/MS和LC-ESI/MS方法驗證 41
4.大規模篩檢塑化劑 47
5.大規模篩檢塑化劑之檢測結果資料統整 50
第二節 LPME取樣探針結合TD-ESI/MS之開發 54
1. LPME/TD-ESI裝置參數探討 54
2.以LPME/TD-ESI技術應用於過期杯水的快速偵測 57
第三節、LPME/TD-ESI技術應用於食品中動物用藥之殘留快速偵測 59
1.動物用藥簡介 59
2. LPME萃取溶劑之探討 60
3. LPME萃取時間之探討 62
4. LPME/TD-ESI/MS再現性之探討 64
5. LPME/TD-ESI/MS偵測極限之探討 66
6. LPME/TD-ESI/MS定量分析之探討 68
7. LPME/TD-ESI/MS和SPME/TD-ESI/MS之比較 70
8.以LPME/TD-ESI/MS對食品中動物用藥之定量分析 72
9.動物用藥的訊號藉由二次質譜法(MS/MS)進行進一步的確認 76
第四章、結論………………………………………………………………………..….78
附錄一…………………………………………………………………..……………...80
參考文獻……………………………………………………………………………….90
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