Please use this identifier to cite or link to this item: http://hdl.handle.net/11455/16826
標題: 質譜術於複雜基質中微量成分檢測之探討
Application of Mass Spectrometry in Determination of Trace Analytes in the Complex Matrix
作者: 李仁傑
Lee, Ren-Jye
關鍵字: mass spectrometry
質譜術
multiple-stage mass spectrometry
purge-assisted solid-hase microextraction
多次串聯質譜術
吹氣輔助微量固相萃取法
出版社: 化學系所
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摘要: 本研究主要利用質譜術於複雜基質中微量成分檢測與定量分析技術之探討。分為三部份,第一部份以多次串聯質譜術鑑定茶葉經高溫處理所產生未知成分,並探討茶中主成分沒食子兒茶素沒食子酸酯(epigallocatechin gallate, EGCG)轉變為沒食子酸(gallic acid, GA)的機制。此方式成功地鑑定三個沒食子兒茶素沒食子酸酯之二聚合相關化合物,並以多次串聯質譜術推論其化學結構以及其他產物;另藉由產物的形成,探討形成沒食子酸之過程與機制。 第二部份以自行改良之吹氣輔助頂空固相微量萃取裝置進行萃取及結合氣相層析質譜儀進行分析。探討水中四種氯酚類化合物之萃取以評估其應用於水中毒性物質分析的可能性。當氮氣流速控制在20 mL/min時透過1公分之中空纖維吹入水中,以85 μm 聚丙烯酸酯(polyacrylate, PA)塗覆材質之纖維於頂空吸附氯酚類化合物30分鐘,並將水溫控制在75℃時可以得到氯酚類化合物之最佳萃取效果。其回收率均大於83%,偵測極限可達sub-fg/mL,偵測極限範圍為0.1 到 0.4 pg/mL之間,相對標準偏差介於4到14%,偵測效果十分理想,並將其應用到垃圾滲出水中微量氯酚類化合物之檢測。以正交表方式評估影響待測物訊號最為顯著之因素,實驗結果顯示萃取溫度的影響最大。 第三部份以雙曲面式四極矩質譜儀應用於尿液中硝甲西泮及其代謝物之檢測。以固相萃取法結合大氣壓化學游離法之高度選擇反應偵測模式進行分析。實驗中將pH 7的尿液樣品一毫升經MP3碟形固相萃取管柱萃取後,再以兩毫升methanol/isopropanol/ NH4OH (78:20:2, v/v/v)混合溶劑沖堤可以得到 最好的萃取效果。其回收率均大於89.6%,最低可確認濃度範圍為0.5 到 1 ng/mL之間,組內(intraday)及組間(interday)精密度以相對標準偏差表示,其範圍分別為3.8%到7.4%以及 10.1%到20.9%之間。為避免偽陽性的分析結果,研究中亦評估將歐盟2002/657/EC對於液相層析串聯質譜術之要求應用於化合物之確認,並將此方法應用於真實尿液樣品之分析。本方法提供一靈敏且可靠的分析方法,可做為尿液中微量違禁藥物分析方法的參考。
The main target of this research was to evaluate the reliability of mass spectrometryin trace analysis of analytes in the complex matrices. The first investigation evalutes the releasing of gallic acid (GA) from (-)-epigallocatechin gallate (EGCG) in old oolong tea by data-dependent multiple-stage mass spectrometry. The possibility of releasing GA from EGCG in old tea preparations was supported by an in vitro observation of GA degraded from EGCG under heating conditions mimicking the drying process. Negative electrospray ionization with the data-dependent mode of MSn was used to study the formation pathway of GA in old oolong tea. The MSn data show the possibility of GA released from the dimer of EGCG. The second investigation evaluates a simple, sensitive and effective method for simultaneous determination of chlorophenols in aqueous samples using purge-assisted headspace solid-phase microextraction (PA/HS-SPME) coupled to gas chromatography-mass spectrometry (GC/MS). In the new method, purging the sample enhances the removal of the trace chlorophenols without derivatization from the matrices to the headspace. Extraction parameters including extraction temperature, purge gas flow rate and extraction time were systematically investigated. Under optimal conditions, the relative standard deviations (RSDs) were 4-11% at 50 pg/mL and 5-14% at 5 pg/mL, respectively. The recoveries were above 83%. Detection limits were determined at the fg level, ranged from 0.1-0.4 pg/mL. The proposed method was successfully applied to the analysis of chlorophenols in landfill leachate. The most affected factor among four main factors was also evaluated via L9(3)4 orthogonal array. In the third evaluation, a rapid method was developed for screening nimetazepam and its metabolites, 7-aminonimetazepam (7-AN) and nitrazepam, in urine using solid-phase extraction combined with liquid chromatography-atmospheric pressure chemical ionization/tandem mass spectrometry (SPE-LC-APCI/MS/MS) with enhanced mass resolution. High extraction efficiency was obtained using a MP3 disk cartridge to extract analytes in a pH 7 urine sample, which was then eluted with a solvent mixture, methanol/isopropanol/NH4OH (78/20/2,v/v/v). Two mass transitions of every drug were utilized for qualitative and quantitative purposes. The limits of confirmation (LOC) were 0.5-1.0 ng/ mL. The linear concentration range was 0.5-50 ng/mL, with coefficients of determination over 0.995. Intraday and interday precision represented in RSD% were in the range of 3.8-7.4% and 10.1-20.9%, respectively. The proposed method offers a rapid and low ng/mL sensitive method for analyzing nimetazepam and its metabolites in urine. The feasibility of applying the proposed method to identify nimetazepam and its metabolites in real samples was examined by analyzing urine samples from patients.
URI: http://hdl.handle.net/11455/16826
其他識別: U0005-2703201123114800
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