RIKILT Institute of Food Safety, Wageningen University and Research Centre, Wageningen, the Netherlands.
Food Addit Contam Part A Chem Anal Control Expo Risk Assess. 2011 Oct;28(10):1405-23. doi: 10.1080/19440049.2011.603704.
A generic method based on LC with full-scan high-resolution (Orbitrap) mass spectrometry (MS) was systematically investigated for the simultaneous detection of a wide range of plant toxins in a variety of food and feed matrices. For a selection of 150 substances, representing various chemical classes, the limit of detection was established using fixed LC-MS conditions. Ion suppression effects and selectivity were evaluated using generic extracts from representative and relevant matrices (food supplement, honey, silage, compound feed). The majority of the substances could be measured as positive ions after electrospray ionisation (ESI(+)). Using a mass resolving power of 100,000 a reliable high mass accuracy was obtained despite the high abundance of co-extractants in the sample extracts. This enabled the use of ±5 ppm mass extraction windows, which in turn resulted in a high degree of selectivity. On the other hand, except for honey, strong ion suppression effects were frequently observed which adversely affected the detection limits. Nevertheless, for the majority of the substances the detection limits were in the range 0.01-0.05 mg kg(-1). Since non-selective sample preparation and non-targeted data acquisition were performed, the presence of plant toxins initially not targeted for during data review can be subsequently investigated, which is a very useful option because for many known toxins no analytical reference standards are yet available. The applicability of the method was demonstrated by analysis of a variety of real-life samples purchased on the market or from cases of intoxication. These included honey, herbal tea, food supplements, poppy seeds, traditional Chinese medicines, compound feed, silage and herb-based feed additives. Plant toxins that were detected included various pyrrolizidine alkaloids, grayanotoxins, opium alkaloids, strychnine, ricinine (a marker for ricin), aconitine, aristolochic acid and cardiac glycosides (e.g. digitoxin, digoxin).
基于 LC 与全扫描高分辨率（轨道阱）质谱（MS）联用的通用方法，系统地研究了在多种食品和饲料基质中同时检测广泛范围植物毒素的方法。对于 150 种代表不同化学类别的物质，采用固定的 LC-MS 条件确定了检测限。采用代表性和相关基质（食品补充剂、蜂蜜、青贮料、配合饲料）的通用提取物评估了离子抑制效应和选择性。在使用电喷雾电离（ESI(+))后，大多数物质可以作为正离子进行测量。在质量分辨率为 100,000 的情况下，尽管样品提取物中存在大量共提取物，仍能获得可靠的高质量精度。这使得可以使用 ±5 ppm 的质量提取窗，从而具有高度的选择性。另一方面，除了蜂蜜外，通常会观察到强烈的离子抑制效应，这会对检测限产生不利影响。尽管如此，对于大多数物质，检测限在 0.01-0.05 mg/kg(-1)范围内。由于采用了非选择性的样品制备和非靶向的数据采集，因此可以随后调查最初在数据审查中未针对的植物毒素的存在，这是一个非常有用的选择，因为对于许多已知的毒素，还没有分析参考标准。该方法的适用性通过分析从市场上购买或中毒案例中采集的各种实际样品得到了证明。这些样品包括蜂蜜、草药茶、食品补充剂、罂粟籽、中药、配合饲料、青贮料和草药饲料添加剂。检测到的植物毒素包括各种吡咯里西啶生物碱、钩吻生物碱、鸦片生物碱、士的宁、蓖麻毒素（蓖麻毒素的标志物）、乌头碱、马兜铃酸和强心苷（如地高辛、洋地黄毒苷）。
