基于~1H-NMR代谢组学初步比较真蜂蜜和掺假蜂蜜差异成分
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摘要
采集蜂蜜样品的核磁共振氢图谱(~1H-NMR),通过多元统计分析及相关系数负载图法找出真蜂蜜和掺假蜂蜜的差异性化学成分。结果表明,在蜂蜜的~1H-NMR图谱中,共有24个物质的~1H-NMR信号,包括7个有机酸,15个糖类和2个其他类物质。通过对真蜂蜜和掺假蜂蜜之间的比较分析,得出真蜂蜜组中的苏氨酸、脯氨酸、松二糖、曲二糖、松三糖和苯基丙氨酸含量高于掺假蜂蜜,而2,3-丁二醇、乙偶姻、甘露糖、5-羟甲基糠醛和甲酸的含量低于掺假蜂蜜组,并且都具有显著性差异(p<0.05)。应用NMR代谢组学技术从整体水平上分析蜂蜜样品的化学成分,可以发现真蜂蜜与掺假蜂蜜之间的差异性化学成分,为蜂蜜真假鉴别提供了新思路。
In order to compare the chemical constituents in honey and adulterated honey,the~1H nuclear magnetic resonance(~1H-NMR)and multivariate statistical analysis was used to analyze the chemical constituents of honey and adulterated honey. Twenty four substances were recognized in the~1H-NMR profiling,including seven organic acids,fifteen saccharide and two other substances. It was found that the levels of threonine,proline,turanose,kojibiose,melezitose and phenylalanine were higher,while 2,3-butanediol,acetoin,mannose,5-hydroxymethyl furfural and formic acid were lower in the honey than in adulterated honey. And all these differences were significant(p<0.05).~1H-NMR based metabolomic study on honey could not only be used to identify of adulterated honey,but also analyze the difference components. And it provided the new way and reasonable idea for quality control study of honey.
In order to compare the chemical constituents in honey and adulterated honey,the~1H nuclear magnetic resonance(~1H-NMR)and multivariate statistical analysis was used to analyze the chemical constituents of honey and adulterated honey. Twenty four substances were recognized in the~1H-NMR profiling,including seven organic acids,fifteen saccharide and two other substances. It was found that the levels of threonine,proline,turanose,kojibiose,melezitose and phenylalanine were higher,while 2,3-butanediol,acetoin,mannose,5-hydroxymethyl furfural and formic acid were lower in the honey than in adulterated honey. And all these differences were significant(p<0.05).~1H-NMR based metabolomic study on honey could not only be used to identify of adulterated honey,but also analyze the difference components. And it provided the new way and reasonable idea for quality control study of honey.
引文
[1]中华人民共和国卫生部. GB 14963-2011食品安全国家标准蜂蜜[S]. 北京:中国标准出版社,2011.
[2]吴国泰,武玉鹏,牛亭惠,等. 蜂蜜的化学、药理及应用研究概况[J]. 蜜蜂杂志,2017,37(1):3-6.
[3]袁玉伟,张志恒,叶雪珠,等. 蜂蜜掺假鉴别技术的研究进展与对策建议[J]. 食品科学,2010,31(9):318-322.
[4]裴高璞,史波林,赵镭,等. 蜂蜜质量市场动态及掺假检测方法现状分析[J]. 食品科学,2013,34(15):329-336.
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[6]中华人民共和国国家质量监督检验检疫总局. GB/T 18932.2-2002 蜜蜂中高果糖淀粉糖浆测定方法:薄层色谱法[S]. 北京:中国标准出版社,2002.
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[9]Karoui R,Durour E,Bosset J O,et al. The use of front face fluorescence spectroscopy to classify the botanical origin of honey samples produced in Switzerland[J]. Food Chemistry,2007,101(1):314-323.
[10]Cordella AC,Antinelli J,Faurieres C,et al. Use of differential scanning calorimetry(DSC)as a new technique for detection of adulteration in honeys.1.Study of adulteration effect on honey thermal behavior[J]. Journal of Agricultural Food Chemistry,2002,50(1):203-208.
[11]Kerkvliet J D,Meijer H A J. Adulteration of honey:relation between microscopic analysis and δ13C measurements[J]. Apidologie,2000,31(6):717-726.
[12]吴燕涛,穆同娜,王绍清,等. 现代分析技术在蜂蜜掺假鉴别中应用研究进展[J]. 食品研究与开发,2015(5):137-142.
