Abstract

This work investigated the biotransformation of ginger constituents (zingerone, [6]-shogaol, [6]-gingerol, and methyl-[6]-gingerol) by the pathogenic fungus Colletotrichum gloeosporioides. Experiments were carried out with and without deuterium-labelled compounds. The product metabolites were analyzed by liquid chromatography coupled to tandem mass spectrometry and liquid chromatography solid phase extraction-nuclear magnetic resonance. Substrates supplied to the fungus were incorporated into metabolic pathways mostly by oxidation reactions, including aromatic carbon–carbon coupling. Zingerone and [6]-gingerol biotransformation products included biphenol dimers. A biodegradation pathway for biphenol formation was proposed based on the presence of the intermediate 4-(2-hydroxyethyl)-2-methoxyphenol, commonly identified from [6]-gingerol and [6]-shogaol biodegradation. This intermediate likely originates from a Baeyer–Villiger reaction followed by hydrolysis. The C–C coupling of molecules could result in phenolic oxidative ortho–ortho coupling, suggesting that biphenol dimers are products of C. gloeosporioides laccase catalysis.

摘要

这项工作研究了病原真菌胶孢炭疽菌对生姜成分（姜油酮、[6]-姜烯酚、[6]-姜酚和甲基-[6]-姜酚）的生物转化。. 在有和没有氘标记的化合物的情况下进行实验。产物代谢物通过液相色谱-串联质谱联用和液相色谱固相萃取-核磁共振进行分析。提供给真菌的底物主要通过氧化反应（包括芳香族碳-碳偶联）进入代谢途径。姜油酮和[6]-姜酚生物转化产物包括双酚二聚体。基于中间体 4-(2-羟乙基)-2-甲氧基苯酚的存在，提出了一种用于形成双酚的生物降解途径，通常从 [6]-姜酚和 [6]-姜烯酚生物降解中鉴定出来。该中间体可能源自拜尔-维利格反应，然后是水解。分子的 C-C 偶联可导致酚类氧化邻 - 邻偶联，表明双酚二聚体是C. gloeosporioides漆酶催化的产物。