建立了一种基于非靶向LC-MS/MS的分子网络方法,用于从真菌培养物和自然污染的样品中自动测定烯尼素和白僵素的变体。使用此方法,可以有效地分析大量样品中是否存在与enniatin和beauvericin相关的化合物。作为概念的证明,26种文化,来自镰刀菌属的13种真菌菌株,Beauveria,和Diaporthe,以及46份食物样本进行了分析。新发现了4种产生enniatin和3种产生beauvericin的真菌。其中,镰刀菌的生产。190-20-2进一步通过在其基因组序列中存在白僵素生物合成基因簇来证实。此外,17个Enniatin同源物,包括一种新的烯化素A异构体,并从产生烯尿素的真菌中检测到三种以前未报告的bassianolide类似物,镰刀菌sp.17-048和一种产生博维菌素的真菌,Beauveriasp.186-069,分别。检测到的化合物的结构是通过其钠加合物的一系列产物离子初步确定的。通过NMR谱进一步证实了新的烯尼素A的异构体。对食品样品的初步调查表明,在所检测的小麦粉和面条样品中,而Beauvericin仅在玉米粉粉末样品中发现。
An untargeted LC-MS/MS-based molecular networking method was established for the automatic determination of variants of
enniatin and beauvericin from both fungal cultures and naturally contaminated samples. Using this method, a large number of samples can be efficiently analyzed for the presence of
enniatin- and beauvericin-related compounds. As proof of concept, 26 cultures, derived from 13 fungal strains in the genera of Fusarium, Beauveria, and Diaporthe, as well as 46 food samples were analyzed. Four
enniatin- and three beauvericin-producing fungi were newly discovered. Among them, the production of beauvericin by Fusarium sp. 190-20-2 was further confirmed by the presence of a beauvericin biosynthesis gene cluster in its genomic sequence. Additionally, 17
enniatin congeners, including one new isomer of
enniatin A, and three previously unreported bassianolide analogues were detected from an enniatin-producing fungus, Fusarium sp. 17-048, and a beauvericin-producing fungus, Beauveria sp. 186-069, respectively. The structures of the detected compounds were tentatively determined by a series of product ions of their sodium adducts. The new isomer of
enniatin A was further confirmed by NMR spectra. A preliminary survey of food samples showed that enniatins were prevalent in the tested wheat flour and noodle samples, whereas beauvericin was only discovered in cornflour powder samples.