香气指纹图谱应用于山西老陈醋的身份识别
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摘要
采用顶空固相微萃取-气相色谱-质谱联用法测试样品,利用共有香气成分建立山西老陈醋香气指纹图谱,并借助聚类分析结合香气风味特性分析实现对其身份识别。结果显示,山西老陈醋香气指纹图谱中共有香气成分44种,包含3种主要风味类型,分别为酸性风味(acidic?avor,AF)、浓厚型香气风味(dense?avor,DF)和清新型香气风味(refreshing?avor,RF);相对于其他名醋,山西老陈醋在AF、DF方面占有优势,而RF方面相对较弱;利用山西老陈醋的乙酸含量(A值)、浓厚型香气含量(D值)、清新型香气含量(F值)建立的香气特性参数Ps值能够放大山西老陈醋与其他名醋的差异性。结果证明,以山西老陈醋香气指纹图谱为参照的聚类分析可以对山西老陈醋样品进行模糊识别;而香气特性参数Ps值在一定程度上提高识别山西老陈醋样品的精确性;香气指纹图谱的聚类分析和Ps值相互补充,应用于山西老陈醋样品的身份识别,结果更加准确可靠。
The present study aimed to develop a novel method to identify Shanxi aged vinegar(SAV) by a combination of aroma ?ngerprinting, hierarchical cluster analysis(HCA) and ?avor characteristics analysis. For this purpose, representative samples of SAV from 4 different manufacturers were used to establish an aroma ?ngerprint based on the aroma compounds common to these samples as determined by headspace solid phase microextraction-gas chromatography-mass spectrometry(HS-SPME-GC-MS). The results showed that a total of 44 aroma compounds were found to be common to all SAV samples,including three main ?avor types, acidic ?avor(AF), dense ?avor(DF) and refreshing ?avor(RF). SAV had stronger AF and DF but weaker RF compared with other vinegars; the characteristic parameter Ps resulting from acetic acid content(A),dense ?avor content(D) and refreshing ?avor content(F) gave a more clear discrimination between SAV and other vinegars.In conclusion, HCA based on the aroma ?ngerprint of SAV is a robust tool for fuzzy identi?cation of SAV. Moreover, the application of Ps can improve the accuracy of identifying SAV. HCA and Ps are complementary in identi?cation of SAV.
The present study aimed to develop a novel method to identify Shanxi aged vinegar(SAV) by a combination of aroma ?ngerprinting, hierarchical cluster analysis(HCA) and ?avor characteristics analysis. For this purpose, representative samples of SAV from 4 different manufacturers were used to establish an aroma ?ngerprint based on the aroma compounds common to these samples as determined by headspace solid phase microextraction-gas chromatography-mass spectrometry(HS-SPME-GC-MS). The results showed that a total of 44 aroma compounds were found to be common to all SAV samples,including three main ?avor types, acidic ?avor(AF), dense ?avor(DF) and refreshing ?avor(RF). SAV had stronger AF and DF but weaker RF compared with other vinegars; the characteristic parameter Ps resulting from acetic acid content(A),dense ?avor content(D) and refreshing ?avor content(F) gave a more clear discrimination between SAV and other vinegars.In conclusion, HCA based on the aroma ?ngerprint of SAV is a robust tool for fuzzy identi?cation of SAV. Moreover, the application of Ps can improve the accuracy of identifying SAV. HCA and Ps are complementary in identi?cation of SAV.
引文
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[18]刘晓伟,杨代明,孙桂芳.食醋有机酸的液相指纹图谱建立方法研究[J].食品工业科技, 2011, 32(5):403-406.
[19]山西大学.山西老陈醋液相指纹图谱的构建方法和应用:201510400315.X[P]. 2015-07-09.
[20]山西大学.山西老陈醋1H-N M R指纹图谱的构建方法和应用:201610317142.X[P]. 2016-05-12.
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[23]刘万仓,孙磊,于孟琦,等.中药指纹图谱模式识别研究进展[J].国际药学研究杂质,2010,37(6):446-449.DOI:10.3969/j.issn.1674-0440.2010.06.006.
