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利用高分辨 LC-Orbitrap™ MS 检测小麦中的新型镰刀菌隐蔽性真菌毒素。

Detection of a new Fusarium masked mycotoxin in wheat grain by high-resolution LC-Orbitrap™ MS.

机构信息

National Agriculture and Food Research Organization (NARO), National Food Research Institute, Tsukuba-shi, Ibaraki, Japan.

出版信息

Food Addit Contam Part A Chem Anal Control Expo Risk Assess. 2011 Oct;28(10):1447-56. doi: 10.1080/19440049.2011.597434. Epub 2011 Aug 15.

Abstract

A new Fusarium mycotoxin glucoside, fusarenon X-glucoside (FUXGlc), is reported for the first time in wheat grain that was artificially infected with Fusarium fungi. This new glucoside was identified using LC Orbitrap high-resolution mass spectrometry (LC-Orbitrap MS) analysis on the basis of accurate mass measurement of characteristic ions and MS/MS fragmentation patterns. Although the absolute structure of FUXGlc was not clarified by LC-MS, 3-OH glucosylation seems to be the most probable structure based on the fragment profile and considering that deoxynivalenol-3-glucoside (DON3Glc) was reported as the predominant glucosylated derivative of the structurally similar mycotoxin, deoxynivalenol (DON). Another mycotoxin glucoside, nivalenol-glucoside (NIVGlc) was also found in the same grain sample. According to the semi-quantification by LC-Orbitrap MS, more than 15% of FUX and NIV were estimated to be converted into respective glucosides. The existence of these masked mycotoxins should be taken into account in risk assessment, since they could be transformed back to the corresponding mycotoxins under certain conditions; for example, through various food processing operations or in the digestive tract of mammals after ingestion.

摘要

一种新型镰刀菌真菌毒素葡萄糖苷,即呋塞米酮 X-葡萄糖苷(FUXGlc),首次在人工感染镰刀菌的小麦籽粒中被发现。该新葡萄糖苷是基于特征离子的精确质量测量和 MS/MS 裂解模式,使用 LC Orbitrap 高分辨率质谱(LC-Orbitrap MS)分析鉴定的。尽管通过 LC-MS 尚未确定 FUXGlc 的绝对结构,但基于片段谱并考虑到结构相似的真菌毒素脱氧雪腐镰刀菌烯醇(DON)的主要葡萄糖化衍生物为脱氧雪腐镰刀菌烯醇-3-葡萄糖苷(DON3Glc),推测 3-OH 葡萄糖化似乎是最有可能的结构。在同一谷物样品中还发现了另一种真菌毒素葡萄糖苷,即玉米赤霉烯酮葡萄糖苷(NIVGlc)。根据 LC-Orbitrap MS 的半定量分析,估计超过 15%的 FUX 和 NIV 转化为各自的葡萄糖苷。在风险评估中应考虑到这些被掩盖的真菌毒素的存在,因为它们在某些条件下(例如通过各种食品加工操作或在哺乳动物摄入后的消化道中)可能会转化回相应的真菌毒素。

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