[13]李玮,姜洁,路勇,等. NMR氢谱定量测定奶酪中总共轭亚油酸的含量[J]. 食品科学,2015,36(10):134-138.
[14]姜洁,李玮,路勇,等. 核磁共振脉冲宽度法测定婴幼儿乳粉中乳糖、蔗糖含量[J]. 食品工业科技,2015,36(8):68-71.
[15]李玮,贾婧怡,姜洁,等. NMR氢谱法分析市售奶油中的脂肪酸[J]. 食品工业科技,2016,37(23):320-324.
[16]李玮,贾婧怡,李龙,等. 核磁共振代谢组学技术鉴别天然奶油与人造奶油[J]. 食品科学,2017,38(12):278-285.
[17]Spiteri M,Rogers K M,Jamin E,et al. Combination of1H NMR and chemometrics to discriminate manuka honey from other floral honey types from Oceania[J]. Food Chemistry,2017,217(15):766-772.
[18]Boffo E F,Tavares L A,Tobias A C T,et al. Identification of components of Brazilian honey by1H NMR and classification ofits botanical origin by chemometric methods[J]. LWT-Food Science and Technology,2012,49(1):55-63.
[19]陈雷,刘红兵,罗立廷. 氢核磁共振结合正交偏最小二乘法对油菜蜜中果葡糖浆掺假的判别分析[J]. 食品科学,2017,38(4):275-282.
[20]刘芸,丁涛,吴斌,等. 核磁共振技术结合化学计量学方法用于蜂蜜的掺假鉴别[J]. 分析测试学报,2016,35(10):1248-1254.
[21]Campo G D,Zuriarrain J,Zuriarrain A,et al. Quantitative determination of carboxylic acids,amino acids,carbohydrates,ethanol and hydroxymethylfurfural in honey by 1H-NMR[J]. Food Chemistry,2016,196(1):1031.
[22]Ohmenhaeuser M,Monakhova Y B,Kuballa T,et al. Qualitative and quantitative control of honeys using NMR spectroscopy and chemometrics[J]. Isrn Analytical Chemistry,2015,2013(4):825318.
[23]Schievano E,Tonoli M,Rastrelli F. NMR quantification of carbohydrates in complex mixtures:A challenge on honey[J]. Analytical Chemistry,2017,89(24):13405-13414.
[24]孙政,程妮,曹炜.蜂蜜中氨基酸应用研究进展[J]. 食品与发酵工业,2016,42(1):260-263.
[25]杨海军. 果葡糖浆的特性及应用[J]. 食品科学,2002,23(2):154-156.
[26]王彤. 天然糖类的高效毛细管电泳分离分析方法构建与应用[D]. 西安:第四军医大学,2012:48.
[27]中华全国供销合作总社. GH/T 18796-2012中华人民共和国供销合作行业标准蜂蜜[S]. 北京:中国标准出版社,2012.
[28]Montenegro G,Gomez M,Casaubon G,et al. Analysis of volatile compounds in three unifloral native Chilean honeys[J]. Phyton(Buenos Aires),2009,78:61-65.
[29]纪晓俊,黄和,李玲,等. 2,3-丁二醇发酵过程中葡萄糖碳流分配数学模型[J]. 化学与生物工程,2007,24(2):32-36.
[2]吴国泰,武玉鹏,牛亭惠,等. 蜂蜜的化学、药理及应用研究概况[J]. 蜜蜂杂志,2017,37(1):3-6.
[3]袁玉伟,张志恒,叶雪珠,等. 蜂蜜掺假鉴别技术的研究进展与对策建议[J]. 食品科学,2010,31(9):318-322.
[4]裴高璞,史波林,赵镭,等. 蜂蜜质量市场动态及掺假检测方法现状分析[J]. 食品科学,2013,34(15):329-336.
[5]Spiteri M,Jamin E,Thomas F,et al. Fast and global authenticity screening of honey using 1H-NMR profiling[J]. Food Chemistry,2015,189(15):60-66.
[6]中华人民共和国国家质量监督检验检疫总局. GB/T 18932.2-2002 蜜蜂中高果糖淀粉糖浆测定方法:薄层色谱法[S]. 北京:中国标准出版社,2002.
[7]中华人民共和国国家质量监督检验检疫总局. GB/T 18932.1-2002蜂蜜中碳-4植物糖含量测定方法稳定碳同位素比率法[S]. 北京:中国标准出版社,2002.