[24]XIAOZ,DAIS,NIUY,etal.DiscriminationofChinesevinegars based on headspace solid-phase microextraction-gas chromatography mass spectrometry of volatile compounds and multivariate analysis[J].Journal of Food Science, 2011, 76(8):C1125-C1135. DOI:10.1111/j.1750-3841.2011.02356.x.
[25]BONONI M, TATEO F. Determination of furan by headspace solidphasemicroextraction-gas-chromatography-massspectrometryin balsamic vinegars of Modena(Italy)[J]. Journal of Food Composition and Analysis, 2009, 22(1):79-82. DOI:10.1016/j.jfca.2008.07.011.
[26]熊越,贺稚非,李洪军,等.顶空固相微萃取-气质联用分析四川麸醋的香气成分[J].食品科学, 2011, 32(2):252-255.
[27]UBEDAC.Determinationofmajorvolititlecompoundsduring theproductionoffruitvinegarsbystaticheadspacesolid-phase microextraction-gas-chromatography-massspectrometrymethod[J].FoodResearchInternational,2011,44(1):259-268.DOI:10.1016/j.foodres.2010.10.025.
[28]YU Y J. HS-SPME/GC-MS and chemometrics for volatile composition of Chinese traditional aromatic vinegar in the Zhenjiang region[J]. Journal of the Institute of Brewing, 2012, 118(1):133-141. DOI:10.1002/jib.20.
[29]郝红梅,张生万,郭彩霞,等.顶空固相微萃取-气相色谱-质谱联用法分析山楂果醋易挥发成分[J].食品科学, 2016, 37(2):138-141.DOI:10.7506/spkx1002-6630-201602024.
[30]孙宗保,赵杰文,邹小波,等. HS-SPME/GC-MS/GC-O对镇江香醋特征香气成分的确定[J].江苏大学学报(自然科学版), 2010, 31(2):139-144. DOI:10.3969/j.issn.1671-7775.2010.02.004.
[31]李新蕊.主成分分析、因子分析、聚类分析的比较和应用[J].山东教育学院学报, 2007, 124(6):23-26.
[32]胡雷芳.五种常用系统聚类分析方法及其比较[J].统计科学与实践,2007(4):11-13. DOI:10.3969/j.issn.1674-8905.2007.04.004.
[33]蔚慧,杨林华,赵芳,等.6种李子果实香气成分的分析研究[J].安徽农业科学,2012,40(24):13601-13604.DOI:10.3969/j.issn.0517-6611.2012.27.134.
[34]国家药品监督管理局.中药注射剂指纹图谱研究的技术要求(暂行)[J].中成药,2000,22(10):671-675.DOI:10.3969/j.issn.1001-1528.2000.10.002.
[35]DAMERAU A, KAMLANG-EK P, MOISIO T, et al. Effect of SPME extractionconditionsandhumidityonthereleaseofvolatilelipid oxidation products from spray-dried emulsions[J]. Food Chemistry,2014, 157(11):1-9. DOI:10.1016/j.foodchem.2014.02.032.
[36]陈树俊,苏静,张海英,等.山西老陈醋功效成分的研究进展[J].农产品加工(创新版),2009(12):45-49.DOI:10.3969/j.issn.1671-9646.2009.12.015.
[37]范文来,徐岩.白酒79个风味化合物嗅觉阈值测定[J].酿酒, 2011,38(4):80-84. DOI:10.3969/j.issn.1002-8110.2011.04.034.
[38]王伟岗,曹伟,朱新生.食醋中有机酸含量的测定及差异性分析[J].食品与发酵科技, 2013, 39(2):81-84. DOI:10.3969/j.issn.1674-506X.2013.02-022.
[2]马永昆,蒋家奎,魏永义,等.基于GC-MS与嗅闻连用的镇江香醋香气指纹图谱研究[J].食品科学, 2007, 28(9):496-499. DOI:10.3321/j.issn:1002-6630.2007.09.121.
