Blackwell B A, Edwards O E, Fruchier A, ApSimon J W, Miller J D
Mycotoxin Research Group, Plant Research Centre, Agriculture Canada, Ottawa.
Adv Exp Med Biol. 1996;392:75-91. doi: 10.1007/978-1-4899-1379-1_7.
Fumonisin B1 (FB1) is the primary mycotoxin produced by Fusarium moniliforme and appears to be responsible for the varied toxigenic effects associated with ingestion of this mold, particularly that of the inhibition of sphingolipid biosynthesis. Understanding the structure and biosynthesis of fumonisins is a key factor in determining structure/activity relationships. To this end, Nuclear Magnetic Resonance (NMR) methods have been used to identify various derivatives of FB1, both naturally occurring and synthetic. With accurate chemical shift assignments, NMR may be used to determine the level of impurities in toxicological grade FB1 preparations. Specifically enriched FB1 was prepared from F. moniliforme cultures using 13C-enriched acetate as well as several 13C-enriched amino acids. 13C NMR analysis indicates that the biosynthesis of fumonisins involves the addition of methionine-derived methyl functions, glutamate-derived tricarballylic ester functions and alanine to an 18 carbon hydrocarbon backbone that is likely polyketide in origin. With the goal of obtaining a crystalline compound for the determination of absolute configuration, several derivatives of FB1 have been prepared, and NMR analysis used to determine the relative and absolute configuration of the 10 stereocenters present in this molecule.
伏马菌素B1（FB1）是串珠镰刀菌产生的主要霉菌毒素，似乎与摄入这种霉菌相关的各种毒性作用有关，特别是对鞘脂生物合成的抑制作用。了解伏马菌素的结构和生物合成是确定结构/活性关系的关键因素。为此，核磁共振（NMR）方法已被用于鉴定FB1的各种天然存在和合成的衍生物。通过准确的化学位移归属，NMR可用于确定毒理学级FB1制剂中的杂质水平。使用13C富集的乙酸盐以及几种13C富集的氨基酸从串珠镰刀菌培养物中制备了特定富集的FB1。13C NMR分析表明，伏马菌素的生物合成涉及将蛋氨酸衍生的甲基官能团、谷氨酸衍生的三羧酸酯官能团和丙氨酸添加到一个18碳的烃骨架上，该骨架可能起源于聚酮化合物。为了获得用于确定绝对构型的结晶化合物，已经制备了几种FB1的衍生物，并使用NMR分析来确定该分子中存在的10个立体中心的相对和绝对构型。
