高效液相色谱-四极杆飞行时间质谱检测中国杨树型蜂胶、巴西绿蜂胶和杨树胶中的酚类化合物及真伪鉴别

doi:10.3724/SP.J.1123.2018.09003

色谱 ›› 2019, Vol. 37 ›› Issue (1): 40-45.DOI: 10.3724/SP.J.1123.2018.09003

• 特别策划：南京海关动植物与食品检测中心专栏 • 上一篇下一篇

高效液相色谱-四极杆飞行时间质谱检测中国杨树型蜂胶、巴西绿蜂胶和杨树胶中的酚类化合物及真伪鉴别

陈磊¹, 刘芸¹, 陈雷¹, 张晓燕¹, 冯峰², 张峰²

1. 南京海关动植物与食品检测中心, 江苏南京 210019;
2. 中国检验检疫科学研究院食品安全研究所, 北京 100176

收稿日期:2018-09-01 出版日期:2019-01-08 发布日期:2014-11-29
通讯作者: 陈磊,Tel:(025)52345193,E-mail:coffeecatchen@163.com.
基金资助:
国家重点研发计划（2017YFF0211000）.

Determination of phenolic compounds in Chinese poplar propolis, Brazil green propolis, and poplar gum by high performance liquid chromatography-quadrupole-time-of-flight mass spectrometry and preliminary study of the identification of adulteration

CHEN Lei¹, LIU Yun¹, CHEN Lei¹, ZHANG Xiaoyan¹, FENG Feng², ZHANG Feng²

1. Animal, Plant and Food Inspection Center, Nanjing Customs, Nanjing 210019, China;
2. Institute of Food Safety, Chinese Academy of Inspection and Quarantine, Beijing 100176, China

Received:2018-09-01 Online:2019-01-08 Published:2014-11-29
Supported by:
National Key Research and Development Project of China (No. 2017YFF0211000).

摘要/Abstract

摘要：

建立了用于检测中国杨树型蜂胶、巴西绿蜂胶和杨树胶中23种酚类化合物的高效液相色谱-四极杆飞行时间质谱（HPLC/Q-TOF MS）法，并进行了差异性分析。蜂胶和树胶样品用甲醇-水（1：1，v/v）溶解后，过0.45 μm有机相滤膜后进样。采用Agilent Eclipse Plus C₁₈色谱柱分离，以乙腈和0.1%（体积分数）甲酸水溶液为流动相进行梯度洗脱，电喷雾正离子模式全扫描方式检测，扫描范围为m/z 100~1000，外标法定量。结果表明，23种酚类化合物在10~200 μg/L范围内线性关系良好，相关系数均大于0.99。桔皮素和刺芒柄花素的检出限和定量限分别为0.2和1 μg/L，其他化合物的检出限和定量限分别为2和10 μg/L。在10、25和50 mg/kg 3个添加水平下，23种酚类化合物在3种样品基质中的提取回收率为70.2%~122.6%，RSD值均小于10%。水杨苷、肉桂酸、咖啡酸和香豆酸可以作为中国杨树型蜂胶掺假鉴别的特征化合物，咖啡酸、阿魏酸、白杨素、咖啡酸苯乙酯、松属素、高良姜素、香豆酸、异鼠李素、山柰素和阿替匹林C可以作为辨别中国杨树型蜂胶和巴西绿蜂胶的特征化合物。该结果对蜂胶产品的质量控制具有一定的参考意义。

关键词: 掺假鉴别, 酚类化合物, 蜂胶, 高效液相色谱-四极杆飞行时间质谱

Abstract:

High-performance liquid chromatography-quadrupole-time-of-flight mass spectrometry (HPLC/Q-TOF MS) was used to analyze 23 phenolic compounds in Chinese poplar propolis, Brazil green propolis, and poplar gum. Propolis and poplar gum samples were dissolved in methanol-water (1:1, v/v) and filtered by 0.45 μm organic phase filtration membrane. The separation was carried out in an Agilent Eclipse Plus C18 column with gradient elution using acetoni-trile and 0.1% (volume percentage) formic acid solution as the mobile phases. The compounds were detected using positive ion electrospray ionization in full scan mode (m/z 100-1000). The quantification analysis was performed by the external standard method. The results showed that all the compounds were linear, with correlation coefficients>0.99, in the range of 10-20 μg/L. The limits of detection and limits of quantification for tangeretin and formononetin were 0.2 and 1 μg/L, respectively, and those for the other compounds were 2 and 10 μg/L, respectively. At the spiked levels of 10, 25, and 50 mg/kg, the recoveries of all the compounds ranged from 70.2% to 122.6%, with relative standard deviations of less than 10%. Salicin, cinnamic acid, caffeic acid, and coumaric acid could be used as markers for detecting adulteration in Chinese poplar propolis, while caffeic acid, ferulic acid, chrysin, caffeic acid phenethyl ester, pinocembrin, galangin, coumaric acid, isorhamnetin, kaempferide, and arte-pillin C could be used as markers for identifying Chinese poplar propolis and Brazil green propolis. The results presented in this paper may be helpful in quality control of propolis products.

Key words: adulteration identification, high performance liquid chromatography-quadrupole-time-of-flight mass spectrometry (HPLC/Q-TOF MS), phenolic compounds, propolis

中图分类号:

O658

陈磊, 刘芸, 陈雷, 张晓燕, 冯峰, 张峰. 高效液相色谱-四极杆飞行时间质谱检测中国杨树型蜂胶、巴西绿蜂胶和杨树胶中的酚类化合物及真伪鉴别[J]. 色谱, 2019, 37(1): 40-45.

