Zhang Yixin, Zhang Cheng, Li Zihan, Zeng Cheng, Xue Zhen, Li Erwei, Li Gang, Li Juan, Shen Guoan, Xu Chaoqun, Wang Yuanyue, Ma Baiping, Zhang Hui, Guo Baolin
Key Laboratory of Bioactive Substances and Resources Utilization of Chinese Herbal Medicines, Ministry of Education, Institute of Medicinal Plant Development, Chinese Academy of Medical Sciences and Peking Union Medical College, Beijing, China.
Key Laboratory of Biodiversity Science and Ecological Engineering, Ministry of Education, College of Life Sciences, Beijing Normal University, Beijing, China.
Front Chem. 2022 Oct 10;10:1014110. doi: 10.3389/fchem.2022.1014110. eCollection 2022.
Phytochemical investigation was carried out for the flowers of Franchet. by first conducting LC-MS analysis, leading to the identification of 32 compounds. Furthermore, guided by LC-MS profiling, three new 8-prenylated quercetin glycosides (3'-hydroxylikarisoside C, 3'-hydroxylepimedoside E, 3'-hydroxyldiphylloside B), one new anthocyanin (delphinidin-3---coumaroyl-sophoroside) and six known compounds were isolated from the flowers of for the first time, and their structures were characterized based on spectroscopic methods including 1D and 2D NMR, and HRESIMS. Combining our discoveries and literature survey, a revised classification of flavonols was proposed as Type A (8-prenylated kaempferol based), which was further subdivided into subtype icaritin and subtype demethylicaritin, and Type B (8-prenylated quercetin based), which was further subdivided into subtype 3'-hydroxylicaritin and subtype 3'-hydroxyldemethylicaritin. The structure-activity relationship (SAR) study was carried out by comparing testosterone production-promoting activities of all the new compounds along with nine related flavonols, revealing that the new 8-prenylated quercetin glycosides (subtype 3'-hydroxyldemethylicaritin in Type B) exhibited lower testosterone production-promoting activities in rat primary Leydig cells than flavonols of subtype demethylicaritin in Type A, but possessed higher activities than the flavonols of subtype icaritin in Type A. These results suggested that either methylation at C-4' position or hydroxylation at C-3' position of ring B could significantly reduce the testosterone production-promoting activities of flavonols.
对长叶胡颓子花进行了植物化学研究，首先进行液相色谱 - 质谱分析，鉴定出32种化合物。此外，在液相色谱 - 质谱分析的指导下，首次从长叶胡颓子花中分离出三种新的8 - 异戊烯基槲皮素苷（3'-羟基淫羊藿苷C、3'-羟基朝藿定苷E、3'-羟基二叶苷B）、一种新的花青素（飞燕草素 - 3 - 香豆酰槐糖苷）和六种已知化合物，并通过包括一维和二维核磁共振以及高分辨电喷雾电离质谱在内的光谱方法对其结构进行了表征。结合我们的发现和文献调研，提出了黄酮醇的修订分类，分为A型（基于8 - 异戊烯基山奈酚），进一步细分为淫羊藿素亚型和去甲基淫羊藿素亚型，以及B型（基于8 - 异戊烯基槲皮素），进一步细分为3'-羟基淫羊藿素亚型和3'-羟基去甲基淫羊藿素亚型。通过比较所有新化合物以及九种相关黄酮醇促进睾酮生成的活性进行了构效关系（SAR）研究，结果表明，新的8 - 异戊烯基槲皮素苷（B型中的3'-羟基去甲基淫羊藿素亚型）在大鼠原代睾丸间质细胞中促进睾酮生成的活性低于A型中的去甲基淫羊藿素亚型黄酮醇，但高于A型中的淫羊藿素亚型黄酮醇。这些结果表明，B环C-4'位甲基化或C-3'位羟基化均可显著降低黄酮醇促进睾酮生成的活性。
