气相色谱-质谱法测定食品中黄樟素及其衍生物含量
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摘要
建立了调味制品(调味料、番茄酱、酱油、花椒)、饮料(碳酸饮料、乳饮料、果汁)、肉制品(香肠、肉罐头、肉汤)、水果制品(果冻、果酱)、水产品(干鱼肉、鱼罐头、鱼肉泥)、小吃类(油炸薯片、糖果、巧克力)等18种食品中黄樟素、异黄樟素、二氢黄樟素含量的分析方法。样品在氯化钠盐析作用下,经二氯甲烷-乙腈提取,无水硫酸钠-氟罗里硅土柱吸附极性物质和水分。复杂样品需再经PRi ME HLB固相萃取柱(SPE)净化,5%苯基-95%甲基聚硅氧烷毛细管气相色谱柱分离,选择离子质谱技术监测,内标法定量。在最佳实验条件下,3种黄樟素在25~5 000μg/kg范围内呈良好的线性关系,相关系数(r2)≥0.9981,方法检出限(LOD)和定量下限(LOQ)分别为20μg/kg和50μg/kg,3个加标水平的回收率为77.6%~100.9%,相对标准偏差(RSD)为3.7%~13.6%。多种实际样品的测定结果表明,该方法准确可靠,适用于食品中3种黄樟素及其衍生物的定量和定性分析。
An analytical method was developed for the determination of safrole( SFL), isosafrole( DSFL) and dihydrosafrole( ISFL) in 18 foods including condiment,tomato,sauce,soy sauce,pepper,carbonated beverage,milk drink,juice,sausage,canned meat,meat soup,jelly,jam,dried fish,canned fish,fish slime,potato chip,candy and chocolate by gas chromatography-mass spectrometry( GC-MS). The sample was extracted with dichloromethane-acetonitrile in the presence of sodium chloride salt-out. Water and polar substances were removed with anhydrous sodium sulfite-florisil column. For complex matrices,further purification was performed with a PRi ME HLB solid-phase extraction columns. The separation was carried out on a 5% phenyl-95% methyl polysiloxane capillary GC column. The detection of compounds was completed in the selected ion monitoring mode( SIM). The quantification analysis was performed by the internal standard method. Good linear relationships( r2≥0. 998 1) betweeen peak areas ratios and concentrations ratios of 3 analytes were obtained in the range of 25-5 000 μg/kg. The limits of detection( LOD) for 3 analytes were 20μg/kg. And the limits of quantitation( LOQ) were 50 μg/kg. The average recoveries of the method varied from 77. 6% to 100. 9% at 3 different spiked levels,with relative standard deviations( RSD)of 3. 7%-13. 6%. By measuring real samples,the results showed that this method was accurate and reliable for quantification and confirmation of SFL,DSFL and ISFL in foodstuffs.
An analytical method was developed for the determination of safrole( SFL), isosafrole( DSFL) and dihydrosafrole( ISFL) in 18 foods including condiment,tomato,sauce,soy sauce,pepper,carbonated beverage,milk drink,juice,sausage,canned meat,meat soup,jelly,jam,dried fish,canned fish,fish slime,potato chip,candy and chocolate by gas chromatography-mass spectrometry( GC-MS). The sample was extracted with dichloromethane-acetonitrile in the presence of sodium chloride salt-out. Water and polar substances were removed with anhydrous sodium sulfite-florisil column. For complex matrices,further purification was performed with a PRi ME HLB solid-phase extraction columns. The separation was carried out on a 5% phenyl-95% methyl polysiloxane capillary GC column. The detection of compounds was completed in the selected ion monitoring mode( SIM). The quantification analysis was performed by the internal standard method. Good linear relationships( r2≥0. 998 1) betweeen peak areas ratios and concentrations ratios of 3 analytes were obtained in the range of 25-5 000 μg/kg. The limits of detection( LOD) for 3 analytes were 20μg/kg. And the limits of quantitation( LOQ) were 50 μg/kg. The average recoveries of the method varied from 77. 6% to 100. 9% at 3 different spiked levels,with relative standard deviations( RSD)of 3. 7%-13. 6%. By measuring real samples,the results showed that this method was accurate and reliable for quantification and confirmation of SFL,DSFL and ISFL in foodstuffs.
