甘油三酯指纹图谱在食用植物油掺伪鉴别中的应用

doi:10.11923/j.issn.2095-4050.cjas20190600065

摘要/Abstract

摘要：

为了构建橄榄油、大豆油、花生油、玉米油、葵花籽油、菜籽油的甘油三酯指纹图谱,采用反相液相色谱-蒸发光散射检测器对6种食用植物油中甘油三酯进行分离,图谱数据采用平均矢量法导入中药色谱指纹图谱相似度评价系统（2012版）,分析指纹图谱的相似度。结果表明,同一种食用植物油不同品牌间的甘油三酯指纹图谱相似度高,不同食用植物油的甘油三酯指纹图谱差异明显。橄榄油与玉米油、大豆油及葵花籽油相似度比较低,分别为0.233、0.086、0.073;与菜籽油、花生油相似度较高,分别为0.830和0.776。当橄榄油中掺入10%的大豆油、玉米油或葵花籽油时,其指纹图谱相似度均低于0.90。橄榄油中掺入菜籽油后其相似度变化不明显。采用面积归一法对指纹图谱特征峰进行分析,掺入比例的检出限低于15%。甘油三酯指纹图谱与面积归一法相结合,可作为食用植物油鉴定及掺伪鉴别的有效手段。

关键词: 食用植物油, 甘油三酯, 指纹图谱, 种类鉴定, 掺伪鉴别

Abstract:

To construct the triglyceride fingerprint of olive oil, soybean oil, peanut oil, corn oil, sunflower oil and rapeseed oil, triglycerides of the six edible vegetable oils were isolated by HPLC-ELSD. The data was imported into the traditional Chinese medicine chromatographic fingerprint similarity evaluation system (version 2012) by the average vector method, and the similarity of the fingerprint was analyzed. The results showed that the fingerprint profile of triglycerides was similar among different brands of the same edible vegetable oil, while was significantly different among various edible vegetable oils. Olive oil had low similarity with corn oil, soybean oil, or sunflower oil, and the similarity was 0.233, 0.086 and 0.073, respectively; however, it had high similarity with rapeseed oil and peanut oil, and the similarity was 0.830 and 0.776, respectively. When olive oil was mixed with 10% corn oil, soybean oil, or sunflower oil, the similarity of triglyceride fingerprint was less than 0.90, but the similarity change was not obvious when mixed with rapeseed oil. Area normalization method was used to analyze the characteristic peak of fingerprint, and the detection limit of adulteration ratio was less than 15%. The combination of triglyceride fingerprint and area normalization method can be an effective method for identification the adulteration of edible vegetable oil.

Key words: edible vegetable oil, triglyceride, fingerprint, identification, adulteration

中图分类号:

TS207.3

翁嘉, 黄秀丽, 朱文娟, 王晓琴. 甘油三酯指纹图谱在食用植物油掺伪鉴别中的应用[J]. 农学学报, 2021, 11(10): 95-101.

Weng Jia, Huang Xiuli, Zhu Wenjuan, Wang Xiaoqin. Application of Triglyceride Fingerprint in Identification of Adulterated Edible Oil[J]. Journal of Agriculture, 2021, 11(10): 95-101.

