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作者:吳文菓
作者(英文):Wen-Guo Wu
論文名稱:使用質譜儀分析農藥代謝物的碎片離子及其機制
論文名稱(英文):Analyzing the product ions and the dissociation mechanisms of pesticide metabolites by mass spectrometry.
指導教授:何彥鵬
指導教授(英文):Yen-Peng HO
口試委員:江政剛
胡安仁
口試委員(英文):Chiang-Cheng Kang
An-Ren Hu
學位類別:碩士
校院名稱:國立東華大學
系所名稱:化學系
學號:610712008
出版年(民國):112
畢業學年度:111
語文別:中文
論文頁數:69
關鍵詞:質譜儀農藥代謝物
關鍵詞(英文):mass spectrometrypesticidemetabolite
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全球人口持續增加,糧食供應的產量無法負荷人口成長的速度,為了解決糧食不足的問題而開始使用農藥,農藥的使用能有效地提升種植效率,但長期地使用農藥對於環境生態與人體健康有安全的疑慮。近年來農藥對健康的影響備受關注,各國也開始訂定相關法規來規範農藥的使用。這些農藥一旦進入人體,將會在尿液中代謝排出,這些代謝物可用於農藥暴露的生物監測,本論文的研究包含常見六種有機磷農藥代謝物 :Dimethylphosphate, DMP、Dimethylthiophosphate, DMTP、Dimethyldithiophosphate, DMDTP、Diethylphosphate, DEP、Diethylthiophosphate, DETP、Diethyldithiophosphate, DEDTP ,與兩種類除蟲菊精類農藥代謝物:3-phenoxybenzoic acid, 3-PBA、3-(2,2-Dichlorovinyl)2,2-dimethylcyclopropanecar boxylic acid, DCCA),之檢測與鑑定,首先我們計算出待測物之前驅物離子的分子量,以離子阱 ( Ion Trap) 分析器鑑定,根據所觀察到的質譜圖 (Mass Spectrum) 推測出其機制是否正確,並與其他文獻所觀測的結果進行比較,由於受1/3原理影響,在使用離子阱質量分析器做碰撞誘導解離時,當產物離子荷質比 (m/z) 小於前驅物離子荷質比(m/z) 1/3 時,無法被觀測,若分析物產生的碎片離子小於前驅物離子質量的1/3時,改由前驅物離子的同位素 (Isotope) 來判斷。本實驗使用離子阱質譜儀,鑑定10種常見農藥代謝物,藉由觀察碎片離子,推測出其機制並與其他質量分析器比對,可以獲得相同檢測結果。
壹、 緒論 1
1、農藥 (Pesticide) 1
1.1簡介 1
1.2、有機磷農藥 (Organophosphate Pesticide) 2
1.3、除蟲菊精類農藥 (Pyrethrin) 6
2、有機磷農藥與類除蟲菊精農藥引起的健康問題 7
3、農藥代謝物檢測儀器及檢測方法 8
3.1、電子捕獲檢測器 (Electron Capture Detector, ECD) 9
3.2、火焰光度計 (Flame Photometric Detector, FPD) 10
3.3、核磁共振儀 (Nuclear Magnetic Resonance , NMR) 11
3.4、質譜法 12
3.4.1、電子游離法 (Electron Ionization, EI ) 13
3.4.2、大氣壓化學游離法 (Atmospheric Pressure Chemical Ionization, APCI) 14
3.4.3、電噴灑游離法 (Electrospray Ionization, ESI) 16
3.4.4、碰撞誘導解離 (Collision-induced dissociation, CID) 17
3.4.5、串聯質譜掃描分析模式 18
3.4.6、四極柱離子阱質量分析器 (Quadrupole Ion-Trap) 20
3.4.7、三段四極柱質量分析器 (Triple-Quadrupole, QqQ) 21
4、研究動機 22
貳、研究內容 23
1、實驗儀器與藥品 23
1.1、儀器設備 23
1.2、藥品 23
1.3、儀器參數 24
2、實驗步驟 25
參、結果與討論 26
3.1、3-苯氧基苯甲酸 (3-phenoxybenzoic acid , 3-PBA) 26
3.2、3-(2,2-二氯乙烯基)-2,2-二甲基環丙烷甲酸 (3-(2,2-Dichlorovinyl)-2,2-dimethylcyclopropanecarboxylic acid , DCCA) 28
3.3、3,5,6-三氯-2-吡啶醇 (3,5,6,-trichloro-2-pyridinol , 3,5,6-TCPy) 30
3.4、4-硝基苯酚(Nitrophenol, PNP) 31
3.6、二甲基硫代磷酸酯 (Dimethylthiophosphate , DMTP) 37
3.7、二甲基二硫代磷酸酯 (Dimethyldithiophosphate , DMDTP) 40
3.8、磷酸二乙酯 (Diethylphosphate, DEP) 43
3.9、二乙基硫代磷酸酯 (Diethylthiophosphate , DETP) 45
3.10、二乙基二硫代磷酸酯 (Diethyldithiophosphate , DEDTP) 49
肆、結論 54
伍、參考文獻 55

1. Casida, J. E.; Gammon, D. W.; Glickman, A. H.; Lawrence, L. J., Mechanisms of selective action of pyrethroid insecticides. Annual review of pharmacology and toxicology 1983, 23, 413-38.
