顶空固相微萃取结合GC-MS测定酱油中的羟甲基糠醛衍生物
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摘要
为研究市售酱油中羟甲基糠醛衍生物的含量差异及评估其安全性,本文收集不同的酱油样品,应用顶空固相微萃取(SPME)结合气相色谱-串联质谱分析(GC-MS)检测其中的羟甲基糠醛衍生物。结果表明,从5种市售酱油中鉴定出3种羟甲基糠醛衍生物,分别为糠醛、2-乙基-1-己醇和5-甲基糠醛。它们在3.33~666.67μg/m L浓度范围内线性关系良好,检测限在3.33×10~(-1)μg/L以下,定量限在3.33μg/L及以下。加标回收率实验表明,对酱油直接进行SPME萃取分析回收率不符合国标要求,而将酱油用蒸馏水稀释5倍后进行SPME萃取分析回收率在82.23%~115.04%之间,日内准确度在93.31%~111.50%之间,日间准确度范围在93.02%~115.91%之间,日内精密度≤4.36%,日间精密度≤8.02%。五种酱油中糠醛含量在70.14~98.75μg/L之间,2-乙基-1-己醇含量在66.61~79.20μg/L之间,5-甲基糠醛含量在221.87~527.40μg/L之间。以上结果表明,虽然不同酱油中羟甲基糠醛衍生物含量有显著差异,但人们日常食用酱油的量,并不足以导致产生羟甲基糠醛衍生物的不良反应。
In order to assay the content of hydroxymethylfurfural derivatives and evaluate the safety of soy sauces, five soy sauces that were collected in the local market were analyzed for the hydroxymethyl furfural derivatives by headspace solid-phase microextraction(SPME) combined with gas chromatography-tandem mass spectrometry(GC-MS). As a result, three kinds of hydroxymethyl furfural derivatives, i.e., furfural, 5-methyl furfural and 2-ethyl-1-hexanol were identified. The linear regressive calibration curve was plotted within the concentration of 3.33~666.67 μg/m L with the LOD of 3.33×10~(-1) μg/L and the LOQ of 3.33 g/L. The original soy sauce showed that the spiked recovery range was out of the national standard, and whereas the soy sauce after 5-fold dilution with distilled water had the recovery range between 82.23%~115.04%, with the inter-day recovery range between 93.31~111.50%. The inter-day recovery rate was ranged from 93.02% to 115.91%. The inter-day and intra-day precisions were 4.36% and 8.02%, respectively. The furfural content in the five soy sauces was between 70.14~98.75 μg/L, the 2-ethyl-1-hexanol content was between 66.61~79.20 μg/L, and the 5-methyl furfural content was between 221.87~527.40 μg/L. The above results indicated that the content of hydroxymethylfurfural derivatives were significantly different in different soy sauces. However, the daily consumption of soy sauce is safe because the intake of hydroxymethyl furfural derivatives is far below the bottom level to cause safety problems.
In order to assay the content of hydroxymethylfurfural derivatives and evaluate the safety of soy sauces, five soy sauces that were collected in the local market were analyzed for the hydroxymethyl furfural derivatives by headspace solid-phase microextraction(SPME) combined with gas chromatography-tandem mass spectrometry(GC-MS). As a result, three kinds of hydroxymethyl furfural derivatives, i.e., furfural, 5-methyl furfural and 2-ethyl-1-hexanol were identified. The linear regressive calibration curve was plotted within the concentration of 3.33~666.67 μg/m L with the LOD of 3.33×10~(-1) μg/L and the LOQ of 3.33 g/L. The original soy sauce showed that the spiked recovery range was out of the national standard, and whereas the soy sauce after 5-fold dilution with distilled water had the recovery range between 82.23%~115.04%, with the inter-day recovery range between 93.31~111.50%. The inter-day recovery rate was ranged from 93.02% to 115.91%. The inter-day and intra-day precisions were 4.36% and 8.02%, respectively. The furfural content in the five soy sauces was between 70.14~98.75 μg/L, the 2-ethyl-1-hexanol content was between 66.61~79.20 μg/L, and the 5-methyl furfural content was between 221.87~527.40 μg/L. The above results indicated that the content of hydroxymethylfurfural derivatives were significantly different in different soy sauces. However, the daily consumption of soy sauce is safe because the intake of hydroxymethyl furfural derivatives is far below the bottom level to cause safety problems.
