Contents lists available at ScienceDirect Journal of Chromatography B journal homepage: www.elsevier.com/locate/jchromb Determination of aflatoxin and zearalenone analogs in edible and medicinal herbs using a group-specific immunoaffinity column coupled to ultra-high- performance liquid chromatography with tandem mass spectrometry Shujuan Sun a,1 , Kai Yao a,1 , Sijun Zhao b , Pimiao Zheng a , Sihan Wang a , Yuyang Zeng a , Demei Liang a , Yuebin Ke c , Haiyang Jiang a, ⁎ a Beijing Advanced Innovation Center for Food Nutrition and Human Health, College of Veterinary Medicine, China Agricultural University, Beijing Key Laboratory of Detection Technology for Animal-Derived Food Safety, Beijing 100193, People's Republic of China b China Animal Health and Epidemiology Center, Qingdao 266032, People's Republic of China c Shenzhen Center for Disease Control and Prevention, Shenzhen 518055, People's Republic of China ARTICLE INFO Keywords: Aflatoxins Zearalenone analogs Edible and medicinal herbs Group-specific Immunoaffinity column UPLC–MS/MS ABSTRACT Six aflatoxins (AFs; AF B 1 ,B 2 ,G 1 ,G 2 ,M 1 and M 2 ) and six zearalenone (ZEN) analogs (ZEN, zearalanone, α- zeralanol, β-zeralanol, α-zearalenol, and β-zearalenol) were simultaneously extracted from edible and medicinal herbs using a group-specific immunoaffinity column (IAC) and then identified by ultra-high-performance liquid chromatography tandem mass spectrometry (UPLC–MS/MS). The IAC was prepared by coupling N-hydro- xysuccinimide-activated Sepharose 4B Fast Flow gel with two group-specific monoclonal antibodies. The column capacities to six AFs and six ZEN analogs ranged from 100.2 ng to 167.1 ng and from 59.5 ng to 244.4 ng, respectively. The IAC–UPLC–MS/MS method was developed and validated with three different matrices (Chinese yam [Dioscorea polystachya], Platycodon grandiflorum and coix seed [Semen Coicis]). Recoveries of twelve ana- lytes from edible and medicinal herbs were in the range of 64.7%–112.1%, with relative standard deviations below 13.7%. The limits of quantification were in the range from 0.08 μg kg -1 to 0.2 μg kg -1 . The method was proven to be sensitive and accurate, and suitable for the determination of real samples. 1. Introduction Herbal medicines have been used for thousands of years in China, and some herbal medicines have been considered as daily food (known as edible and medicinal herbs) because of their health-promoting functions and disease treatment properties [1]. With the improvement of people's living standards, individuals increasingly care more about their health. To remain healthy, individuals have used many kinds of edible and medicinal herbs, such as Chinese yam, Platycodon grand- iflorum, and coix seed, as alternative medicines. A survey conducted by World Health Organization showed that about 70%–80% of the world populations rely on non-conventional medicines comprised mainly of herbal sources in their primary healthcare [2]. Although many health benefits are present in edible and medicinal herbs, the safe consump- tion of these products has gained much concern because of con- taminations in raw materials by aflatoxins (AFs) and zearalenone (ZEN) structural analogs during cultivating, harvesting, processing and sto- rage [3]. AFs are produced by fungi belonging to Aspergillus flavus and Aspergilllus parasiticus under warm and moist conditions, which are designated as a group 1 carcinogenic compound by the International Agency for Research on Cancer [3]. AF B 1 ,B 2 ,G 1 ,G 2 ,M 1 and M 2 (Fig. 1; AFB 1 , AFB 2 , AFG 1 , AFG 2 , AFM 1 and AFM 2 , respectively) are the most ubiquitous members of AF family and have received increasing attention because of their great harm to the liver [4]. Recently, AFs have been widely detected in herbal medicines [5–8]. Han et al. re- ported the mean levels (incidence) of AFB 1 ,B 2 ,G 1 and G 2 in herbal medicines samples were 1.40 (68.8%), 1.27 (50.0%), 0.50 (43.8%) and 0.94 (43.8%) μg kg -1 ; AFM 1 was also detected with maximum con- centrations of 0.70 μg kg -1 [6]. ZEN has also been found in herbal medicines [9, 10], but has not been studied as extensively as AFs. Zhang et al. detected ZEN in coix seed, with levels ranging from 18.7 μg kg -1 to 211.4 μg kg -1 . ZEN is a naturally occurring nonsteroidal estrogenic mycotoxin produced by genus Fusarium [11], and its derivatives (Fig. 1; zearalanone [ZAN], α-zeralanol [α-ZAL], β-zeralanol [β-ZAL], α-zear- alenol [α-ZOL], β-zearalenol [β-ZOL]) have also been characterized https://doi.org/10.1016/j.jchromb.2018.06.012 Received 20 April 2018; Received in revised form 4 June 2018; Accepted 6 June 2018 ⁎ Corresponding author. 1 These authors contributed equally to this work. E-mail address: haiyang@cau.edu.cn (H. Jiang). Journal of Chromatography B 1092 (2018) 228–236 Available online 07 June 2018 1570-0232/ © 2018 Elsevier B.V. All rights reserved. T