[3]孙宗保,邹小波,赵杰文.几种中国传统名醋挥发性风味成分的比较研究[J].中国调味品, 2010, 35(9):34-41. DOI:10.3969/j.issn.1000-9973.2010.09.004.
[4]李慧,韩建欣,李婷,等.四大名醋挥发性香气成分的测定与比较分析[J].中国调味品, 2017, 42(4):154-158. DOI:10.3969/j.issn.1000-9973.2017.04.035.
[5]CIRLINI M, CALIGIANI A, PALLA L, et al. HS-SPME/GC-MS and chemometrics for the classi?cation of balsamic vinegars of Modena of different maturation and ageing[J]. Food Chemistry, 2011, 124(4):1678-1683. DOI:10.1016/j.foodchem.2010.07.065.
[6]苗志伟,刘玉平,陈海涛,等.两种陈酿期山西老陈醋挥发性成分分析[J].食品科学, 2010, 31(24):380-384.
[7]CHENT,GUIQ,SHIJJ,etal.Analysisofvariationofmain components during aging process of Shanxi aged vinegar[J]. Acetic Acid Bacteria, 2013, 2(Suppl1):6. DOI:10.4081/aab.2013.s1.e6.
[8]李弘文,王旭萍,杨小兰.不同熏醅工艺对山西老陈醋香气成分的影响[J].食品科学, 2015, 36(20):90-94. DOI:10.7506/spkx1002-6630-201520016.
[9]魏永义,张东升.食醋香气感官评定研究[J].中国调味品,2015,40(12):123-125.
[10]魏永义,王飞.食醋香气成分及其检测方法研究进展[J].中国调味品, 2011, 36(11):59-61. DOI:10.3969/j.issn.1000-9973.2011.11.017.
[11]胡红娟.山西老陈醋酿造技艺[J].食品工程,2015(3):18-20.DOI:10.3969/j.issn.1673-6044.2015.03.006.
[12]李丽,路海峰,梁丽绒,等.山西老陈醋香气成分分析[J].山西大学学报(自然科学版),2005,28(2):209-213.DOI:10.3969/j.issn.0253-2395.2005.02.027.
[13]袁仲,李哲斌.气相色谱/质谱法联用分析山西老陈醋香味成分[J].中国调味品,2011,36(5):105-108.DOI:10.3969/j.issn.1000-9973.2011.05.030.
[14]苗志伟,刘玉平,黄明泉,等.HS-SPME和GC-MS联用分析山西老陈醋中挥发性香味成分[J].中国食品学报, 2011, 11(8):197-202.DOI:10.3969/j.issn.1009-7848.2011.08.031.
[15]魏永义.镇江香醋香气检测及其香气指纹图谱的研究[D].镇江:江苏大学, 2007:33.
[16]解华东,布丽君,李志西.基于紫外指纹图谱技术的食醋品种检测方法[J].农业机械学报, 2009, 40(4):133-138.
[17]刘晓伟,李忠海,杨代明,等.高效液相色谱指纹图谱对食醋的掺伪判定研究[J].中国调味品, 2010, 35(6):96-105. DOI:10.3969/j.issn.1000-9973.2010.06.024.
[18]刘晓伟,杨代明,孙桂芳.食醋有机酸的液相指纹图谱建立方法研究[J].食品工业科技, 2011, 32(5):403-406.
[19]山西大学.山西老陈醋液相指纹图谱的构建方法和应用:201510400315.X[P]. 2015-07-09.
[20]山西大学.山西老陈醋1H-N M R指纹图谱的构建方法和应用:201610317142.X[P]. 2016-05-12.
[21]武振宇,朱静.指纹图谱技术在食醋检测中的应用[J].农业品加工,2013, 332(10):69-70. DOI:10.3969/jissn.1671-9646(X).2013.10.051.
[22]孙国祥,闫波,侯志飞,等.中药色谱指纹图谱评价方法研究进展[J].中南药学,2015,13(7):673-681.DOI:10.7539/j.issn.1672-2981.2015.07.001.