引文
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[12]Stuppner H,Ganzera M.Chromatographia,1998,47(11/12):686-688.
[13]Zhou Y B,Teng M D,Zhang M S.Physi.Test.Chem.Anal.:Chem.Anal.(周贻兵,滕明德,张明时.理化检验-化学分册),2011,47(1):39-40.
[14]Han Y,Zhang C M,Yu K,Meng X,Chen Y K,Miao M M.Flavour Fragrance Cosmetics(韩熠,张承明,喻坤,孟霞,陈永宽,缪明明.香料香精化妆品),2013,16(1):45-49.
[15]Siano F,Ghizzoni C,Gionfriddo F,Colombo E,Servillo L,Castaldoa D.Food Chem.,2003,81:469-475.
[2]Stanfill S B,Ashley D L.J.Chromatogr.A,1999,858:79-89.
[3]Martati E,Boonpawa R,Berg J H,Paini A,Spenkelink A,Punt A,Vervoort J,Bladeren P J,Rietjens I M.Food Chem.Toxi.,2014,66(4):373-384.
[4]Shen L C,Chiang S Y,Lin M H,Chung W S,Wu K Y.Toxicol.Lett.,2012,213(9):309-315.
[5]Raffo A,Aloise A D,MagrìA L,Leclercq C.Food Chem.Toxicol.,2013,59(9):626-635.
[6]European Commission.Flavourings&Certain Food Ingredients.http://eur-lex.europa.eu/eli/reg/2008/1334/oj.
[7]Huang S S,Fan Z,Huang S J,Wang W G,Jiang H L,Zhu J,Lu B L.J.Anhui Agric.Sci.(黄善松,范忠,黄世杰,王维刚,蒋宏霖,朱静,陆冰琳.安徽农业科学),2014,42(20):6805-6806.
[8]Li Y,Wang H Y,Liao X L,Xiao S H,Chen H.Tobac.Sci.Technol.(李韵,汪宏毅,廖晓玲,肖少红,陈慧.烟草科技),2014,47(12):32-35.
[9]Li C Y,Li Z G,Zhou S Y,Ye D F,Mo W M.Physi.Test.Chem.Anal.:Chem.Anal.(李长于,李祖光,周示玉,叶丹凤,莫卫民.理化检验-化学分册),2013,49(2):216-218.
[10]Wang X,Cai T P,Wang C,Xiao H Q,Zhang F,Liu L.J.Environ.Health(王星,蔡天培,王超,肖海清,张帆,刘柳.环境与健康杂志),2007,24(5):355-359.
[11]Zhu X L,Hong S Q,Li P P,Gao Y,Liu Y G.J.Instrum.Anal.(朱晓兰,洪深求,李盼盼,高芸,刘渊根.分析测试学报),2012,31(3):351-354.
[12]Stuppner H,Ganzera M.Chromatographia,1998,47(11/12):686-688.
[13]Zhou Y B,Teng M D,Zhang M S.Physi.Test.Chem.Anal.:Chem.Anal.(周贻兵,滕明德,张明时.理化检验-化学分册),2011,47(1):39-40.
[14]Han Y,Zhang C M,Yu K,Meng X,Chen Y K,Miao M M.Flavour Fragrance Cosmetics(韩熠,张承明,喻坤,孟霞,陈永宽,缪明明.香料香精化妆品),2013,16(1):45-49.
[15]Siano F,Ghizzoni C,Gionfriddo F,Colombo E,Servillo L,Castaldoa D.Food Chem.,2003,81:469-475.