Determination and Analysis of 16 Mycotoxins in Medicinal and Edible Traditional Chinese Medicine

LI Fenghua; LI Zuohua; YANG Li; YUAN Yongchun; WANG Suxiang; WANG Aixiang; LI Wei; ZHENG Fengjia

doi:10.13386/j.issn1002-0306.2021080109

Volume 43 Issue 9

Apr. 2022

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Science and Technology of Food Industry > 2022 > 43(9): 268-275. > DOI: 10.13386/j.issn1002-0306.2021080109

LI Fenghua, LI Zuohua, YANG Li, et al. Determination and Analysis of 16 Mycotoxins in Medicinal and Edible Traditional Chinese Medicine [J]. Science and Technology of Food Industry, 2022, 43(9): 268−275. (in Chinese with English abstract). doi: 10.13386/j.issn1002-0306.2021080109.

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Determination and Analysis of 16 Mycotoxins in Medicinal and Edible Traditional Chinese Medicine

1.
Shandong Center for Disease Control and Prevention, Jinan 250014, China
2.
Shandong Quality & Security Trust Technical Services Co., Ltd., Jinan 250000, China
3.
All Mine Testing Co., Ltd., Heze 274000, China

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Received Date: August 10, 2021
Accepted Date: February 22, 2022
Available Online: March 03, 2022

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Abstract

Abstract

Objective: An analytical method was established for the determination of 16 mycotoxins in traditional Chinese medicines (TCM) by isotope labeling-ultra performance liquid chromatography tandem mass spectrometry (UPLC-MS/MS), and 483 medicinal and edible homologous samples from the markets were detected using this method. Method: The samples were extracted with acetonitrile-water (50/50, V/V), and then purified by the MycoSpin^TM 400 multifunction clean-up columns. Then the samples were detected and confirmed by UPLC-MS/MS, and quantified by isotope labeled internal standards. Rapid separation of 16 mycotoxins was successfully achieved on an Acquity UPLC BEH C₁₈ column（100 mm×2.1 mm, 1.7 μm）with gradient elution. Simultaneous acquisition was performed in multiple reaction monitoring (MRM) mode with electrospray ionization (ESI) source operated in both positive and negative ionization modes. Result: The established method provided good linearities for the 16 mycotoxins within their respective linear ranges with high correlation coefficients (R>0.998), and the detection limits of this method were 0.1~4.0 μg/kg. The average recoveries of the 16 mycotoxins ranged from 83.4% to 102.3% at the three spiked levels, and the relative standard deviations (RSD, n=6) were in the range of 2.08%~13.6%. In the detection of 483 actual samples, 10 mycotoxins were detected, and the other 6 mycotoxins were not detected. The toxin compound with the highest detection rate was zearalenone (ZEN), with an average content of positive samples 71.2 μg/kg, and 3.11% of the samples exceeded the reference limit specified in the national food safety standard. Conclusion: This method used isotope dilution and multifunction clean-up columns to purify the samples, which reduced the matrix interference in the medicinal and edible homologous samples. The detection limits could meet the requirement of methods. The method was accurate and rapid, and could be used for the detection and analysis of multi residues of mycotoxins in a large number of samples.

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References (33)

