Oxylipins designate oxygenated unsaturated C₁₈ fatty acids. Readers of Molecular Plant Pathology were asked to nominate the 10 most important plant-pathogenic fungi. Studies of them have revealed dioxygenases (DOX) in oxylipin biosynthesis with homology to human cyclooxygenases. These enzymes have also been studied extensively in Aspergilli. They contain a DOX domain, which is often fused to a functional cytochrome P450 at the C-terminal end. A Tyr radical in the DOX domain initiates dioxygenation of linoleic acid by hydrogen abstraction with formation of 8-, 9-, or 10-hydroperoxy metabolites. The P450 domains can catalyze heterolytic cleavage of 8- and 10-hydroperoxides with oxidation of the heme thiolate iron for hydroxylation at C-5, C-7, C-9, or C-11 and for epoxidation of the 12Z double bond; thus displaying linoleate diol synthases (LDS) and epoxy alcohol synthase (EAS). They are present in Rice blast (8R-DOX-7,8-LDS), Grey mould (8R-DOX-5,8-LDS), and Black scurf (8R-DOX-8,9-oleate diol synthase). 10R-DOX-EAS has been found in Rice blast and Fusarium oxysporum. The P450 domains may also catalyze homolytic cleavage of 8- and 9-hydroperoxy fatty acids and dehydration to produce epoxides with an adjacent double bond, i.e., allene oxides, thus displaying 8- and 9-DOX-allene oxide synthases (AOS). F. oxysporum, F. graminearum, and Rhizoctania solani express 9S-DOX-AOS and Zymoseptoria tritici 8S-and 9R-DOX-AOS. Homologues are present in endemic human-pathogenic fungi. 8R-and 10R-DOX appear to bind fatty acids “headfirst” in the active site, whereas 9S-DOX binds them “tail first” in analogy with cyclooxygenases. The biological relevance of 8R-DOX-5,8-LDS (also designated PpoA) was first discovered in relation to sporulation of Aspergillus nidulans and recently for development and programmed hyphal branching of A. fumigatus. Gene deletion DOX-AOS homologues in F. verticillioides, A. flavus, and A. nidulans alters, inter alia, mycotoxin production, sporulation, and gene expression. These enzymes may have comparable functions in endemic human-pathogenic fungi.

Oxylipins 表示氧化的不饱和 C ₁₈脂肪酸。《分子植物病理学》的读者被要求提名 10 种最重要的植物病原真菌。对它们的研究揭示了氧化脂生物合成中的双加氧酶 (DOX) 与人类环加氧酶具有同源性。这些酶也在曲霉中进行了广泛的研究。它们包含一个 DOX 结构域，该结构域通常在 C 末端与功能性细胞色素 P450 融合。DOX 结构域中的 Tyr 自由基通过夺氢引发亚油酸的双氧合，形成 8-、9-或 10-氢过氧代谢物。P450 结构域可以催化 8-和 10-氢过氧化物的异裂裂解，同时氧化血红素硫醇铁以在 C-5、C-7、C-9 或 C-11 上进行羟基化，并用于 12 Z的环氧化双键；因此显示亚油酸二醇合酶（LDS）和环氧醇合酶（EAS）。它们存在于稻瘟病 (8 R -DOX-7,8-LDS)、灰霉病 (8 R -DOX-5,8-LDS) 和黑头屑 (8 R -DOX-8,9-oleate diol synthase ) 中）。10 R -DOX-EAS 已在稻瘟病和尖孢镰刀菌中发现。P450结构域还可以催化8-和9-氢过氧脂肪酸的均裂和脱水以产生具有相邻双键的环氧化物，即丙二烯氧化物，从而展示8-和9-DOX-丙二烯氧化物合酶(AOS)。F. oxysporum、F. graminearum和Rhizoctania solani表达 9 S -DOX-AOS 和Zymoseptoria tritic i 8 S -和 9 R -DOX-AOS。同源物存在于地方性人类病原真菌中。8 R -和 10 R -DOX 似乎在活性位点“头先”结合脂肪酸，而 9 S -DOX 与环氧合酶类似，“尾先”结合它们。8 R -DOX-5,8-LDS（也称为 PpoA）的生物学相关性首次被发现与构巢曲霉的孢子形成有关，最近与烟曲霉的发育和程序化菌丝分枝有关。F. verticillioides、A. flavus和A. nidulans中的基因缺失 DOX-AOS 同源物改变，尤其是、霉菌毒素的产生、孢子形成和基因表达。这些酶在地方性人类病原真菌中可能具有类似的功能。