CHEN Lei, LIU Yun, CHEN Lei, ZHANG Xiaoyan, FENG Feng, ZHANG Feng. Determination of phenolic compounds in Chinese poplar propolis, Brazil green propolis, and poplar gum by high performance liquid chromatography-quadrupole-time-of-flight mass spectrometry and preliminary study of the identification of adulteration[J]. Chinese Journal of Chromatography, 2019, 37(1): 40-45.

参考文献

[1] Xu X, Zhang H C, Dong J. Science and Technology of Food Industry, 2008, 29(9):286 徐响, 张红城, 董捷. 食品工业科技, 2008, 29(9):286
[2] Zhang C P, Hu F L. Natural Product Research and Development, 2009, 21(6):1084 张翠平, 胡福良. 天然产物研究与开发, 2009, 21(6):1084
[3] Zhang C P, Wang K, Hu F L. Chinese Journal of Modern Applied Pharmacy, 2013, 30(1):102 张翠平, 王凯, 胡福良. 中国现代应用药学, 2013, 30(1):102
[4] Zhang C P, Si J J, Hong Q H, et al. Journal of Bee, 2018, 38(1):5 张翠萍, 思娟娟, 洪奇华, 等. 蜜蜂杂志, 2018, 38(1):5
[5] Luo Z M.[MS Dissertation]. Beijing:Chinese Academy of Agricultural Sciences, 2013 罗照明.[硕士学位论文]. 北京:中国农业科学院, 2013
[6] Gao L M, Xu X, Gao P B, et al. Journal of Chinese Institute of Food Science and Technology, 2018, 18(3):221 高丽苗, 徐响, 高蓬勃, 等. 中国食品学报, 2018, 18(3):221
[7] Banskota A H, Tezuka Y, Kadota S. Phytother Res, 2001, 15(7):561
[8] Khalil M L. Asian Pac J Cancer Prev, 2006, 7(1):22
[9] Kalogeropoulos N, Konteles S J, Troullidou E, et al. Food Chem, 2009, 116(2):452
[10] Gao P B, Xu X, Gao L M, et al. Journal of Food Safety and Quality, 2015, 6(8):3172 高蓬勃, 徐响, 高丽苗, 等. 食品安全质量检测学报, 2015, 6(8):3172
[11] Zhou M Y, Xu R H, Huang W, et al. Apiculture of China, 2010, 61(3):5 周梦遥, 徐瑞晗, 黄微, 等. 中国蜂业, 2010, 61(3):5
[12] Zhang C P, Ping S, Huang S, et al. Chinese Pharmaceutical Journal, 2013, 48(22):1889 张翠平, 平舜, 黄帅, 等. 中国药学杂志, 2013, 48(22):1889
[13] Wang Y H, Fu C L, Zhang L, et al. Food Research and Development, 2016, 37(21):1 王月华, 付崇罗, 张丽, 等. 食品研究与开发, 2016, 37(21):1
[14] Zhang T T.[MS Dissertation]. Nanchang:Nanchang University, 2017 张婷婷.[硕士学位论文]. 南昌:南昌大学, 2017
[15] Chen B.[MS Dissertation]. Nanchang:Nanchang University, 2010 陈滨.[硕士学位论文]. 南昌:南昌大学, 2010
[16] Wang Y H, Chang H S, Yin X S, et al. Natural Product Research and Development, 2017, 29(6):924 王月华, 常化松, 尹旭升, 等. 天然产物研究与开发, 2017, 29(6):924
[17] Cao X P, Hu F L. Apiculture of China, 2015, 66(10):46 曹雪萍, 胡福良. 中国蜂业, 2015, 66(10):46
[18] Cao W, Fu J F, Suo Z R, et al. Food and Fermentation Industries, 2007, 33(7):162 曹炜, 符军放, 索志荣, 等. 食品与发酵工业, 2007, 33(7):162
[19] Zhang C P, Huang S, Wei W T, et al. J Food Sci, 2014, 79(7):1315
[20] Zhang C P, Zheng H Q, Liu G, et al. Food Chem, 2011, 127(1):345
[21] Wang K, Zhang C P, Hu F L. Natural Product Research and Development, 2013, 25(1):140 王凯, 张翠平, 胡福良. 天然产物研究与开发, 2013, 25(1):140
[22] Kumazaki M, Shinohara H, Taniguchi K, et al. Phytomedicine, 2014, 21(8/9):1070
[23] Shen X G, Zhang C P, Hu F L. Natural Product Research and Development, 2015, 27(5):915 申小阁, 张翠平, 胡福良. 天然产物研究与开发, 2015, 27(5):915
[24] Wang C L. Food Research and Development, 2016, 37(1):39 王春玲. 食品研究与开发, 2016, 37(1):39
[25] Zhou P, Shao Q Y, Xu Q H, et al. Journal of Bee, 2013, 33(4):4 周萍, 邵巧云, 徐权华, 等. 蜜蜂杂志, 2013, 33(4):4
[26] GB/T 19427-2003
[27] Zhao X Y, Wang H W, Wang P, et al. Journal of Analytical Science, 2016, 32(5):679 赵晓亚, 王华伟, 王鹏, 等. 分析科学学报, 2016, 32(5):679
[28] Park Y K, Koo M H. Arq Bio Technol, 1997, 40(1):79

高效液相色谱-四极杆飞行时间质谱检测中国杨树型蜂胶、巴西绿蜂胶和杨树胶中的酚类化合物及真伪鉴别

Determination of phenolic compounds in Chinese poplar propolis, Brazil green propolis, and poplar gum by high performance liquid chromatography-quadrupole-time-of-flight mass spectrometry and preliminary study of the identification of adulteration

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