Please use this identifier to cite or link to this item: http://hdl.handle.net/11455/96321
標題: Identification of Degradation Products of Herbicides in Soybean Oil after Frying Process by Using LLE-LC-MS/MS and HS-SPME-GC-MS
液液萃取結合液相層析串聯質譜與頂空固相微萃取結合氣相層析質譜應用於大豆油中除草劑經高溫油炸後降解產物之鑑定
作者: Jia -Hao Wu
吳家豪
關鍵字: 除草劑
大豆油
降解產物
液相層析高解析串聯質譜術
液液萃取
氣象層析質譜術
頂空固相微萃取
主成分分析法
非目標性
Herbicides
Soybean oil
degradation products
LC-HRMS/MS
LLE
GC-MS
HS-SPME
PCA
non-targeted
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摘要: Recently, the soybean oil is the most useful edible oil in the word. During the soybean cultivation, the herbicides such as glyphosate, glufosinate, and atrazine are widely used for increasing harvest, hence, the low concentration of herbicides may remain in the soybean or soybean oil. Moreover, high temperature thermal processing methods, likes frying and stir-frying, are very popular in traditional Chinese cooking methods. The degradation compounds of glyphosate, glufosinate, and atrazine in soybean oil after thermal processing might cause damage of human health. In this study, LLE-LC-HRMS/MS and HS-SPME-GC-MS methods were developed for identification of degradation products of herbicides in soybean oil after thermal process. Liquid-liquid extraction (LLE) was used as a sample pretreatment in LC-HRMS/MS analysis which standard oil was spkied by herbicides and extracted with 1 mL ACN. The 700 μL supernatants was dried under nitrogen stream then reconstituted with 300 μL MeOH. In headspace solid phase microextraction (HS-SPME), the oil spkied by herbicides incubated at 175℃ then extracted for 30 min. The PCA, the most widely multivariate statistical methods , were used for differentiating the LC-MS and GC-MS data to compare the nonvolatile and volatile compounds between unspiked and spiked standard soybean oil. In LC analysis, 10 degradants of atrazine were found by Compound Discover 2.0 dealing with high resolution data in fried soybean oil. In GC-MS analysis, the degradation compounds were detected in soybean oil spiked with glyphosate, glufosinate, and atrazine after being heated were 6, 6 and 3, respectively. The methods developed in this study can be used for evaduating the degradation of pesticide residues in edible oil after heating processing.
本研究利用液液萃取法結合液相層析高解析質譜與頂空固相微萃取法結合氣相層析質譜鑑定大豆油中的微量除草劑經高溫油炸後產生的降解產物與新生成物。本實驗主要比較含有除草劑於食用油加熱前後的差異,再以液液萃取法結合液相層析高解析質譜分析加熱前後 0.5 g 含有嘉磷塞 (10 µg/mL)、固殺草 (2 µg/mL)、草脫凈 (0.25 µg/mL)之標準大豆油,加入 1.0 mL 乙腈,經渦流震盪和離心後取 700 μL 上清液以氮氣吹乾,最後用 300 μL 甲醇回溶。於頂空固相為萃取法結合氣相層析質譜部分,取 4 mL含有嘉磷塞 (10 µg/mL)、固殺草 (2 µg/mL)、草脫凈 (0.25 µg/mL) 之大豆油標準品,分別使用三種萃取纖維PDMS /DVB、CAR/PDMS 及 DVB/CAR/PDMS 進行實驗,於平衡時間 3分鐘、萃取時間 30 分鐘時可以得到最佳的萃取效果。   添加除草劑的大豆油標準品,於加熱前後經探討的最佳萃取條件萃取後,以主成分分析法皆可明確地發現加熱前後大豆油中除草劑的量有明顯差異,其中嘉磷塞和固殺草於加熱後沒有偵測到訊號,草脫淨仍有殘留。接著也比較有無添加除草劑於加熱後的差異,進一步透過統計軟體分析與資料庫搜尋,找出可能的降解及新生成物。實驗結果顯示,液相層析高解析質譜部分找出 10 個草脫淨經油炸後產生之降解產物:Hydroxyatrazine、Desisopropylatrazine、Desethylatrazine、Desethyldesisopropylatrazine、N-Isopropylammelide、Desisopropylhydroxyatrazine、N-Ethylammelide、Desethylhydroxyatrazine、N-Ethyl-N'-isopropyl-1,3,5-triazine-2、4-diamine、Ammeline。氣相層析部分找出6個添加嘉磷塞於油中經加熱產生之揮發性化合物:Pentadecanoic acid、2,5-Furandione, dihydro-3-methylene-、Phenol, 3-methyl-、2-Acetyl-5-methylfuran、Propanediamide、Bis(2-ethylhexyl) phthalate,6個添加固殺草於油中經加熱產生之揮發性化合物:2-Hexanone,4-methyl-、Ethyl N,N-dimethyloxamate、2,3-Butanedione、Nonanoic acid、3,4-Hexanedione、Hexadecanoic acid、methyl ester,3個添加草脫凈於油中經加熱產生之揮發性化合物: 2-Pentanone, 4,4-dimethyl-、Pentanoic acid, 4-oxo-、cis-9-Tetradecen-1-ol。因此可將本研究開發之方法應用於評估食用油中殘留農藥經高溫加熱後產生之降解產物。
URI: http://hdl.handle.net/11455/96321
文章公開時間: 10000-01-01
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