2. Le Couteur, D. G.; McLean, A. J.; Taylor, M. C.; Woodham, B. L.; Board, P. G., Pesticides and Parkinson's disease. Biomedicine & Pharmacotherapy 1999, 53 (3), 122-130.
3. Evangelou, E.; Ntritsos, G.; Chondrogiorgi, M.; Kavvoura, F. K.; Hernandez, A. F.; Ntzani, E. E.; Tzoulaki, I., Exposure to pesticides and diabetes: A systematic review and meta-analysis. Environment International 2016, 91, 60-68.
4. Bennett, B.; Workman, T.; Smith, M. N.; Griffith, W. C.; Thompson, B.; Faustman, E. M., Longitudinal, Seasonal, and Occupational Trends of Multiple Pesticides in House Dust. Environmental health perspectives 2019, 127 (1), 17003.
5. Li, A. J.; Chen, Z.; Lin, T. C.; Louis, G. M. B.; Kannan, K., Association of urinary metabolites of organophosphate and pyrethroid insecticides, and phenoxy herbicides with endometriosis. Environment International 2020, 136.
6. Colume, A.; Cardenas, S.; Gallego, M.; Valcarcel, M., Semiautomatic multiresidue gas chromatographic method for the screening of vegetables for 25 organochlorine and pyrethroid pesticides. Analytica Chimica Acta 2001, 436 (1), 153-162.
7. Wilson, N. K.; Chuang, J. C.; Lyu, C., Levels of persistent organic pollutants in several child day care centers. Journal of Exposure Analysis and Environmental Epidemiology 2001, 11 (6), 449-458.
8. Podhorniak, L. V.; Negron, J. F.; Griffith, F. D. J. J. o. A. i., Gas chromatography with pulsed flame photometric detection multiresidue method for organophosphate pesticide and metabolite residues at the parts-per-billion level in representative commodities of fruit and vegetable crop groups. 2001, 84 (3), 873-890.
9. Fujisawa, T.; Kurosawa, M.; Katagi, T., Uptake and transformation of pesticide metabolites by duckweed (Lemna gibba). Journal of Agricultural and Food Chemistry 2006, 54 (17), 6286-6293.
10. Sarkouhi, M.; Shamsipur, M.; Hassan, J., P-31-NMR evaluation of organophosphorus pesticides degradation through metal ion promoted hydrolysis. Environmental Monitoring and Assessment 2012, 184 (12), 7383-7393.
11. Schettgen, T.; Dewes, P.; Kraus, T., A method for the simultaneous quantification of eight metabolites of synthetic pyrethroids in urine of the general population using gas chromatography-tandem mass spectrometry. Analytical and Bioanalytical Chemistry 2016, 408 (20), 5467-5478.