引文
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[8]冯云子.高盐稀态酱油关键香气物质的变化规律及形成机理的研究[D].广州:华南理工大学,2015FENGYun-zi.TheEvolutionandformationmechanismof key aroma compounds during the process of high-salt liquid fermentationsoysauce[D].Guangzhou:SouthChina University of Technology, 2015
[9]赵吉兴.红曲红色素在酱油增色方面的应用研究[J].中国酿造,2012,31(8):132-135ZHAOJi-xing.Applicationresearchonredmonascus pigmentofcolorenhancementonsoysauce[J].China Brewing, 2012, 31(8):132-135
[10]刘非,杜丽平,肖冬光.酱油挥发性成分固相微萃取条件的优化[J].食品与发酵工业,2017,43(7):70-75LIUFei,DULi-ping,XIAODong-guang.Optimizationof extraction conditions for volatile compounds in soy sauce by solid-phasemicroextrac[J].FoodandFermentation Industries, 2017, 43(7):70-75
[11]肖昭竞,李根容,段云鹏,等.酱油香精和焦糖中挥发性成分分析[J].精细化工,2009,26(12):1200-1205XIAOZhao-jing,LIGen-rong,DUANYun-peng,etal.Analysis of volatile components from essence of soy sauces and caramels[J]. Fine Chemicals, 2009, 26(12):1200-1205
[12]相欢,尹文颖,崔春.SPME-DSE联用分析不同固形物浓度发酵对酱油香气物质的影响[J].现代食品科技,2016,32(10):259-267XIANGHuan,YINWen-ying,CUIChun.Effectsof differentconcentrationsofsolidsduringfermentationon thearomacompoundsofsoysauceassessedbySPME-DSE[J].ModernFoodScienceandTechnology,2016,32(10):259-267
[13]赵迎晨,梁晶,毛森,等.三重四级杆气相色谱-质谱联用仪检出限评定方法[J].上海计量测试,2016,43(3):12-13ZHAOYing-chen,LIANGJin,MAOSen,etal.An evaluation method for the detection limit of triple quadrupole gaschromatographymassspectrometrys[J].Shanghai Measurement and Testing, 2016, 43(3):12-13
[14]田强兵.分析化学中检出限和测定下限的探讨[J].化学分析计量,2007,16(3):72-73TIANQiang-bing.Discussionondetectionlimitandlower limitofdeterminationinanalyticalchemistry[J].Chemical Analysis and Meterage, 2007, 16(3):72-73
[15]吴香姣.加标回收率及质量控制图在环境监测实验室中的应用[J].资源节约与环保,2016,2:119-12WUXiang-jiao.Applicationofrecoveryrateandquality controlchartinenvironmentalmonitoringlaboratory[J].Resources Economization&Environmental Protection, 2016,2:119-120
[16]张玉玉,宋弋,李全宏.食品中糠醛和5-羟甲基糠醛的产生机理、含量检测及安全性评价研究进展[J].食品科学,2012,33(5):275-280ZHANGYu-yu,SONGYi,LIQuan-hong.Areviewon formationmechanism,determinationandsafetyassessment of furfural and 5-Hydroxymethylfurfural(HMF)in foods[J].Food Science, 2012, 33(5):275-280
[17]PripdeevechP,MachanT.Fingerprintofvolatileflavour constituentsandantioxidantactivitiesofteasfromThailand[J]. Food Chemistry, 2011, 125(2):797-802
[18]Fanaro G B D R, Santillo A G. Evaluation ofγ-radiation on Oolongteaodorvolatiles[J].RadiationPhysicsand Chemistry, 2012, 81(8):1152-1156
[19]ZHUJ,CHENF,WANGL,etal.Comparisonof aroma-activevolatilesinOolongteainfusionsusing GC-olfactometry,GC-FPD,andGC-MS[J].Journalof Agricultural and Food Chemistry, 2015, 63(34):7499-7510
