UHPLC-LTQ-Orbitrap分析硫磺熏蒸麦冬中高异黄酮硫酸酯和亚硫酸酯

为了阐明麦冬中高异黄酮类成分在硫磺熏蒸过程中的变化,采用UHPLC-LTQ-Orbitrap高分辨质谱法,利用Waters HSS T3UPLC色谱柱(2.1mm×100mm×1.7μm),以0.1%甲酸水(A)-乙腈/甲醇(3∶1,V/V)(B)为流动相进行梯度洗脱,并采用ESI离子源负离子扫描模式对样品进行分析。根据得到的高分辨质谱数据及多级质谱裂解碎片离子,从硫磺熏蒸麦冬药材中筛选了41个高异黄酮含硫衍生物,并对其中的31个化合物进行了结构鉴定,包括16个硫酸酯和15个亚硫酸酯。结果表明,麦冬高异黄酮在硫磺熏蒸过程中除了发生硫酸酯化和亚硫酸酯化外,其自身母核结构也可能发生改变。本研究阐明了麦冬中高异黄酮在硫磺熏蒸过程中的转变情况,可以为硫磺熏蒸麦冬药材中化学成分的体内ADME过程、药效学以及毒理学等研究奠定基础。

Rapid Identification of Homoisoflavonid Sulfated Derivatives in Sulfated Fumigated Ophiopogon japonicus by UHPLC-LTQ-Orbitrap Mass Spectrometry

Over recent decades, sulfur fumigation has been becoming abused in processing some fresh Chinese herbal medicines due to its benefits containing simple operation, declined cost, and bleaching color characteristics. However, it has recently emerged as a controversial topic with respect to the potential detrimental effects, such as chemical transformation of inherent constituents and consequently the generation of potential toxicities. Radix Ophiopogon, the root of Liliaceae Ophiopogon japonicus (Thunb.) Ker Gawl, is a kind of traditional Chinese medicine that always suffers sulfur fumigated (SF). The modern phytochemistry researches have demonstrated that homoisoflavones, steroidal saponins and polysaccharides are the dominant components of this Chinese medicine. Although several researches have focused on the sulfur fumigated Ophiopogon japonicus till now, there was no study to reveal the phenomenon of chemical transformation of inherent constituents. Herein, in this study, the new generated homoisoflavones sulfur derivatives were researched to preliminarily clarify its transformation pathways during sulfur fumigation process based on UHPLC-LTQ-Orbitrap mass spectrometry. The separation was conducted on a Waters Acuqity UPLC HSS T3 C18 column with the gradient elution of 0.1% formic acid aqueous solution (A) and acetonitrile/methanol (3∶1, V/V) (B). To reduce interference of other substances and avoid the missing of the trace sulfur derivatives, the parent ion list-dynamic exclusion in negative mode based data-acquisition method was established. As a result, 41 homoisoflavones sulfated derivatives are detected. Among them, 31 are identified based on the high-resolution MS/MS datasets. This study tentatively clarified the transformation pathways of homoisoflavones during sulfur fumigation, and provided some useful information for the following relevant studies.