Abstract：
Different Senecio species, especially S. inaequidens - a neophyte native to South Africa - have widely spread across Europe and now are found worldwide. The entire genus is known to contain toxic pyrrolizidine alkaloids (PAs), which renders them a possible health hazard to humans and livestock. As they can enter the food chain or occur as contaminants in herbal crops and phytopharmaceutical formulations (e.g. teas), efficient and straightforward assays for their qualitative and quantitative analysis are in high demand. Different techniques have been used for this purpose, most commonly HPLC or GC. As the analysis of PAs is a challenging task, alternative methodologies like ultra-high performance SFC (UHPSFC) may offer an additional benefit in terms of their separation efficiency and orthogonal selectivity. In this study an UHPSFC approach for the simultaneous determination of six PAs (free bases as well as N-oxides) is presented, which achieved the baseline separation of all standard compounds in seven min. Optimal separation was carried out in gradient mode on a Torus™ DEA column with 0.05% ammonia in methanol as modifier. The column temperature was 25 °C, ABPR 1900 psi and flow rate 1.1 mL/min, with a detection wavelength of 215 nm. The assay was validated and fulfilled all ICH criteria exhibiting good linearity (R2 ≥ 0.9994), precision (inter-day variance ≤ 3.67%, intra-day variance ≤ 3.92%) and recovery rates (96.3-104.1%), with detection limits typical for SFC-PDA (≤ 4.24 µg/mL). Furthermore, it could conveniently be coupled to MS-detection, which increased the sensitivity significantly. To confirm practical suitability of the method, different Senecio samples were analyzed, indicating a high qualitative as well as quantitative difference in their PA profile (e.g. total amounts of PA between 0.09 and 4.63 mg/g).
摘要：
不同的Senecio物种，特别是S.inaequidens-一种原产于南非的新手-已经在欧洲广泛传播，现在在世界各地都有发现。已知整个属含有有毒的吡咯烷嗪生物碱（PA），这使得它们可能对人类和牲畜的健康造成危害。因为它们可以进入食物链或作为草药作物和植物药物制剂（例如茶）中的污染物出现，对其定性和定量分析的有效和直接的分析有很高的需求。为此使用了不同的技术，最常见的是HPLC或GC。由于对PA的分析是一项具有挑战性的任务，例如超高性能SFC(UHPSFC)的替代方法可以在它们的分离效率和正交选择性方面提供额外的益处。在这项研究中，提出了一种同时测定六种PAs（游离碱和N-氧化物）的UHPSFC方法，在7分钟内实现了所有标准化合物的基线分离。以梯度模式在Torus™DEA柱上进行最佳分离,其中甲醇中的0.05%氨作为改性剂。柱温为25℃,ABPR1900psi,流速1.1mL/min,检测波长为215nm。该测定经过验证，符合所有具有良好线性（R2≥0.9994）的ICH标准，精度(日内方差≤3.67%，日内方差≤3.92%)和回收率(96.3-104.1%)，SFC-PDA的典型检出限（≤4.24µg/mL）。此外，它可以方便地耦合到MS检测，显著提高了灵敏度。为了确认该方法的实际适用性，分析了不同的Senecio样本，表明它们的PA谱具有很高的定性和定量差异（例如，PA的总量在0.09和4.63mg/g之间）。