[23]刘万仓,孙磊,于孟琦,等.中药指纹图谱模式识别研究进展[J].国际药学研究杂质,2010,37(6):446-449.DOI:10.3969/j.issn.1674-0440.2010.06.006.
[24]XIAOZ,DAIS,NIUY,etal.DiscriminationofChinesevinegars based on headspace solid-phase microextraction-gas chromatography mass spectrometry of volatile compounds and multivariate analysis[J].Journal of Food Science, 2011, 76(8):C1125-C1135. DOI:10.1111/j.1750-3841.2011.02356.x.
[25]BONONI M, TATEO F. Determination of furan by headspace solidphasemicroextraction-gas-chromatography-massspectrometryin balsamic vinegars of Modena(Italy)[J]. Journal of Food Composition and Analysis, 2009, 22(1):79-82. DOI:10.1016/j.jfca.2008.07.011.
[26]熊越,贺稚非,李洪军,等.顶空固相微萃取-气质联用分析四川麸醋的香气成分[J].食品科学, 2011, 32(2):252-255.
[27]UBEDAC.Determinationofmajorvolititlecompoundsduring theproductionoffruitvinegarsbystaticheadspacesolid-phase microextraction-gas-chromatography-massspectrometrymethod[J].FoodResearchInternational,2011,44(1):259-268.DOI:10.1016/j.foodres.2010.10.025.
[28]YU Y J. HS-SPME/GC-MS and chemometrics for volatile composition of Chinese traditional aromatic vinegar in the Zhenjiang region[J]. Journal of the Institute of Brewing, 2012, 118(1):133-141. DOI:10.1002/jib.20.
[29]郝红梅,张生万,郭彩霞,等.顶空固相微萃取-气相色谱-质谱联用法分析山楂果醋易挥发成分[J].食品科学, 2016, 37(2):138-141.DOI:10.7506/spkx1002-6630-201602024.
[30]孙宗保,赵杰文,邹小波,等. HS-SPME/GC-MS/GC-O对镇江香醋特征香气成分的确定[J].江苏大学学报(自然科学版), 2010, 31(2):139-144. DOI:10.3969/j.issn.1671-7775.2010.02.004.
[31]李新蕊.主成分分析、因子分析、聚类分析的比较和应用[J].山东教育学院学报, 2007, 124(6):23-26.
[32]胡雷芳.五种常用系统聚类分析方法及其比较[J].统计科学与实践,2007(4):11-13. DOI:10.3969/j.issn.1674-8905.2007.04.004.
[33]蔚慧,杨林华,赵芳,等.6种李子果实香气成分的分析研究[J].安徽农业科学,2012,40(24):13601-13604.DOI:10.3969/j.issn.0517-6611.2012.27.134.
[34]国家药品监督管理局.中药注射剂指纹图谱研究的技术要求(暂行)[J].中成药,2000,22(10):671-675.DOI:10.3969/j.issn.1001-1528.2000.10.002.
[35]DAMERAU A, KAMLANG-EK P, MOISIO T, et al. Effect of SPME extractionconditionsandhumidityonthereleaseofvolatilelipid oxidation products from spray-dried emulsions[J]. Food Chemistry,2014, 157(11):1-9. DOI:10.1016/j.foodchem.2014.02.032.
[36]陈树俊,苏静,张海英,等.山西老陈醋功效成分的研究进展[J].农产品加工(创新版),2009(12):45-49.DOI:10.3969/j.issn.1671-9646.2009.12.015.
[37]范文来,徐岩.白酒79个风味化合物嗅觉阈值测定[J].酿酒, 2011,38(4):80-84. DOI:10.3969/j.issn.1002-8110.2011.04.034.
[38]王伟岗,曹伟,朱新生.食醋中有机酸含量的测定及差异性分析[J].食品与发酵科技, 2013, 39(2):81-84. DOI:10.3969/j.issn.1674-506X.2013.02-022.