图/表 7

参考文献 27

[1]	籍淑贤, 魏芳, 胡娜, 等. 食用植物油中甘油三酯色谱分析方法研究进展[J]. 分析测试学报, 2014, 33(1):112-118.
[2]	朱桃花, 范璐, 钱向明, 等. HPLC分析植物油脂甘油三酯结构组成的研究现状[J]. 中国油脂, 2011, 36(5):59-63.
[3]	张东, 龙伶俐, 薛雅琳, 等. 液质联用分析常见植物油甘油三酯[J]. 粮油食品科技, 2012, 20(6):33-37.
[4]	管方方, 何卓琼, 方燕, 等. GC-MS 分析食用油中甘油三酯的研究进展[J]. 中国油脂, 2014, 39(5):76-80.
[5]	赵海珍, 陆兆新, 别小妹, 等. 高效液相色谱法测定猪油甘油三酯中的脂肪酸位置分布[J]. 色谱, 2005(2):142-145.
[6]	何榕, 山晓琳, 董方圆, 等. 反相超效液相色谱–质谱联用分离分析食用油中的甘油三酯[J]. 分析化学, 2015, 43(9):1377-1382.
[7]	Byrdwell W C, Emken E A, Nef W E, et al. Quantitative analysis of triglycerides using atmospheric pressure chemical ionization mass spectrometry[J]. Lipids, 1996, 31(9):919-935. pmid: 8882971
[8]	张樱, 王豪, 林振兴, 等. 内燃机油高效液相指纹图谱的建立[J]. 分析测试学报, 2013, 32(6):737-741.
[9]	Hamdy E L, Fizgank E L. Detection of olive oil adulteration by measuring its authenticity factor using reversed-phase high-performance liquid chromatography[J] J. Chromatogr. A, 1995, 708(2):351-355. doi: 10.1016/0021-9673(95)00415-J URL
[10]	Rayda B, Naziha K G, Ahmed R. Compr. Rev. Food Sci. Food Safety, 2013, 12(2):218-227.
[11]	Nef W E, Byrdwell W C. Soybean oil triacylglycerol analysis by reversed-phase high performance liquid chromatography coupled with atmospheric pressure chemical ionization mass spectrometry[J]. Journal of the American oil chemists’society, 1995, 72(10):1185-1191.
[12]	Parcerisa J, Casals I, Boatella J, et al. Analysis of olive and hazelnut oil mixtures by high-performance liquid chromatography-atmospheric pressure chemical ionization mass spectrometry of triacylglycerols and gas-liquid chromatography of non-saponifiable compounds (tocopherols and sterols)[J]. Journal of Chromatography A, 2000, 881(1/2):149-158. doi: 10.1016/S0021-9673(00)00352-6 URL
[13]	宁德山, 唐青涛, 陈路林. 液相色谱指纹图法鉴别灵芝孢子油掺伪研究[J]. 临床医学工程, 2009, 16(12):65-66.
[14]	姚云平, 李昌模, 刘慧琳, 等. 指纹图谱技术在植物油鉴定和掺假中的应用[J]. 中国油脂, 2012, 37(7):51-54.
[15]	李雪琴, 黎海红, 苗笑亮. 指纹图谱相似度在芝麻油掺伪检测中的应用[J]. 食品科技, 2009, 34(3):259-264.
[16]	兰庆丰, 梁敏. 气相色谱法鉴别掺假食用油的研究[J]. 刑事技术, 2006(1):37-39.
[17]	张国文, 倪永年, 涂北平. 食用植物油的分类和质量鉴别的模式识别研究[J]. 食品科学, 2005(1):71-75.
[18]	鲍方宇, 张敏. 薄层色谱法测定油脂中甘油三酯含量[J]. 食品科学, 2013, 34(4):125-128.
[19]	耿曼璐, 赵贝贝, 兰韬, 等. 食用油甘油三酯及其氧化聚合物分析方法研究进展[J]. 中国油脂, 2017, 42(1):134-138.
[20]	洪颖. 食用油脂甘油三酯组成特征及HPLC测定方法研究[D]. 无锡:江南大学, 2015.
[21]	孟祥河, 章银军, 毛忠贵. 甘油酯的分析方法[J]. 中国油脂, 2004, 29(1):44-46.
[22]	刘涛, 尹春华, 谭天伟. 高效液相色谱–蒸发光散射检测器测定脂肪酸和甘油酯的含量[J]. 中国油脂, 2005, 30(9):52-55.
[23]	张文婷, 程夏倩, 徐靖, 等. HPLC-ELSD测定灵芝孢子油中甘油三酯的含量[J]. 中国现代应用药学, 2017, 34(5):719-722.
[24]	GH/T 1087—2013蜂胶真实性鉴别方法高效液相色谱指纹图谱法.
[25]	DB33/T 735—2009 掺假山茶油定性鉴别气相色谱法.
[26]	陈辉, 戚建良, 李玉华, 等. 利用GC-MS指纹图谱技术快速检测掺伪大豆油的橄榄油[J]. 粮油加工:电子版, 2014(9):46-47,50.
[27]	张青龄. 气相色谱法鉴别橄榄油掺伪的研究[J]. 粮食储藏, 2014, 43(4):36-38.

精密度		重复性		稳定性		加标回收
对照品连续进样 6针峰面积	RSD/ %	平行6份样品的含量/%	RSD/ %	样品放置1~6 h的含量/ %	RSD/ %	6份样品回收率/%	平均回收率/ %
1550560	0.4	15.13	1.3	15.52	0.4	101.10	101.4
1552735		15.32		15.48		103.25
1558359		15.42		15.59		102.68
1558727		15.66		15.45		98.74
1544298		15.50		15.52		102.37
1545139		15.23		15.39		100.52

精密度		重复性		稳定性		加标回收
对照品连续进样 6针峰面积	RSD/ %	平行6份样品的含量/%	RSD/ %	样品放置1~6 h的含量/ %	RSD/ %	6份样品回收率/%	平均回收率/ %
1550560	0.4	15.13	1.3	15.52	0.4	101.10	101.4
1552735		15.32		15.48		103.25
1558359		15.42		15.59		102.68
1558727		15.66		15.45		98.74
1544298		15.50		15.52		102.37
1545139		15.23		15.39		100.52

	菜籽油	大豆油	玉米油	葵花籽油	花生油	橄榄油
菜籽油	1.000	0.333	0.529	0.303	0.894	0.830
大豆油	0.333	1.000	0.937	0.933	0.535	0.086
玉米油	0.529	0.937	1.000	0.917	0.728	0.233
葵花籽油	0.303	0.933	0.917	1.000	0.526	0.073
花生油	0.894	0.535	0.728	0.526	1.000	0.776
橄榄油	0.830	0.086	0.233	0.073	0.776	1.000

	菜籽油	大豆油	玉米油	葵花籽油	花生油	橄榄油
菜籽油	1.000	0.333	0.529	0.303	0.894	0.830
大豆油	0.333	1.000	0.937	0.933	0.535	0.086
玉米油	0.529	0.937	1.000	0.917	0.728	0.233
葵花籽油	0.303	0.933	0.917	1.000	0.526	0.073
花生油	0.894	0.535	0.728	0.526	1.000	0.776
橄榄油	0.830	0.086	0.233	0.073	0.776	1.000

菜籽油掺入比例/%	与橄榄油相似度	大豆油掺入比例/%	与橄榄油相似度	玉米油掺入比例/%	与橄榄油相似度	葵花籽油油掺入比例/%	与橄榄油相似度
10	1.000	10	1.000	10	0.999	10	1.000
20	0.999	20	0.999	20	0.999	20	0.994
40	0.994	40	0.983	40	0.956	40	0.933
60	0.978	60	0.879	60	0.761	60	0.699
80	0.940	80	0.501	80	0.385	80	0.327