改进碱水解气相色谱-串联质谱法分析食品中3-氯丙醇酯和缩水甘油酯  

Improved Alkaline Hydrolysis Gas Chromatography-Tandem Mass Spectrometry for the Analysis of 3-Chloropropanol Ester and Glycidyl Ester in Food

作　　者：朱子翔 孙文彬 胡思杰 祝晨程 袁海娜 肖功年 施川川 ZHU Zixiang;SUN Wenbin;HU Sijie;ZHU Chencheng;YUAN Haina;XIAO Gongnian;SHI Chuanchuan(College of Biology and Chemical Engineering,Zhejiang University of Science and Technology/Zhejiang Provincial Key Laboratory of Agricultural Product Chemistry and Biotechnology,Hangzhou,Zhejiang 310023;Panda Dairy Group Co.,Ltd.,Wenzhou,Zhejiang 325800)

机构地区：[1]浙江科技大学生物与化学工程学院/浙江省农产品化学与生物加工技术重点实验室,浙江杭州310023 [2]熊猫乳品集团股份有限公司,浙江温州325800

出　　处：《核农学报》2025年第4期800-809,共10页Journal of Nuclear Agricultural Sciences

基　　金：浙江省基础公益研究计划项目(LGN22C200019);浙江省市场监督管理局“雏鹰计划”培育项目(CY2022345);温州市科研项目三区五县揭榜挂帅(ZNF2023009)。

摘　　要：近年,植物油脂和含油食品中氯丙醇酯(MCPDE)和缩水甘油酯(GEs)类污染物的暴露情况备受关注。为进一步提升3-氯丙醇酯(3-MCPDE)和缩水甘油酯的碱水解气相色谱-质谱联用(GC-MS)分析方法的稳定性,采用0.3 mol·L^(-1)液体甲醇钠-甲醇溶液反应3 min,冰乙酸终止水解反应并控制微酸环境,以NaCl为盐析试剂优化碱水解工艺,并考察部分市售植物油和婴幼儿配方奶粉中3-MCPDE和GEs的污染情况。结果表明,碱水解过程中,液体甲醇钠-甲醇溶液水解3-MCPDE和GEs的反应均一性和稳定性均优于固体甲醇钠的甲醇溶液;可能存在氯丙醇和缩水甘油间的相互转化,影响3-MCPDE和GEs分析结果的稳定性;3-氯丙醇单酯的水解效率是3-氯丙醇双酯的2.2倍;本试验以七氟丁酰基咪唑(HFBI)作为氯丙醇衍生试剂,发现试验环境中微量水分影响HFBI的稳定性;改进碱水解GC-MS法加标回收试验的回收率为85.7%~98.4%,相对标准偏差(RSD)为0.7%~4.3%。分析杭州市售14种食用油和5个品牌婴幼儿配方奶粉(Ⅰ、Ⅱ和Ⅲ段)发现,样品中3-MCPDE检出率为100%,GE检出率分别为7.1%和47%;植物油中3-MCPDE的污染情况与其来源密切相关,而不同压榨或浸提工艺的影响较小。本研究结果可为碱水解GC-MS法分析食品中MCPDE和GEs提供技术支持,也可为我国建立食品中此类污染物限量标准提供有益参考。In recent years,the exposure risk of chloropropanol ester(MCPDE)and glycidyl ester(GEs)pollutants in edible vegetable oils and oily foods have attracted much attention.Alkaline hydrolysis process of 3-chloropropanol ester(3-MCPDE)and GEs determined by applying gas chromatography-mass spectrometry(GC-MS)method were optimized to improve their analysis stability.The contamination statuses of 3-MCPDE and GEs in some vegetable oils and infant formulas were assessed.3-MCPDE and GEs were hydrolyzed in 0.3 mol·L^(−1) sodium methylate/methanol(liquid)exactly for 3 min.Acetic acid was added into above hydrolysate solution to terminate the hydrolysis reaction and to provide a slightly acidic condition.NaCl was finallly used as salting out reagent.The results showed that sodium methylate/methanol in liquid state was superior to powder sodium methylate solved in methanol in terms of hydrolyzing homogeneity and stability.Furthermore,occurred conversion reaction between chloropropanol and glycidol in the alkaline condition would affect the analyzed concentration stabilities of 3-MCPDE and GEs.In addition,the hydrolysis efficiency of 3-chloropropanol monoester was 2.2 times that of 3-chloropropanol diesters.When heptafluorobutyryl imidazole(HFBI)was applied to be as derivatization reagent,the trace moisture from experimental environment was found to affect its stability.The recovery rate was exhibited at range of 85.7%-98.4%and relative standard deviation(RSD)was 0.7%-4.3%by improved alkaline hydrolysis combined with GC-MS.Results of 14 edible vegetable oils and 5 brands of infant formula milk powder(I,II and III phase)in Hangzhou market showed that the detection rate of 3-MCPDE was 100%in all samples.It was 7.1%in vegetable oils and 47%in infant formula milk powder for GEs,respectively.The exposure risk of 3-MCPDE in vegetable oil was closely related to its source,while different processing technologies exhibited neglectable influence.The results provide technical support for analyzing 3-MCPDE and GEs in food by alkaline hyd

关 键 词：婴幼儿配方奶粉 食用油 氯丙醇酯 缩水甘油酯 

分 类 号：TS207.3[轻工技术与工程—食品科学] O657.63[轻工技术与工程—食品科学与工程]