Berestetskiy Alexander, Dmitriev Andrey, Mitina Galina, Lisker Iosif, Andolfi Anna, Evidente Antonio
All-Russian Institute of Plant Protection, Russian Academy of Agricultural Sciences, Pushkin, Saint-Petersburg 196608, Russia.
Phytochemistry. 2008 Feb;69(4):953-60. doi: 10.1016/j.phytochem.2007.11.003. Epub 2007 Dec 21.
A structure-activity relationships study was conducted assaying 15 natural analogues and derivatives belonging to two groups of organic compounds, nonenolides and cytochalasins, for their toxicity against the composite perennial weeds Cirsium arvense and Sonchus arvensis occurring through the temperate region of world. The toxic nonenolides (stagonolide, putaminoxin, pinolidoxin) and cytochalasins (deoxaphomin, cytochalasins A, B, F, T, Z2 and Z3) were isolated from phytopathogenic Stagonospora, Phoma and Ascochyta spp. The pinolidoxin (7,8-O,O'-diacetyl- and 7,8-O,O'-isopropylidene-pinolidoxin) and cytochalasins B (21,22-dihydro-, 7-O-acetyl- and 7,20-O,O'-diacetyl-cytochalasin B) derivatives were obtained by chemical modifications of the corresponding toxins. Among the 15 compounds tested, stagonolide and deoxaphomin proved to be the most phytotoxic to C. arvense and S. arvensis leaves, respectively. The tested phytotoxic nonenolides were stronger inhibitors of photosynthesis in C. arvense leaves than cytochalasines A and B. Stagonolide had less effect on membrane permeability in C. arvense leaves than cytochalasin B. Significant changes of light absorption by C. arvense leaves in visible and infrared spectra were caused by stagonolide. The functional groups and the conformational freedom of the ring, appear to be important structural features for the nonenolides toxicity, whereas and the presence of the hydroxy group at C-7, the functional group at C-20 and the conformational freedom of the macrocyclic ring are important for the cytochalasins toxicity.
开展了一项构效关系研究，测定了属于两类有机化合物（非烯内酯和细胞松弛素）的15种天然类似物和衍生物对分布于世界温带地区的多年生杂草田蓟和苣荬菜的毒性。毒性非烯内酯（匍柄霉内酯、腐皮镰刀菌素、吡咯二酮毒素）和细胞松弛素（脱氧凹顶孢素、细胞松弛素A、B、F、T、Z2和Z3）是从植物病原葡萄座腔菌属、茎点霉属和壳二孢属物种中分离得到的。吡咯二酮毒素（7,8 - O,O'-二乙酰基 - 和7,8 - O,O'-异亚丙基 - 吡咯二酮毒素）和细胞松弛素B（21,22 - 二氢 - 、7 - O - 乙酰基 - 和7,20 - O,O'-二乙酰基 - 细胞松弛素B）衍生物是通过对相应毒素进行化学修饰获得的。在所测试的15种化合物中，匍柄霉内酯和脱氧凹顶孢素分别被证明对田蓟和苣荬菜的叶片具有最强的植物毒性。所测试的具有植物毒性的非烯内酯对田蓟叶片光合作用的抑制作用比细胞松弛素A和B更强。匍柄霉内酯对田蓟叶片膜通透性的影响比细胞松弛素B小。匍柄霉内酯导致田蓟叶片在可见光和红外光谱中的光吸收发生显著变化。对于非烯内酯的毒性而言，官能团和环的构象自由度似乎是重要的结构特征，而对于细胞松弛素的毒性而言，C - 7位羟基的存在、C - 20位的官能团以及大环的构象自由度是重要的。
