G.B. Elyakov Pacific Institute of Bioorganic Chemistry, Far Eastern Branch of the Russian Academy of Sciences, Pr. 100-letya Vladivostoka 159, 690022 Vladivostok, Russia.
Mar Drugs. 2021 Mar 27;19(4):187. doi: 10.3390/md19040187.
Nine new mono-, di-, and trisulfated triterpene penta- and hexaosides, kurilosides A (), D (), G (), H (), I (), I (), J (), K (), and K () and two desulfated derivatives, DS-kuriloside L (), having a trisaccharide branched chain, and DS-kuriloside M (), having hexa--lanostane aglycone with a 7(8)-double bond, have been isolated from the Far-Eastern deep-water sea cucumber (Levin) and their structures were elucidated based on 2D NMR spectroscopy and HR-ESI mass-spectrometry. Five earlier unknown carbohydrate chains and two aglycones (having a 16,(20S)-dihydroxy-fragment and a 16-acetoxy,(20S)-hydroxy fragment) were found in these glycosides. All the glycosides - have a sulfate group at C-6 Glc, attached to C-4 Xyl1, while the positions of the other sulfate groups vary in different groups of kurilosides. The analysis of the structural features of the aglycones and the carbohydrate chains of all the glycosides of showed their biogenetic relationships. Cytotoxic activities of the compounds - against mouse neuroblastoma Neuro 2a, normal epithelial JB-6 cells, and erythrocytes were studied. The highest cytotoxicity in the series was demonstrated by trisulfated hexaoside kuriloside H (), having acetoxy-groups at C(16) and C(20), the latter one obviously compensated the absence of a side chain, essential for the membranolytic action of the glycosides. Kuriloside I (), differing from in the lacking of a terminal glucose residue in the bottom semi-chain, was slightly less active. The compounds -, , and did not demonstrate cytotoxic activity due to the presence of hydroxyl groups in their aglycones.
已从远东海参（Levin）中分离出九种新的单、二和三硫酸化三萜五元和六糖酯，分别为 kuriloside A()、D()、G()、H()、I()、I()、J()、K()和 K()，以及两种去硫酸化衍生物 DS-kuriloside L()和 DS-kuriloside M()，它们都具有三糖支链，并且 DS-kuriloside M()具有带有 7(8)-双键的六-羊毛甾烷糖苷配基。基于二维 NMR 光谱和高分辨率电喷雾质谱法（HR-ESI-MS），阐明了它们的结构。在这些糖苷中发现了五个先前未知的糖链和两个糖苷配基（具有 16,（20S）-二羟基片段和 16-乙酰氧基，（20S）-羟基片段）。所有糖苷 - 在 C-6 Glc 上都具有一个硫酸基，连接到 C-4 Xyl1，而其他硫酸基的位置在不同的 kuriloside 组中有所不同。对所有糖苷的糖苷配基和糖链的结构特征进行分析表明了它们的生物发生关系。研究了这些化合物对小鼠神经母细胞瘤 Neuro 2a、正常上皮 JB-6 细胞和红细胞的细胞毒性。在该系列中，具有乙酰氧基基团的三硫酸化六糖酯 kuriloside H()表现出最高的细胞毒性，后者明显弥补了糖苷膜溶解作用所必需的侧链的缺失。与 不同，在底半链中缺少末端葡萄糖残基的 kuriloside I()活性略低。由于糖苷配基中存在羟基，化合物 - ，和 没有表现出细胞毒性活性。
