七种新的单硫酸三萜苷,djakonoviosidesA(1),A1(2)、A2(3)、和B1-B4(4-7),以及之前在其他黄瓜物种中发现的三种已知的糖苷,分别是okhotosideA1-1,黄瓜A0-1和正面D,已从远东海参Cucumariadjakonovi(Cucumariidae,Dendrochirotida)。在对1D和2DNMR光谱进行广泛分析的基础上建立了结构,并通过HR-ESI-MS数据进行了确认。A和B组化合物的碳水化合物链彼此不同,即单硫酸化四糖链是基团A和具有一个硫酸基团的五糖链固有的,由C-2Qui2分支,是B组的特征。djakonoviosidesA2(3)的苷元,B2(5)、和B4(7)的特点是独特的结构特征,首先在海参糖苷中发现的23,16-半缩酮片段。讨论了其形成的生物合成途径。由于存在新的糖苷配基,因此C.djakonovi糖苷的糖苷配基具有物种特异性。同时,在C.djakonovi中发现了较早从其他黄瓜物种中分离出的已知糖苷,以及所有研究的黄瓜属代表的糖苷特有的一组碳水化合物链,证明了这些糖苷作为化学分类学标记的重要性。化合物1-7和已知的糖苷okhotosideA1-1,黄瓜苷A0-1和frondsideD的膜分解作用,从C.djakonovi中分离出人类细胞系,包括红细胞和乳腺癌细胞(MCF-7,T-47D,和三负MDA-MB-231),以及白血病HL-60和胚胎肾HEK-293细胞系,已经研究过了。OkhotosideA1-1是该系列中最具活性的化合物,因为存在具有7(8)-双键和16β-O-乙酰氧基的四糖线性链和全甾烷糖苷配基,黄瓜苷A0-1,具有相同的苷元,由于在C-2Qui2处存在分支木糖残基,因此活性略低。一般来说,A组djakonoviosides的活性高于含有相同糖苷配基的B组djakonoviosides的活性,表明包含四个单糖残基的线性链对于证明糖苷的膜分解作用的重要性。所有含有半缩酮碎片的化合物,djakonoviosideA2(3),B2(5)、和B4(7),几乎不活跃。与其他癌细胞相比,最具侵袭性的三阴性MDA-MB-231乳腺癌细胞系对糖苷作用最敏感。OkhotosideA1-1和黄瓜苷A0-1对MDA-MB-231细胞具有良好的效果。显著抑制迁移,以及形成和成长,殖民地。
Seven new monosulfated triterpene glycosides, djakonoviosides A (1), A1 (2), A2 (3), and B1-B4 (4-7), along with three known glycosides found earlier in the other
Cucumaria species, namely okhotoside A1-1, cucumarioside A0-1, and frondoside D, have been isolated from the far eastern sea cucumber
Cucumaria djakonovi (Cucumariidae, Dendrochirotida). The structures were established on the basis of extensive analysis of 1D and 2D NMR spectra and confirmed by HR-ESI-MS data. The compounds of groups A and B differ from each other in their carbohydrate chains, namely monosulfated tetrasaccharide chains are inherent to group A and pentasaccharide chains with one sulfate group, branched by C-2 Qui2, are characteristic of group B. The aglycones of djakonoviosides A2 (3), B2 (5), and B4 (7) are characterized by a unique structural feature, a 23,16-hemiketal fragment found first in the sea cucumbers\' glycosides. The biosynthetic pathway of its formation is discussed. The set of aglycones of C. djakonovi glycosides was species specific because of the presence of new aglycones. At the same time, the finding in C. djakonovi of the known glycosides isolated earlier from the other species of
Cucumaria, as well as the set of carbohydrate chains characteristic of the glycosides of all investigated representatives of the genus
Cucumaria, demonstrated the significance of these glycosides as chemotaxonomic markers. The membranolytic actions of compounds 1-7 and known glycosides okhotoside A1-1, cucumarioside A0-1, and frondoside D, isolated from C. djakonovi against human cell lines, including erythrocytes and breast cancer cells (MCF-7, T-47D, and triple negative MDA-MB-231), as well as leukemia HL-60 and the embryonic kidney HEK-293 cell line, have been studied. Okhotoside A1-1 was the most active compound from the series because of the presence of a tetrasaccharide linear chain and holostane aglycone with a 7(8)-double bond and 16β-O-acetoxy group, cucumarioside A0-1, having the same aglycone, was slightly less active because of the presence of branching xylose residue at C-2 Qui2. Generally, the activity of the djakonoviosides of group A was higher than that of the djakonoviosides of group B containing the same aglycones, indicating the significance of a linear chain containing four monosaccharide residues for the demonstration of membranolytic action by the glycosides. All the compounds containing hemiketal fragments, djakonovioside A2 (3), B2 (5), and B4 (7), were almost inactive. The most aggressive triple-negative MDA-MB-231 breast cancer cell line was the most sensitive to the glycosides action when compared with the other cancer cells. Okhotoside A1-1 and cucumarioside A0-1 demonstrated promising effects against MDA-MB-231 cells, significantly inhibiting the migration, as well as the formation and growth, of colonies.