Ptaquiloside (PTA) is an illudane glycoside partly responsible for the carcinogenicity of bracken ferns (Pteridium sp.). The PTA analogues ptesculentoside (PTE) and caudatoside (CAU) have similar biochemical reactivity. However, both compounds are highly under-investigated due to the lack of analytical standards and appropriate methods. This study presents a robust method for preparation of analytical standards of PTE, CAU, PTA, the corresponding hydrolysis products: pterosins G, A and B, and an LC-MS based method for simultaneous quantification of the six compounds in bracken. The chromatographic separation of analytes takes 5 minutes. The observed linear range of quantification was 20 – 500 µg/L for PTA and pterosin B, and 10 – 250 µg/L for the remaining compounds (r > 0.999). The limits of detection were 0.08 – 0.26 µg/L for PTE, CAU and PTA and 0.01 – 0.03 µg/L for the pterosins, equivalent to 2.0 – 6.5 µg/g and 0.25 – 0.75 µg/g in dry weight, respectively. The method was applied on 18 samples of dried fern leaves from 6 continents. Results demonstrated high variation in concentrations of PTE, CAU and PTA with levels prior to hydrolysis up to 3,900, 2,200 and 2,100 µg/g respectively. This is the first analytical method for simultaneous and direct measurement of all six compounds. Its application demonstrated that bracken ferns contain significant amounts of PTE and CAU relative to PTA.

Ptaquiloside（PTA）是illudane糖苷为蕨菜蕨类的致癌性的部分原因（蕨sp。）。PTA类似物翼骨苷（PTE）和丁香苷（CAU）具有相似的生化反应性。但是，由于缺乏分析标准品和适当的方法，这两种化合物的研究仍很不足。这项研究为制备PTE，CAU，PTA分析标准品，相应的水解产物：蝶呤G，A和B，以及基于LC-MS的方法同时测定蕨菜中的六种化合物提供了一种可靠的方法。分析物的色谱分离需要5分钟。观察到的线性定量范围为：PTA和翼蛋白B为20 – 500 µg / L，其余化合物为10 – 250 µg / L（r> 0.999）。PTE，CAU和PTA的检出限为0.08 – 0.26 µg / L，而蝶呤的检出限为0.01 – 0.03 µg / L，相当于干重2.0 – 6.5 µg / g和0.25 – 0.75 µg / g，分别。该方法应用于来自六大洲的18个干燥蕨叶样品。结果表明，水解前PTE，CAU和PTA的浓度差异很大，分别高达3,900、2,200和2,100 µg / g。这是同时和直接测量所有六种化合物的第一种分析方法。它的应用表明蕨菜蕨相对于PTA含有大量PTE和CAU。