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研究生: 江坤壕
Chiang, Kun-Hao
論文名稱: 藉由混合模式液相層析質譜技術分析高極性農藥
Analysis of Highly Polar Pesticides Using Mixed Mode Liquid Chromatography Tandem Mass Spectrometry
指導教授: 陳頌方
Chen, Sung-Fang
口試委員: 曾素香
Tseng, Su-Hsiang
葉怡均
Yeh, Yi-Chun
陳頌方
Chen, Sung-Fang
口試日期: 2023/07/25
學位類別: 碩士
Master
系所名稱: 化學系
Department of Chemistry
論文出版年: 2024
畢業學年度: 112
語文別: 中文
論文頁數: 100
中文關鍵詞: 高極性農藥液相層析質譜
英文關鍵詞: Highly polar pesticides, Liquid chromatography, Mass spectrometry
研究方法: 實驗設計法
DOI URL: http://doi.org/10.6345/NTNU202400637
論文種類: 學術論文
相關次數: 點閱:100下載:0
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  • 農藥廣泛地用於現今的農業當中,其伴隨的效益不僅可大幅降低人類的種植成本,更可以穩定且充足的產出作物以供應市場需求。然而,隨著農藥的使用不斷增加,食品安全問題以及檢驗方法的議題逐漸被重視。根據農藥的辛醇-水分配係數(Kow)可分為疏水性農藥和高極性農藥。高極性農藥因為其 logP 小且具有兩性離子特性,不易藉由逆相層析質譜進行分析。在本研究中,對益收生長素(Ethephon)、福賽得(Fosetyl-Al)、抑芽素(Maleic hydrazide)、嘉磷塞(Glyphosate)、固殺草(Glufosinate)及其代謝物等9種高極性農藥,使用混合模式管柱和醯胺管柱進行分離並使用液相層析串聯質譜法進行分析。藉由調整移動相的組成比例和層析梯度的改變來進行層析條件的優化。分別針對混合模式管柱和醯胺管柱進行探討,發現在移動相中加入甲酸對混合模式管柱和醯胺管柱至為重要。在優化後的層析條件下,混合模式管柱能夠有效地滯留9個高極性農藥並能在5分鐘內完成分離;而醯胺管柱亦可在10分鐘內完成。9種分析物的線性定量範圍為 0.5-100 ngmL-1,R2 > 0.995。優化後的分析方法結合Quick Polar Pesticide (QuPPe) 方法未來可應用於食物樣品分析。

    Pesticides are widely used in daily agriculture and the use of them is a major food safety concern. Considering the octanol-water distribution coefficient (Kow) of pesticides, they can be categorized to hydrophobic and highly polar pesticides (HPP). Highly polar pesticides are not easy to be analyzed by reverse phase LC-MS because their small logP and zwitterionic characteristics. In this study, nine HPP including ethephon, fosetyl-Al, maleic hydrazide, glyphosate, glufosinate and their metabolites were analyzed by mixed mode and amide liquid chromatography tandem mass spectrometry. The chromatographic conditions, including mobile phase compositions and gradients, for Obelisc N and amide columns were investigated and optimized for the separation of HPP. Addition of formic acid in the mobile phase was crucial for both Obelisc N and amide chromatography. With optimized conditions, all nine HPP were effectively retained and resolved by Obelisc N and amide columns in 15 min. The linear quantitative range of nine analytes was ranged 0.5-100 ngmL-1 with R2 > 0.995. The optimized LC-MS combined with Quick Polar Pesticides methods (QuPPe) will be further applied for food samples using HPP.

    謝誌 I 摘要 II Abstract III 目錄 IV 表目錄 VII 圖目錄 VIII 第一章 序論 1 第一節 農藥的種類及應用 1 一、農藥 1 二、高極性與疏水性農藥之定義 3 三、高極性農藥之種類 4 四、高極性農藥之應用 7 五、高極性農藥之檢測 8 第二節 高效能液相層析技術 9 一、高效能液相層析法 9 二、層析管柱 12 三、偵測器 14 第三節 質譜儀技術 15 一、質譜法 15 二、電灑游離法 18 三、三段四極桿串聯式質譜儀 20 第四節 多重反應監測之定量分析 22 第五節 實驗動機與目的 24 第二章 實驗材料與分析方法 25 第一節 實驗試劑 25 第二節 實驗樣品 26 第三節 實驗設備 26 第四節 實驗方法 28 一、 分配係數 28 二、 極性與極性表面積 29 三、 Quick Polar Pesticides (QuPPe) 29 四、 高效能液相層析參數設定 30 五、 質譜儀參數設定 32 六、 檢量線 33 七、 方法確效 34 第三章 結果與討論 35 第一節 高效能液相層析參數 35 一、 層析管柱的選擇 35 二、 移動相 37 三、 梯度最佳化 40 第二節 最佳化質譜儀參數設定 42 一、 電灑游離法參數 42 二、 離子對的選擇與電壓優化 43 第三節 層析管柱比較 46 一、 混合模式管柱 Obelisc N column 46 二、 醯胺管柱 Amide column 54 三、 矽膠管柱 Silica column 59 四、 碳十八管柱 C18 column 60 五、 五氟苯基管柱 F5 column 61 六、 氰基管柱 CN column 62 七、 六支管柱之滯留性評比 63 八、 基質評估 65 第四節 方法確效 68 一、 專一性 68 二、 檢量線 70 三、 準確度與精密度 77 四、 偵測極限與定量極限 80 第五節 回顧與比較其他文獻之檢驗方法 81 第四章 結論與未來展望 85 參考文獻 86 附錄 97

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