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应用无靶向串联质谱与分子网络技术检测复杂样品中的恩镰菌素和 beauvericin 类毒素。

Application of untargeted tandem mass spectrometry with molecular networking for detection of enniatins and beauvericins from complex samples.

机构信息

CAMS Key Laboratory of Synthetic Biology for Drug Innovation, Institute of Medicinal Biotechnology, Chinese Academy of Medical Sciences & Peking Union Medical College, Tiantan xili No.1, Beijing 100050, China.

CAMS Key Laboratory of Synthetic Biology for Drug Innovation, Institute of Medicinal Biotechnology, Chinese Academy of Medical Sciences & Peking Union Medical College, Tiantan xili No.1, Beijing 100050, China.; NHC Key Laboratory of Biotechnology of Antibiotics, Institute of Medicinal Biotechnology, Chinese Academy of Medical Sciences & Peking Union Medical College, Tiantan xili No.1, Beijing 100050, China..

出版信息

J Chromatogr A. 2020 Dec 20;1634:461626. doi: 10.1016/j.chroma.2020.461626. Epub 2020 Oct 22.

DOI:10.1016/j.chroma.2020.461626
PMID:33166889
Abstract

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.

摘要

建立了一种基于非靶向 LC-MS/MS 的分子网络方法,用于自动测定真菌培养物和天然污染样品中恩镰菌素和 beauvericin 的变体。使用这种方法,可以有效地分析大量样品以确定是否存在恩镰菌素和 beauvericin 相关化合物。作为概念验证,分析了来自镰刀菌属、拟青霉属和间座壳属的 13 个真菌菌株的 26 个培养物以及 46 个食品样品。新发现了 4 种产恩镰菌素和 3 种产 beauvericin 的真菌。其中,通过其基因组序列中存在 beauvericin 生物合成基因簇,进一步证实了 Fusarium sp. 190-20-2 产生 beauvericin。此外,从产恩镰菌素真菌 Fusarium sp. 17-048 和产 beauvericin 真菌 Beauveria sp. 186-069 中分别检测到 17 种恩镰菌素同系物,包括恩镰菌素 A 的一种新异构体和三种以前未报道的 bassianolide 类似物。通过它们的钠加合物的一系列产物离子,初步确定了所检测化合物的结构。恩镰菌素 A 的新异构体通过 NMR 光谱进一步证实。对食品样品的初步调查显示,恩镰菌素在测试的小麦粉和面条样品中普遍存在,而 beauvericin 仅在玉米粉样品中发现。

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