12. Olsson, A. O.; Baker, S. E.; Nguyen, J. V.; Romanoff, L. C.; Udunka, S. O.; Walker, R. D.; Flemmen, K. L.; Barr, D. B., A liquid chromatography-tandem mass spectrometry multiresidue method for quantification of specific metabolites of organophosphorus pesticides, synthetic pyrethroids, selected herbicides, and DEET in human urine. Analytical Chemistry 2004, 76 (9), 2453-2461.
13. Baker, S. E.; Olsson, A. O.; Barr, D. B., Isotope dilution high-performance liquid chromatography-tandem mass Spectrometry method for quantifying urinary metabolites of synthetic pyrethroid insecticides. Archives of Environmental Contamination and Toxicology 2004, 46 (3), 281-288.
14. Sancho, J. V.; Pozo, O. J.; Hernandez, F., Direct determination of chlorpyrifos and its main metabolite 3,5,6-trichloro-2-pyridinol in human serum and urine by coupled-column liquid chromatography/electrospray-tandem mass spectrometry. Rapid Communications in Mass Spectrometry 2000, 14 (16), 1485-1490.
15. Sancho, J. V.; Pozo, O. J.; Lopez, F. J.; Hernandez, F., Different quantitation approaches for xenobiotics in human urine samples by liquid chromatography/electrospray tandem mass spectrometry. Rapid Communications in Mass Spectrometry 2002, 16 (7), 639-645.
16. Behniwal, P. K.; She, J. W., Development of HPLC-MS/MS method for the simultaneous determination of metabolites of organophosphate pesticides, synthetic pyrethroids, herbicides and DEET in human urine. International Journal of Environmental Analytical Chemistry 2017, 97 (6), 548-562.
17. López-García, M.; Romero-González, R.; Garrido Frenich, A., Monitoring of organophosphate and pyrethroid metabolites in human urine samples by an automated method (TurboFlow(™)) coupled to ultra-high performance liquid chromatography-Orbitrap mass spectrometry. Journal of pharmaceutical and biomedical analysis 2019, 173, 31-39.
18. Morishetti, K. K.; Sripadi, P.; Mariappanadar, V.; Ren, J. H., Generation and characterization of distonic dehydrophenoxide radical anions under electrospray and atmospheric pressure chemical ionizations. International Journal of Mass Spectrometry 2011, 299 (2-3), 169-177.
19. Dulaurent, S.; Saint-Marcoux, F.; Marquet, P.; Lachatre, G., Simultaneous determination of six dialkylphosphates in urine by liquid chromatography tandem mass spectrometry. Journal of Chromatography B-Analytical Technologies in the Biomedical and Life Sciences 2006, 831 (1-2), 223-229.
20. Odetokun, M. S.; Montesano, M. A.; Weerasekera, G.; Whitehead, R. D.; Needham, L. L.; Barr, D. B., Quantification of dialkylphosphate metabolites of organophosphorus insecticides in human urine using 96-well plate sample preparation and high-performance liquid chromatography-electrospray ionization-tandem mass spectrometry. Journal of Chromatography B-Analytical Technologies in the Biomedical and Life Sciences 2010, 878 (27), 2567-2574.
21. Sinha, S. N.; Reddy, B. V.; Vasudev, K.; Rao, M. V. V.; Ahmed, M. N.; Ashu, S.; Kumari, A.; Bhatnagar, V., Analysis of dialkyl urine metabolites of organophosphate pesticides by a liquid chromatography mass spectrometry technique (vol 6, pg 1825, 2014). Analytical Methods 2018, 10 (36), 4471-4471.
22. Cequier, E.; Sakhi, A. K.; Haug, L. S.; Thomsen, C., Development of an ion-pair liquid chromatography-high resolution mass spectrometry method for determination of organophosphate pesticide metabolites in large-scale biomonitoring studies. Journal of Chromatography A 2016, 1454, 32-41.
23. Bueno, M. J. M.; Aguera, A.; Gomez, M. J.; Hernando, M. D.; Garcia-Reyes, J. F.; Fernandez-Alba, A. R., Application of liquid chromatography/quadrupole-linear ion trap mass spectrometry and time-of-flight mass spectrometry to the determination of pharmaceuticals and related contaminants in wastewater. Analytical Chemistry 2007, 79 (24), 9372-9384.
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