巯基对脱氧雪腐镰刀菌烯醇的亲核加成。
Nucleophilic Addition of Thiols to Deoxynivalenol.
机构信息
Norwegian Veterinary Institute , P.O. Box 750 Sentrum, NO-0106 Oslo, Norway.
Department of Chemistry, University of Oslo , P.O. Box 1033 Blindern, NO-0315 Oslo, Norway.
出版信息
J Agric Food Chem. 2015 Sep 2;63(34):7556-66. doi: 10.1021/acs.jafc.5b02864. Epub 2015 Aug 21.
Conjugation of deoxynivalenol (DON) with sulfur compounds is recognized as a significant reaction pathway, and putative DON-glutathione (DON-GSH) conjugates have been reported in planta. To understand and control the reaction of trichothecenes with biologically important thiols, we studied the reaction of DON, T-2 tetraol, and de-epoxy-DON with a range of model thiols. Reaction conditions were optimized for DON with 2-mercaptoethanol. Major reaction products were identified using HRMS and NMR spectroscopy. The results indicate that thiols react reversibly with the double bond (Michael addition) and irreversibly with the epoxide group in trichothecenes. These reactions occurred at different rates, and multiple isomers were produced including diconjugated forms. LC-MS analyses indicated that glutathione and cysteine reacted with DON in a similar manner to the model thiols. In contrast to DON, none of the tested mercaptoethanol adducts displayed toxicity in human monocytes or induced pro-inflammatory cytokines in human macrophages.
脱氧雪腐镰刀菌烯醇（DON）与含硫化合物的结合被认为是一个重要的反应途径，并且已经在植物体内报道了假定的 DON-谷胱甘肽（DON-GSH）轭合物。为了理解和控制三萜烯与生物重要的硫醇的反应，我们研究了 DON、T-2 四醇和脱环氧-DON 与一系列模型硫醇的反应。使用 2-巯基乙醇优化了 DON 的反应条件。使用高分辨质谱和 NMR 光谱鉴定了主要的反应产物。结果表明，硫醇与双键（迈克尔加成）可逆反应，与三萜烯的环氧化物基团不可逆反应。这些反应的速率不同，生成了多种异构体，包括二共轭形式。LC-MS 分析表明，谷胱甘肽和半胱氨酸与 DON 的反应方式与模型硫醇相似。与 DON 不同，在人单核细胞中，没有一种测试的 2-巯基乙醇加合物显示出毒性，也没有诱导人巨噬细胞产生促炎细胞因子。
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