真菌中酚类生物合成的研究。粉红粘帚霉I.M.I. 93 065中3,4-二甲氧基-6-甲基甲苯醌和胶霉毒素的生物合成。

Studies on the biosynthesis of phenols in fungi. Biosynthesis of 3,4-dimethoxy-6-methyltoluquinol and gliorosein in Gliocladium roseum I.M.I. 93 065.

作者信息

Packter N M, Steward M W

出版信息

Biochem J. 1967 Jan;102(1):122-32. doi: 10.1042/bj1020122.

DOI:10.1042/bj1020122

PMID:6067663

原文链接:https://pmc.ncbi.nlm.nih.gov/articles/PMC1270218/

Abstract

Gliorosein was obtained in excellent yield (150mg./200ml. of Raulin-Thom medium) from surface cultures of Gliocladium roseum. Its nuclear-magnetic-resonance spectrum showed conclusively that it is 1,6-dihydro-3,4-dimethoxy-6-methyltoluquinone. 2. Sodium [2-(14)C]acetate was incorporated into gliorosein and the related products (3.3% conversion). The specific activities of these substances increased in the order gliorosein, 3,4-dimethoxy-6-methyltoluquinol, the related quinhydrone and quinone, indicating that gliorosein was the actual metabolite that was secreted and that the other compounds were derived from it in the medium. 3. 6-Methylsalicylic acid was not taken up by the mycelium and could be recovered unchanged. Orsellinic acid was decarboxylated by G. roseum and an equivalent amount of orcinol was secreted into the medium. The methyl esters of 6-methylsalicylic acid and orsellinic acid were both hydrolysed by an esterase present in the mycelium. Some of the 6-methylsalicylic acid thus produced was secreted into the medium and the orsellinic acid was decarboxylated. 4. Washed mycelium of G. roseum converted aurantiogliocladin and 3,4-dimethoxy-6-methyltoluquinol quantitatively into gliorosein within 18hr. More critical experiments with (14)C-labelled substrates demonstrated that 3-hydroxy-4-methoxy-6-methyltoluquinol and 3,4-dimethoxy-6-methyltoluquinol, and their respective quinones, were effectively incorporated into gliorosein and related products (49, 68, 30 and 57% respectively). 5. The following sequence of reactions is proposed for the biosynthesis of gliorosein: acetyl-CoA+3 malonyl-CoA+S-adenosyl-methionine --> 5-methylorsellinic acid --> 3-hydroxy-4-methoxy-6-methyltoluquinol --> 3,4-dimethoxy-6-methyltoluquinol --> gliorosein. 6. Since gliorosein is optically active (dextrorotatory), the final tautomerization reaction leading to its formation must be enzyme-catalysed.

摘要

从粉红粘帚霉的表面培养物中以优异的产率（每200毫升劳林 - 汤姆培养基可得150毫克）获得了胶霉毒素。其核磁共振谱确凿地表明它是1,6 - 二氢 - 3,4 - 二甲氧基 - 6 - 甲基甲苯醌。2. 用[2 - (14)C]醋酸钠掺入胶霉毒素及相关产物中（转化率为3.3%）。这些物质的比活性按胶霉毒素、3,4 - 二甲氧基 - 6 - 甲基甲苯酚、相关的醌氢醌和醌的顺序增加，这表明胶霉毒素是实际分泌的代谢产物，而其他化合物是在培养基中由它衍生而来的。3. 6 - 甲基水杨酸未被菌丝体吸收，可原样回收。玫瑰色酸被粉红粘帚霉脱羧，等量的苔黑酚分泌到培养基中。6 - 甲基水杨酸和玫瑰色酸的甲酯均被菌丝体中存在的酯酶水解。由此产生的一些6 - 甲基水杨酸分泌到培养基中，而玫瑰色酸被脱羧。4. 洗涤过的粉红粘帚霉菌丝体在18小时内将橙黄粘帚菌素和3,4 - 二甲氧基 - 6 - 甲基甲苯酚定量转化为胶霉毒素。用(14)C标记底物进行的更严格实验表明，3 - 羟基 - 4 - 甲氧基 - 6 - 甲基甲苯酚和3,4 - 二甲氧基 - 6 - 甲基甲苯酚及其各自的醌有效地掺入胶霉毒素及相关产物中（分别为49%、68%、30%和57%）。5. 提出了胶霉毒素生物合成的以下反应序列：乙酰辅酶A + 3丙二酰辅酶A + S - 腺苷甲硫氨酸→5 - 甲基玫瑰色酸→3 - 羟基 - 4 - 甲氧基 - 6 - 甲基甲苯酚→3,4 - 二甲氧基 - 6 - 甲基甲苯酚→胶霉毒素。6. 由于胶霉毒素具有光学活性（右旋），导致其形成的最终互变异构反应必定是酶催化的。