[20]林晓珊,黄晓兰,吴惠勤,等.气相色谱-串联质谱法快速测定调味品中3种糠醛类物质[J].分析测试学报,2012,31(11):1345-1351LINXiao-shan,HUANGXiao-lan,WUHui-qin,etal.Determinationofthreefurfuralsincondimenbygas chromatography-tandemmassspectrometry[J].Journalof Instrumental Analysis, 2012, 31(11):1345-1351
[21]GB/T 27404-2008,实验室质量控制规范食品理化检测[S]GB/T27404-2008,Laboratoryqualitycontrolspecification Food Physical and Chemical Testing[S]
[22]郭天鑫.5-羟甲基糠醛的检测方法及其在食品中产生研究[D].天津:天津科技大学,2010GUOTian-xin.Studyonthedetectionmethodof5-hydroxymethylfurfuralanditsgenerationinfoods[D].Tianjin:Tianjin University of Science and Technology, 2010
[23]AbrahamK,GürtlerR,BergK,etal.Toxicologyandrisk assessmentof5-hydroxymethylfurfuralinfood[J].Molecular Nutrition&Food Research, 2011, 55(5):667-678
[2]曾世通,卢斌斌,李鹏,等.丙氨酸与葡萄糖美拉德反应体系中HMF的形成分析[J].中国食品学报,2017,17(4):289-293ZENG Shi-tong, LU Bin-bin, LI Peng, et al. Analysis of the5-hydroxymenthylfurfualformationinmaillardreaction system of alanine and glucose[J]. Journal of Chinese Institute of Food Science and Technology, 2017, 17(4):289-293
[3]汪辉,黎瑛,夏立新,等.高效液相色谱法测定葡萄干中糠醛类物质[J].理化检验(化学分册),2014,50(11):1377-1381WANG Hui, LI Ying, XIA Li-xin, et al. HPLC determination offurfuralsinraisins[J].PhysicalTestingandChemical Analysis Part B:Chemical Analysis, 2014, 50(11):1377-1381
[4]GB/T2760-2014,食品安全国家标准食品添加剂使用标准[S]GB/T2760-2014,NationalFoodSafetyStandardFood Additives Standard[S]
[5]任呼博,别振英,朱友,等.超高效液相色谱法同时测定烟用香精料液中的糠醛、5-羟甲基糠醛与5-甲基糠醛[J].分析测试学报,2015,34(11):1291-1295REN Hu-bo, BIE Zhen-ying, ZHU You, et al. Simultaneous determinationoffurfural,5-hydroxymethylfurfuraland5-methylfurfuralincigarettefragrancesbyultra-high performanceliquidchromatography[J].Journalof Instrumental Analysis, 2015, 34(11):1291-1295
[6]吴惠勤,林晓珊,黄芳.气相色谱/质谱法在抢救病人中的应用[C].中国质谱学会第七届学术交流会论文集.杭州:2003:167-170WU Hui-qin, LIN Xiao-shan, HUANG Fang. Application of gaschromatography/massspectrometryinrescuingpatients[C]. The 7th Academic Exchange Conference of China Mass Spectrometry Society. Hangzhou:2003:167-170
[7]KatayamaH,TatemichiY,NakajimaA.Simultaneous quantification of twenty Amadori products in soy sauce using liquidchromatography-tandemmassspectrometry[J].Food Chemistry, 2017, 228:279-286
[8]冯云子.高盐稀态酱油关键香气物质的变化规律及形成机理的研究[D].广州:华南理工大学,2015FENGYun-zi.TheEvolutionandformationmechanismof key aroma compounds during the process of high-salt liquid fermentationsoysauce[D].Guangzhou:SouthChina University of Technology, 2015
[9]赵吉兴.红曲红色素在酱油增色方面的应用研究[J].中国酿造,2012,31(8):132-135ZHAOJi-xing.Applicationresearchonredmonascus pigmentofcolorenhancementonsoysauce[J].China Brewing, 2012, 31(8):132-135
[10]刘非,杜丽平,肖冬光.酱油挥发性成分固相微萃取条件的优化[J].食品与发酵工业,2017,43(7):70-75LIUFei,DULi-ping,XIAODong-guang.Optimizationof extraction conditions for volatile compounds in soy sauce by solid-phasemicroextrac[J].FoodandFermentation Industries, 2017, 43(7):70-75