References

[1]	李雅静, 秦曙, 杨艳梅, 等. 中国谷物真菌毒素污染研究现状[J]. 中国粮油学报,2020,35(3):186−194. [LI Yajing, QIN Shu, YANG Yanmei, et al. Research status of mycotoxin contamination in grains in China[J]. Journal of the Chinese Cereals and Oils Association,2020,35(3):186−194. doi: 10.3969/j.issn.1003-0174.2020.03.030
[2]	KIM D H, HONG S Y, KANG J W, et al. Simultaneous determination of multi-mycotoxins in cereal grains collected from South Korea by LC/MS/MS[J]. Toxins, 2017, 9(3): 106.
[3]	COLLI L D, ELLIOTT C, FINNAN J, et al. Determination of 42 mycotoxins in oats using a mechanically assisted QuEChERS sample preparation and UHPLC-MS/MS detection[J]. Journal of Chromatography B,2020,1150:122187. doi: 10.1016/j.jchromb.2020.122187
[4]	王晓红, 豆金彦, 肖正国. 不同储藏条件下薏苡仁中真菌毒素含量变化的研究[J]. 西部中医药,2018,31(8):20−23. [WANG Xiaohong, DOU Jinyan, XIAO Zhengguo. Study on the content changes of fungal toxin in YiYiRen under different storage conditions[J]. Western Journal of Traditional Chinese Medicine,2018,31(8):20−23. doi: 10.3969/j.issn.1004-6852.2018.08.007
[5]	MATUMBA L, NAMAUMBO S, NGOMA T, et al. Five keys to prevention and control of mycotoxins in grains: A proposal[J]. Global Food Security,2021,30:100562. doi: 10.1016/j.gfs.2021.100562
[6]	王少敏, 黄晓静, 毛丹, 等. QuEChERS-超高效液相色谱串联质谱法同时测定中药瓜蒌皮中22种真菌毒素[J]. 食品安全质量检测学报,2018,9(22):5843−5850. [WANG Shaomin, HUANG Xiaojing, MAO Dan, et al. Simultaneous determination of 22 kinds of mycotoxins in Trichosanthis pericarpium by ultra performance liquid chromatography-tandem mass spectrometry[J]. Journal of Food Safety and Quality,2018,9(22):5843−5850. doi: 10.3969/j.issn.2095-0381.2018.22.009
[7]	FELIPE P T, RATCHANEEWAN K A, VERONIKA N, et al. Mycotoxins, phytoestrogens and other secondary metabolites in austrian pastures: Occurrences, contamination levels and implications of geo-climatic factors[J]. Toxins,2021,13(7):460. doi: 10.3390/toxins13070460
[8]	张鑫, 王福, 陈鸿平, 等. 中药材真菌及真菌毒素污染研究现状[J]. 世界科学技术-中医药现代化,2015,17(11):2381−2388. [ZHANG Xin, WANG Fu, CHEN Hongping, et al. Research progress on fungi and mycotoxin infection of Chinese medicinal materials[J]. World Science and Technology/Modernization of Traditional Chinese Medicine and Materia Medica,2015,17(11):2381−2388. doi: 10.11842/wst.2015.11.033
[9]	FAO/WHO. Codex general standard for contaminants and toxins in food and feed: CODEX STAN 193-1995[EB/OL]. (2011-09-21) [2021-10-10]. http://down.foodmate.net/standard/sort/11/3329.html.
[10]	Commission of the European Communities. Setting maximum levels for certain contaminants in foodstuffs: (EC) No 1881/2006 [EB/OL]. (2007-01-08) [2021-10-10]. http://law.foodmate.net/show-169747.html.
[11]	Commission of the European Communities. A mending regulation (EC) No 1881/2006 as regards the maximum level of ochratoxin A in Capsicum spp. spices[EB/OL]. (2015-08-03) [2021-10-10]. http://law.foodmate.net/show-186931.html
[12]	FDA. Guidance for industry: Action levels for poisonous or deleterious substances in human food and animal feed[EB/OL]. (2000-07-31) [2021-10-10]. https://www.regulations.gov/document/FDA-2020-D-1956-0001
