Institute of Pharmacy, Pharmacognosy, CMBI, University of Innsbruck, Innrain 80-82, 6020 Innsbruck, Austria.
Institute of Biological Sciences, Applied Ecology & Phycology, University of Rostock, Albert-Einstein-Str. 3, 18059 Rostock, Germany.
Molecules. 2018 Oct 23;23(11):2735. doi: 10.3390/molecules23112735.
The siphonous green algae form a morphologically diverse group of marine macroalgae which include two sister orders (Bryopsidales and Dasycladales) which share a unique feature among other green algae as they are able to form large, differentiated thalli comprising of a single, giant tubular cell. Upon cell damage a cascade of protective mechanisms have evolved including the extrusion of sulfated metabolites which are involved in the formation of a rapid wound plug. In this study, we investigated the composition of sulfated metabolites in (Dasycladales) which resulted in the isolation of two phenolic acids and four coumarins including two novel structures elucidated by nuclear magnetic resonance spectroscopy (NMR) as 5,8'-di-(6(6'),7(7')-tetrahydroxy-3-sulfoxy-3'-sulfoxycoumarin), a novel coumarin called dasycladin A and 7-hydroxycoumarin-3,6-disulfate, which was named dasycladin B. In addition, an analytical assay for the chromatographic quantification of those compounds was developed and performed on a reversed phase C-18 column. Method validation confirmed that the new assay shows good linearity (R² ≥ 0.9986), precision (intra-day R.S.D ≤ 3.71%, inter-day R.S.D ≤ 7.49%), and accuracy (recovery rates ranged from 104.06 to 97.45%). The analysis of several samples of from different collection sites, water depths and seasons revealed differences in the coumarin contents, ranging between 0.26 to 1.61%.
虹吸管绿藻形成了一个形态多样的海洋大型藻类群，其中包括两个姐妹目（Bryopsidales 和 Dasycladales），它们在其他绿藻中具有独特的特征，因为它们能够形成由单个巨大管状细胞组成的大型分化藻体。在细胞受到损伤时，会进化出一系列保护机制，包括排出参与快速伤口堵塞形成的硫酸化代谢物。在这项研究中，我们研究了（Dasycladales）中硫酸化代谢物的组成，结果分离出两种酚酸和四种香豆素，其中两种新结构通过核磁共振波谱（NMR）阐明为 5,8'-二-(6(6'),7(7')-四羟基-3-磺酸基-3'-磺酸基香豆素），一种新型香豆素称为 dasycladin A 和 7-羟基香豆素-3,6-二硫酸盐，命名为 dasycladin B。此外，还开发并在反相 C-18 柱上对这些化合物的色谱定量分析进行了分析。方法验证证实，新的分析方法具有良好的线性（R²≥0.9986）、精密度（日内 R.S.D≤3.71%，日间 R.S.D≤7.49%）和准确性（回收率范围为 104.06%至 97.45%）。对来自不同采集地点、水深和季节的几种 样本的分析显示，香豆素含量存在差异，范围在 0.26 至 1.61%之间。