[11]肖昭竞,李根容,段云鹏,等.酱油香精和焦糖中挥发性成分分析[J].精细化工,2009,26(12):1200-1205XIAOZhao-jing,LIGen-rong,DUANYun-peng,etal.Analysis of volatile components from essence of soy sauces and caramels[J]. Fine Chemicals, 2009, 26(12):1200-1205
[12]相欢,尹文颖,崔春.SPME-DSE联用分析不同固形物浓度发酵对酱油香气物质的影响[J].现代食品科技,2016,32(10):259-267XIANGHuan,YINWen-ying,CUIChun.Effectsof differentconcentrationsofsolidsduringfermentationon thearomacompoundsofsoysauceassessedbySPME-DSE[J].ModernFoodScienceandTechnology,2016,32(10):259-267
[13]赵迎晨,梁晶,毛森,等.三重四级杆气相色谱-质谱联用仪检出限评定方法[J].上海计量测试,2016,43(3):12-13ZHAOYing-chen,LIANGJin,MAOSen,etal.An evaluation method for the detection limit of triple quadrupole gaschromatographymassspectrometrys[J].Shanghai Measurement and Testing, 2016, 43(3):12-13
[14]田强兵.分析化学中检出限和测定下限的探讨[J].化学分析计量,2007,16(3):72-73TIANQiang-bing.Discussionondetectionlimitandlower limitofdeterminationinanalyticalchemistry[J].Chemical Analysis and Meterage, 2007, 16(3):72-73
[15]吴香姣.加标回收率及质量控制图在环境监测实验室中的应用[J].资源节约与环保,2016,2:119-12WUXiang-jiao.Applicationofrecoveryrateandquality controlchartinenvironmentalmonitoringlaboratory[J].Resources Economization&Environmental Protection, 2016,2:119-120
[16]张玉玉,宋弋,李全宏.食品中糠醛和5-羟甲基糠醛的产生机理、含量检测及安全性评价研究进展[J].食品科学,2012,33(5):275-280ZHANGYu-yu,SONGYi,LIQuan-hong.Areviewon formationmechanism,determinationandsafetyassessment of furfural and 5-Hydroxymethylfurfural(HMF)in foods[J].Food Science, 2012, 33(5):275-280
[17]PripdeevechP,MachanT.Fingerprintofvolatileflavour constituentsandantioxidantactivitiesofteasfromThailand[J]. Food Chemistry, 2011, 125(2):797-802
[18]Fanaro G B D R, Santillo A G. Evaluation ofγ-radiation on Oolongteaodorvolatiles[J].RadiationPhysicsand Chemistry, 2012, 81(8):1152-1156
[19]ZHUJ,CHENF,WANGL,etal.Comparisonof aroma-activevolatilesinOolongteainfusionsusing GC-olfactometry,GC-FPD,andGC-MS[J].Journalof Agricultural and Food Chemistry, 2015, 63(34):7499-7510
[20]林晓珊,黄晓兰,吴惠勤,等.气相色谱-串联质谱法快速测定调味品中3种糠醛类物质[J].分析测试学报,2012,31(11):1345-1351LINXiao-shan,HUANGXiao-lan,WUHui-qin,etal.Determinationofthreefurfuralsincondimenbygas chromatography-tandemmassspectrometry[J].Journalof Instrumental Analysis, 2012, 31(11):1345-1351
[21]GB/T 27404-2008,实验室质量控制规范食品理化检测[S]GB/T27404-2008,Laboratoryqualitycontrolspecification Food Physical and Chemical Testing[S]
[22]郭天鑫.5-羟甲基糠醛的检测方法及其在食品中产生研究[D].天津:天津科技大学,2010GUOTian-xin.Studyonthedetectionmethodof5-hydroxymethylfurfuralanditsgenerationinfoods[D].Tianjin:Tianjin University of Science and Technology, 2010
[23]AbrahamK,GürtlerR,BergK,etal.Toxicologyandrisk assessmentof5-hydroxymethylfurfuralinfood[J].Molecular Nutrition&Food Research, 2011, 55(5):667-678