Herter Sven-Oliver, Haase Hajo, Koch Matthias
Division 1.7 Organic Trace and Food Analysis, Bundesanstalt für Materialforschung und -prüfung (BAM), Richard-Willstätter-Str. 11, 12489 Berlin, Germany.
Department of Food Chemistry and Toxicology, Technische Universität Berlin, Gustav-Meyer-Allee 25, 13355 Berlin, Germany.
J Agric Food Chem. 2025 Jul 23;73(29):18412-18419. doi: 10.1021/acs.jafc.5c03345. Epub 2025 Jul 11.
Ergot alkaloids (EAs) are prevalent food contaminants affecting cereals, such as rye, wheat, and barley worldwide. To ensure EU safety standards, the six most common EAs: ergometrine, ergotamine, ergosine, ergocornine, ergocristine, and ergocryptine, and their epimers, are quantified using HPLC-MS/MS, as described in the European Standard Method EN 17425:2021. However, this can be challenging and time-consuming in food matrices without appropriate internal standards and highlights the need for more robust and precise analytical tools to support their monitoring. The development of isotope-labeled EAs directly addresses this gap, offering improved accuracy and leading to more consistency across laboratories and consequently to more consumer safety. Therefore, we developed a semisynthetic approach, building upon our previous work where native ergotamine was -demethylated to norergotamine and subsequently remethylated using iodomethane (CD-I). Herein, we are now able to present the successful synthesis of all of the isotopically labeled priority EAs. These isotope-labeled standards were tested against their native counterparts using HPLC coupled with HR-MS/MS. The chromatographic and mass spectrometric properties of the unlabeled and isotopically labeled EAs match exactly, confirming their successful synthesis and structure. These standards can now be utilized to enhance the accuracy and reliability of EA quantification in food and feed.
麦角生物碱（EAs）是影响全球谷物（如黑麦、小麦和大麦）的常见食品污染物。为确保欧盟安全标准，按照欧洲标准方法EN 17425:2021所述，使用高效液相色谱-串联质谱法（HPLC-MS/MS）对六种最常见的EAs：麦角新碱、麦角胺、麦角异胺、麦角柯宁碱、麦角克碱和麦角隐亭及其差向异构体进行定量。然而，在没有合适内标的食品基质中，这可能具有挑战性且耗时，这凸显了需要更强大、更精确的分析工具来支持其监测。同位素标记的EAs的开发直接解决了这一差距，提高了准确性，并在各实验室之间实现了更高的一致性，从而提高了消费者安全性。因此，我们在之前的工作基础上开发了一种半合成方法，在之前的工作中，天然麦角胺被去甲基化为去甲麦角胺，随后使用碘甲烷（CD-I）进行重新甲基化。在此，我们现在能够展示所有同位素标记的优先EAs的成功合成。使用HPLC与高分辨质谱-串联质谱联用对这些同位素标记的标准品与它们的天然对应物进行了测试。未标记和同位素标记的EAs的色谱和质谱特性完全匹配，证实了它们的成功合成和结构。这些标准品现在可用于提高食品和饲料中EAs定量的准确性和可靠性。
