基于HPLC-ELSD和偏最小二乘判别分析法的蜂蜜掺假鉴别
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摘要
为了实现蜂蜜掺假的简便、快速识别,应用高效液相色谱技术和化学计量学手段建立了一种蜂蜜掺假检测的新方法。该研究收集了中国不同品种、不同地域的典型天然蜂蜜样品,根据目前市场上常见的蜂蜜掺假手段、掺假物质及相对含量情况模拟制备系列掺假蜂蜜样品,利用HPLC-ELSD对样品中糖类物质进行分离测定,并采用PLS-DA统计学方法进行蜂蜜掺假识别研究。研究结果表明:掺入质量分数10%以上果葡糖浆和麦芽糖浆的掺假蜂蜜样品均能利用本方法予以鉴别,其校正集的正确判别率达到92.5%,验证集的正确判别率为100%。
In order to identify the honey adulteration,this paper present a new high performance liquid chromatography method,coupled with chemometric analysis,used to identification of adulterated honey. The sugar composibion of 33 honey samples obtained from different areas were separated and detected by HPLC-ELSD equipped with Amide column,The method relies on the use of chemometric methods to process chromatograms in order to achieve a better discrimination between authentic and adulterated honeys by partial least squares-discriminant analysis(PLS-DA). This approach was investigated using honey samples adulterated from 10% to 30% with high fructose syrup and maltose syrup. Good result were obtained in the characterization of authentic and adulterated samples:92.5% of good classification in the training set and 100% in the test set.
In order to identify the honey adulteration,this paper present a new high performance liquid chromatography method,coupled with chemometric analysis,used to identification of adulterated honey. The sugar composibion of 33 honey samples obtained from different areas were separated and detected by HPLC-ELSD equipped with Amide column,The method relies on the use of chemometric methods to process chromatograms in order to achieve a better discrimination between authentic and adulterated honeys by partial least squares-discriminant analysis(PLS-DA). This approach was investigated using honey samples adulterated from 10% to 30% with high fructose syrup and maltose syrup. Good result were obtained in the characterization of authentic and adulterated samples:92.5% of good classification in the training set and 100% in the test set.
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]中华全国供销总社. GH/T 18796-2012蜂蜜[S].北京:国家标准出版社,2012.
[3] LEI Ming,HE Jinzhe,SUN Peilong. Review of detecting techniques of honey adulteration[J]. Food Science and Technology,2012,37(7):283-287.(in Chinese)
[4] RUIZ-MATUTE A I,SORIA A C,MARTINEZ-CASTRO I,et al. A new methodology based on GC-MS to det-ect honey adulteration with commercial syrups[J]. Journ-al of Agricultural and Food Chemistry,2007,55:7264-7269.
[5] RUIZ-MATUTE A I,SANZ M L,MARTINEZ-CASTRO I. Use of gas chromatography-mass spectrometry for identification of a new disaccharide in honey[J]. Journal of Chromatography A,2007,1157:480-483.
[6] RUIZ-MATUTE A I,RODRIGUEZ-SANCHEZ S,SANZ M L,et al. Detection of adulterations of honey with high fructose syrups from inulin by GC analysis[J]. Journal of Food Composition and Analysis,2010,23:273-276.
[7] MEHDI M,BERNARD H,RENE F,et al. Polysaccharides as a marker for detection of corn sugar syrup addition in honey[J].Journal of Agricultural and Food Chemistry,2009,57:2105-2111.
[8] LI Shuifang. Qualitive and quantitative detective of beet syrup adulteration of honey by Near-Infrared spectroscopy:a feasibility study[J]. Spectroscropy and Spectral Analysis,2013,33(10):2637-2641.(in Chinese)
[9] DAVIDE B,MASSIMO L. Detection of honey adulteration by sugar syrups using one-dimensional and two-dimensional high-resolution nuclear magnetic resonance[J]. Journal of Agricultural and Food Chemistry,2010,58:8495-8501.
[10] MURAT T. Detection of adulteration in honey samples added various sugar syrups with 13c/12c isotope ratio analysis method[J].Food Chemistry,2013,138:1629-1632.
[11] DAI Jun. Progress in application of liquid chromatography in the analysis of sugars[J]. Chinese Journal of Chromatograp-hy,2012,30(2):113-115.(in Chinese)
[12] YU Juan. Detemination of sugars in honey by HPLC-ELSD method[J]. Guangxi Journal of Light Industry,2006,6:20-21.(in Chinese)
[13] WANG Zhen. Detemination of four sugars in honey by HPLC-ELSD method[J]. Gansu Science and Technology,2014,30(7).(in Chinese)
[14] YANG Z M,HU J,ZHAO M Y. Isolation and quantitative determination of in-ulin-type oligosaccharides in ro-ots of morinda officinalis[J]. Carbohydrate Polymers,2011,83:1997-2004.
[15] Serap B. Cinar,Aziz Eksi,Ilknur Coskun. Carbon isotope ratio(13C/12C)of pine honey and detection of HFCS adulteration[J].Food Chemistry,2014,157:10-13.
[16] CHRISTOPHE C,JULIO S L T M. Detection and quantification of honey adulteration via direct incorpora-tion of sugar syrups or bee-feeding:preliminary study using High-Performance Anion Exchange Chromatography with pulsed Amperometric Detec-tion(HPAEC-PAD)and chem ometrics[J]. Analytica Chimica Acta,2005,531:239-248.
[17] ELISABETTA S,EVARISTO P. 1H nuclear magnetic resonance spectra of c-hloroform extracts of honey for c-hemometric determination of its botanical origin[J]. Jo-urnal of Agricultural and Food Chemistry,2010,58:57-65.