[13]	中华人民共和国国家卫生和计划生育委员会, 国家食品药品监督管理总局. GB 2761-2017食品安全国家标准食品中真菌毒素限量[S]. 北京: 中国标准出版社, 2017. National Health and Family Planning Commission of the People's Republic of China, China Food and Drug Administration. GB 2761-2017 National food safety standard: Limits of mycotoxins in foods[S]. Beijing: Standards Press of China, 2017.
[14]	王彤颖, 陈媛媛, 高璇, 等. 中药材中黄曲霉毒素B1免疫学快速检测方法研究[J]. 现代医药卫生,2017,33(2):177−179. [WANG Tongying, CHEN Yuanyuan, GAO Xuan, et al. Study on rapid immunological detection method for determining AFB1 in traditional Chinese medicines[J]. Journal of Modern Medicine & Health,2017,33(2):177−179. doi: 10.3969/j.issn.1009-5519.2017.02.005
[15]	TANSAKUL N, JALA P, LAOPIEM S, et al. Co-occurrence of five Fusarium toxins in corn-dried distiller’s grains with solubles in Thailand and comparison of ELISA and LC-MS/MS for fumonisin analysis[J]. Mycotoxin Research,2013,29(4):255−260. doi: 10.1007/s12550-013-0173-z
[16]	柯颖, 徐昕怡, 洪小栩. ELISA法检测中药材及中药饮片真菌毒素的探讨[J]. 中国合理用药探索,2020,17(4):17−21. [KE Ying, XU Xinyi, HONG Xiaoxu. Discussion on the application of ELISA detection for mycotoxins in traditional Chinese medicine and Chinese herbal pieces[J]. Chinese Journal of Rational Drug Use,2020,17(4):17−21.
[17]	TEIXEIRA T R, HOELTZ M, EINLOFT T C, et al. Determination of ochratoxin A in wine from the southern region of Brazi by thin layer chromatography with a charge-coupled detector[J]. Food Additives & Contaminants: Part B,2011,4(4):289−293.
[18]	ZHAO X, YUAN Y, ZHANG X, et al. Identification of ochratoxin A in Chinese spices using HPLC fluorescent detectors with immunoaffinity column cleanup[J]. Food Control,2014,46:332−337. doi: 10.1016/j.foodcont.2014.05.052
[19]	刘柱, 陈万勤, 沈潇水, 等. 多功能柱净化-柱后光化学衍生-高效液相色谱法同时检测玉米和花生中9种真菌毒素[J]. 分析科学学报,2014,30(2):168−172. [LIU Zhu, CHEN Wanqin, SHEN Xiaoshui, et al. Simultaneous determination of mycotoxins in corn and peanut samples by multifunctional column clean-up and high performance liquid chromatography coupled with post-column photochemical derivatization[J]. Journal of Analytical Science,2014,30(2):168−172.
[20]	ZHANG Yingyue, PEI Fei, FANG Yong, et al. Comparison of concentration and health risks of 9 Fusarium mycotoxins in commercial whole wheat flour and refined wheat flour by multi-IAC-HPLC[J]. Food Chemistry,2019,275:763−769. doi: 10.1016/j.foodchem.2018.09.127
[21]	邵亮亮, 应美蓉, 杜京霖, 等. 复合免疫亲和柱净化高效液相色谱法同时测定小麦中的4种真菌毒素[J]. 食品科技,2021,46(2):328−334. [SHAO Liangliang, YING Meirong, DU Jinglin, et al. Simultaneous determination of four mycotoxins in wheat by high performance liquid chromatography with combination immunoaffinity column purification[J]. Food Science and Technology,2021,46(2):328−334.
[22]	张正炜, 成玮, 沈慧梅, 等. 小麦粉中脱氧雪腐镰刀菌烯醇(DON)毒素的气相色谱法检测及毒素污染去除分析[J]. 农药科学与管理,2018,39(4):44−50. [ZHANG Zhengwei, CHENG Wei, SHEN Huimei, et al. Determination of deoxynivalenol(DON) toxins in wheat flour by gas chromatography and analysis of toxin pollution removal[J]. Pesticide Science and Administration,2018,39(4):44−50. doi: 10.3969/j.issn.1002-5480.2018.04.014
[23]	林缨, 陈佳, 吴弼东, 等. 固相萃取-气相色谱-串联质谱法检测粮食作物中的T-2与HT-2毒素[J]. 军事医学,2013,37(5):381−384. [LIN Ying, CHEN Jia, WU Bidong, et al. Determination of T-2 and HT-2 toxins in cereal grains by solid phase extraction and gas chromatography-tandem mass spectrometry[J]. Military Medical Sciences,2013,37(5):381−384.
