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研究生:蔣沛廷
研究生(外文):Chiang, Pei-Ting
論文名稱:比較電灑游離法與大氣壓化學游離法結合液相層析串聯式質譜儀對農藥檢測之差異
論文名稱(外文):Comparison of electrospray ionization and atmospheric-pressure chemical ionization in pesticide analysis using LC-MS/MS
指導教授:陳頌方
指導教授(外文):Chen, Sung-Fang
學位類別:碩士
校院名稱:國立臺灣師範大學
系所名稱:化學系
學門:自然科學學門
學類:化學學類
論文出版年:2021
畢業學年度:109
語文別:中文
論文頁數:133
中文關鍵詞:農藥大氣壓游離法液相層析-串聯式質譜儀定量
外文關鍵詞:PesticidesAtmospheric pressure chemical ionizationLC-MS/MSQuantification
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農藥的使用使人類文明蓬勃發展,其帶來的效益讓作物能夠穩定生長並提供我們足夠的食物。但隨著農藥的用量越來越多,對環境跟人體的會造成不同程度的毒性影響身體健康甚至生命安全。依據2017年我國衛生福利部食品藥物管理署的規範,食品中殘留農藥的檢測方法訂定了373項,利用液相層析串聯質譜儀搭配電灑游離法和氣相層析串聯質譜儀搭配電子游離法進行分析。本實驗利用液相層析串聯式質譜儀的技術針對現行農藥殘留公告方法中農藥進行實驗,移動相使用甲酸銨水溶液搭配甲醇,比較大氣壓化學游離法與電灑游離法對於各農藥之游離效率。原以電灑游離法分析之196項農藥中,有6項農藥在大氣壓化學游離法下有比電灑游離法更佳的靈敏度;原以電子游離法分析之177項農藥中找出43項化合物以大氣壓化學游離法配合液相層析質譜法進行分析,並能夠符合現行法規之定量極限。結果顯示大氣壓化學游離法對擁有Triazine、Imidazole、Triazole、Pyrazole等官能基之農藥游離效率極佳。線性範圍落在1 - 200 ng/mL之間,相關係數皆在r = 0.996以上;準確度介於 86.7% - 138.8%;精密度使用變異係數表示數值介於0.19% - 13.87%。
The use of pesticides has made human civilization to flourish, and its benefits have allowed crops to grow steadily and provide us with sufficient food. However, the increasing use of pesticides let the environment and the human body expose to different levels of toxicity, which affects health even life safety. According to the regulation of the Taiwan Food and Drug Administration (TFDA) in 2017, there are 373 pesticides detection with the test methodfor pesticide residues in food, which are analyzed by liquid chromatography tandem mass spectrometry (LC-MS/MS) with electrospray ionization (ESI) and gas chromatography tandem mass spectrometry (GC-MS/MS) with electron ionization (EI). In this study, the pesticides were separated using an aqueous solution of ammonium formate with methanol as the mobile phase, and ionization efficiency comparison was made between atmospheric pressure chemical ionization (APCI) and electrospray ionization (ESI). Among the 196 pesticides originally analyzed by the ESI method, 6 pesticides had better peak areas and better signal-to-noise ratios using APCI; 43 pesticides originally analyzed by the EI method, and good analytical results were also obtained by APCI method.. Among them, the APCI method provided superior efficiency for pesticides which had Triazine, Imidazole, Triazole, Pyrazole functional groups. The linear range was from 1 to 200 ng/mL, and the coefficient of determination were all above r = 0.996. The accuracy ranged from 81.8% to 138.8%, and the precision was between 0.19% and 13.87%.
第一章 序論 1
第一節 農藥之發展與歷史 1
一、農藥 1
二、農藥之毒性以及分級 3
三、農藥之作用機制 5
第二節 高效能液相層析技術 7
一、高效能液相層析法 7
二、層析管柱 9
三、偵測器 11
第三節 質譜儀技術 12
一、電子游離法 16
二、大氣壓化學游離法 18
三、電灑游離法 21
四、游離源差異比較 23
五、三段四極桿串聯式質譜儀 25
六、電子倍增管 27
第四節 多重反應監測之定量分析 29
第五節 實驗動機與目的 31
第二章 實驗材料與分析方法 32
第一節 實驗試劑 32
第二節 實驗樣品 33
第三節 實驗設備 33
第四節 實驗方法 34
一、分配係數 34
二、極性與極性表面積 35
三、高效能液相層析參數設定 35
四、質譜儀參數設定 36
五、檢量線 38
六、方法驗證 39
第三章 結果與討論 40
第一節 高效能液相層析參數 40
一、層析管柱的選擇 40
二、移動相 42
三、梯度最佳化 43
第二節 最佳化質譜儀參數設定 45
一、電灑游離法參數 45
二、大氣壓化學游離法參數 46
三、離子對的選擇與電壓優化 52
第三節 游離源比較 54
一、LC農藥標準品 54
二、GC農藥標準品 70
第四節 方法驗證 88
一、專一性 88
二、檢量線 89
三、準確度與精密度 94
四、同日間精密度與異日間精密度 99
五、偵測極限與定量極限 103
第五節 回顧與比較其他文獻之檢驗方法 105
第四章 結論與未來展望 107
參考文獻 109
附錄 113
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