[18] TANG Jun,LIAO Xiang. GC-MS combined with PLS-DA to discriminate the varieties of XinJiang lavender essential oil[J].Computers and Applied Chemistry,2014,31(6):701-704.(in Chinese)
[19] LI Libing,CHEN Kangning,WANG Jiajun,et al. Classification of tobacco flavors by PLS-DA combined with Multi-Bounce attenuated total reflectance IR fingerprint spectra[J]. Tobacco Chemistry,2014,7:37-39.(in Chinese)
[20] ERIKSSON L,JOHANSSON E,KETTANEH-WOLD N,et al. Multi-and Megavariate. Data analysis. part:basic principles and applications[M]. Sweden:Umetrics AB,2006.
[21] WANG Zhenbin,SHAO Shuping. Application of principal component analysis in comprehensive assessment of ultrasound treatment on vinegar[J]. Journal of Food and Biotechnology,2015,34(6):627-633.(in Chinese)
[2]中华全国供销总社. GH/T 18796-2012蜂蜜[S].北京:国家标准出版社,2012.
[3] LEI Ming,HE Jinzhe,SUN Peilong. Review of detecting techniques of honey adulteration[J]. Food Science and Technology,2012,37(7):283-287.(in Chinese)
[4] RUIZ-MATUTE A I,SORIA A C,MARTINEZ-CASTRO I,et al. A new methodology based on GC-MS to det-ect honey adulteration with commercial syrups[J]. Journ-al of Agricultural and Food Chemistry,2007,55:7264-7269.
[5] RUIZ-MATUTE A I,SANZ M L,MARTINEZ-CASTRO I. Use of gas chromatography-mass spectrometry for identification of a new disaccharide in honey[J]. Journal of Chromatography A,2007,1157:480-483.
[6] RUIZ-MATUTE A I,RODRIGUEZ-SANCHEZ S,SANZ M L,et al. Detection of adulterations of honey with high fructose syrups from inulin by GC analysis[J]. Journal of Food Composition and Analysis,2010,23:273-276.
[7] MEHDI M,BERNARD H,RENE F,et al. Polysaccharides as a marker for detection of corn sugar syrup addition in honey[J].Journal of Agricultural and Food Chemistry,2009,57:2105-2111.
[8] LI Shuifang. Qualitive and quantitative detective of beet syrup adulteration of honey by Near-Infrared spectroscopy:a feasibility study[J]. Spectroscropy and Spectral Analysis,2013,33(10):2637-2641.(in Chinese)
[9] DAVIDE B,MASSIMO L. Detection of honey adulteration by sugar syrups using one-dimensional and two-dimensional high-resolution nuclear magnetic resonance[J]. Journal of Agricultural and Food Chemistry,2010,58:8495-8501.
[10] MURAT T. Detection of adulteration in honey samples added various sugar syrups with 13c/12c isotope ratio analysis method[J].Food Chemistry,2013,138:1629-1632.
[11] DAI Jun. Progress in application of liquid chromatography in the analysis of sugars[J]. Chinese Journal of Chromatograp-hy,2012,30(2):113-115.(in Chinese)
[12] YU Juan. Detemination of sugars in honey by HPLC-ELSD method[J]. Guangxi Journal of Light Industry,2006,6:20-21.(in Chinese)
[13] WANG Zhen. Detemination of four sugars in honey by HPLC-ELSD method[J]. Gansu Science and Technology,2014,30(7).(in Chinese)
[14] YANG Z M,HU J,ZHAO M Y. Isolation and quantitative determination of in-ulin-type oligosaccharides in ro-ots of morinda officinalis[J]. Carbohydrate Polymers,2011,83:1997-2004.
[15] Serap B. Cinar,Aziz Eksi,Ilknur Coskun. Carbon isotope ratio(13C/12C)of pine honey and detection of HFCS adulteration[J].Food Chemistry,2014,157:10-13.
[16] CHRISTOPHE C,JULIO S L T M. Detection and quantification of honey adulteration via direct incorpora-tion of sugar syrups or bee-feeding:preliminary study using High-Performance Anion Exchange Chromatography with pulsed Amperometric Detec-tion(HPAEC-PAD)and chem ometrics[J]. Analytica Chimica Acta,2005,531:239-248.
[17] ELISABETTA S,EVARISTO P. 1H nuclear magnetic resonance spectra of c-hloroform extracts of honey for c-hemometric determination of its botanical origin[J]. Jo-urnal of Agricultural and Food Chemistry,2010,58:57-65.
[18] TANG Jun,LIAO Xiang. GC-MS combined with PLS-DA to discriminate the varieties of XinJiang lavender essential oil[J].Computers and Applied Chemistry,2014,31(6):701-704.(in Chinese)
[19] LI Libing,CHEN Kangning,WANG Jiajun,et al. Classification of tobacco flavors by PLS-DA combined with Multi-Bounce attenuated total reflectance IR fingerprint spectra[J]. Tobacco Chemistry,2014,7:37-39.(in Chinese)
[20] ERIKSSON L,JOHANSSON E,KETTANEH-WOLD N,et al. Multi-and Megavariate. Data analysis. part:basic principles and applications[M]. Sweden:Umetrics AB,2006.
[21] WANG Zhenbin,SHAO Shuping. Application of principal component analysis in comprehensive assessment of ultrasound treatment on vinegar[J]. Journal of Food and Biotechnology,2015,34(6):627-633.(in Chinese)