[24]	范妙璇, 董娇娇, 王京辉, 等. QuEChERS-超高效液相-三重四极杆串联质谱测定白茅根中 16 种真菌毒素[J]. 中国中药杂志,2017,42(19):3770−3775. [FAN Miaoxuan, DONG Jiaojiao, WANG Jinghui, et al. Simultaneous determination of sixteen mycotoxins contaminants in cogon rootstalk by QuEChERS-UPLC-QqQ mass spectrometry[J]. China Journal of Chinese Materia Medica,2017,42(19):3770−3775.
[25]	王少敏, 杜春晓, 刘贤贤, 等. QuEChERS-超高效液相色谱串联质谱法同时测定三七中26种真菌毒素[J]. 世界中医药,2019,14(4):798−804. [WANG Shaomin, DU Chunxiao, LIU Xianxian, et al. Simultaneous determination of 26 mycotoxins in Notoginseng Radix et Rhizoma by QuEChERS-ultra-high-performance liquid chromatography-tandem mass spectrometry[J]. World Chinese Medicine,2019,14(4):798−804. doi: 10.3969/j.issn.1673-7202.2019.04.003
[26]	JIANG D, WEI D, Wang L, et al. Multiwalled carbon nanotube for one-step cleanup of 21 mycotoxins in corn and wheat prior to ultraperformance liquid chromatography-tandem mass spectrometry analysis[J]. Toxins,2018,10(10):409−425. doi: 10.3390/toxins10100409
[27]	YAN Pianpian, LIU Zhezhe, LIU Shiqiao, et al. Natural occurrence of deoxynivalenol and its acetylated derivatives in Chinese maize and wheat collected in 2017[J]. Toxins,2020,12(3):200. doi: 10.3390/toxins12030200
[28]	RAUSCH A K, BROCKMEYER R, SCHWERDTLE T. Development and validation of a QuEChERS-based liquid chromatography tandem mass spectrometry multi-method for the determination of 38 native and modified mycotoxins in cereals[J]. Agricultural and Food Chemistry,2020,68:4657−4669. doi: 10.1021/acs.jafc.9b07491
[29]	胡佳哲, 吴凤丹, 陈俏, 等. 同位素标记-高效液相色谱-串联质谱法测定中药材中8种真菌毒素[J]. 中国卫生检验杂志,2020,30(5):513−517. [HU Jiazhe, WU Fengdan, CHEN Qiao, et al. Determination of 8 mycotoxins in Chinese medical materials by isotope labeling-high performance liquid chromatography-tandem mass spectrometry[J]. Chinese Journal of Health Laboratory Technology,2020,30(5):513−517.
[30]	WU Yu, YE Jin, XUAN Zhihong, et al. Development and validation of a rapid and efficient method for simultaneous determination of mycotoxins in coix seed using one-step extraction and UHPLC-HRMS[J]. Food Additives & Contaminants: Part A,2021,38(1):148−159.
[31]	中华人民共和国国家质量监督检验检疫总局. SN/T 4604-2016 中华人民共和国出入境检验检疫行业标准进出口中药材中真菌毒素的测定[S]. 北京: 中国标准出版社, 2017. General Administration of Quality Supervision, Inspection and Quarantine of the People's Republic of China. SN/T 4604-2016 Entry-exit inspection and quarantine industry standard of the People's Republic of China. Determination of mycotoxins in Chinese herbal medicine for import and export[S]. Beijing: Standards Press of China, 2017.
[32]	郑润生, 肖启衍, 邱薇, 等. 10种中药材和3种食品污染赭曲霉毒素A的LC-MS/MS检测研究[J]. 药物分析杂志,2015,35(2):289−294. [ZHENG Runsheng, XIAO Qiyan, QIU Wei, et al. Determination of contaminant ochratoxin A in 10 traditional Chinese medicines and 3 food samples by LC-MS/MS[J]. Chinese Journal of Pharmaceutical Analysis,2015,35(2):289−294.
[33]	毛丹, 叶林链, 王少敏, 等. LC-MS/MS法同时测定中药肉豆蔻中12种真菌毒素[J]. 中国药师,2020,23(7):1311−1315. [MAO Dan, YE Linlian, WANG Shaomin, et al. Simultaneous determination of 12 mycotoxins in myristicae semen by LC-MS/MS[J]. China Pharmacist,2020,23(7):1311−1315. doi: 10.3969/j.issn.1008-049X.2020.07.015

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