[8]中华人民共和国国家质量监督检验检疫总局. GB/T 18932.22-2003.蜂蜜中果糖、葡萄糖、蔗糖、麦芽糖含量的测定方法-液相色谱示差折光检测法[S]. 北京:中国标准出版社,2002.
[9]Karoui R,Durour E,Bosset J O,et al. The use of front face fluorescence spectroscopy to classify the botanical origin of honey samples produced in Switzerland[J]. Food Chemistry,2007,101(1):314-323.
[10]Cordella AC,Antinelli J,Faurieres C,et al. Use of differential scanning calorimetry(DSC)as a new technique for detection of adulteration in honeys.1.Study of adulteration effect on honey thermal behavior[J]. Journal of Agricultural Food Chemistry,2002,50(1):203-208.
[11]Kerkvliet J D,Meijer H A J. Adulteration of honey:relation between microscopic analysis and δ13C measurements[J]. Apidologie,2000,31(6):717-726.
[12]吴燕涛,穆同娜,王绍清,等. 现代分析技术在蜂蜜掺假鉴别中应用研究进展[J]. 食品研究与开发,2015(5):137-142.
[13]李玮,姜洁,路勇,等. NMR氢谱定量测定奶酪中总共轭亚油酸的含量[J]. 食品科学,2015,36(10):134-138.
[14]姜洁,李玮,路勇,等. 核磁共振脉冲宽度法测定婴幼儿乳粉中乳糖、蔗糖含量[J]. 食品工业科技,2015,36(8):68-71.
[15]李玮,贾婧怡,姜洁,等. NMR氢谱法分析市售奶油中的脂肪酸[J]. 食品工业科技,2016,37(23):320-324.
[16]李玮,贾婧怡,李龙,等. 核磁共振代谢组学技术鉴别天然奶油与人造奶油[J]. 食品科学,2017,38(12):278-285.
[17]Spiteri M,Rogers K M,Jamin E,et al. Combination of1H NMR and chemometrics to discriminate manuka honey from other floral honey types from Oceania[J]. Food Chemistry,2017,217(15):766-772.
[18]Boffo E F,Tavares L A,Tobias A C T,et al. Identification of components of Brazilian honey by1H NMR and classification ofits botanical origin by chemometric methods[J]. LWT-Food Science and Technology,2012,49(1):55-63.
[19]陈雷,刘红兵,罗立廷. 氢核磁共振结合正交偏最小二乘法对油菜蜜中果葡糖浆掺假的判别分析[J]. 食品科学,2017,38(4):275-282.
[20]刘芸,丁涛,吴斌,等. 核磁共振技术结合化学计量学方法用于蜂蜜的掺假鉴别[J]. 分析测试学报,2016,35(10):1248-1254.
[21]Campo G D,Zuriarrain J,Zuriarrain A,et al. Quantitative determination of carboxylic acids,amino acids,carbohydrates,ethanol and hydroxymethylfurfural in honey by 1H-NMR[J]. Food Chemistry,2016,196(1):1031.
[22]Ohmenhaeuser M,Monakhova Y B,Kuballa T,et al. Qualitative and quantitative control of honeys using NMR spectroscopy and chemometrics[J]. Isrn Analytical Chemistry,2015,2013(4):825318.
[23]Schievano E,Tonoli M,Rastrelli F. NMR quantification of carbohydrates in complex mixtures:A challenge on honey[J]. Analytical Chemistry,2017,89(24):13405-13414.
[24]孙政,程妮,曹炜.蜂蜜中氨基酸应用研究进展[J]. 食品与发酵工业,2016,42(1):260-263.
[25]杨海军. 果葡糖浆的特性及应用[J]. 食品科学,2002,23(2):154-156.
[26]王彤. 天然糖类的高效毛细管电泳分离分析方法构建与应用[D]. 西安:第四军医大学,2012:48.
[27]中华全国供销合作总社. GH/T 18796-2012中华人民共和国供销合作行业标准蜂蜜[S]. 北京:中国标准出版社,2012.
[28]Montenegro G,Gomez M,Casaubon G,et al. Analysis of volatile compounds in three unifloral native Chilean honeys[J]. Phyton(Buenos Aires),2009,78:61-65.
[29]纪晓俊,黄和,李玲,等. 2,3-丁二醇发酵过程中葡萄糖碳流分配数学模型[J]. 化学与生物工程,2007,24(2):32-36.