穗花杉双黄酮罗伯斯特双黄酮质谱裂解特征研究

来源期刊:中南大学学报(自然科学版)2012年第4期

论文作者:黎霜 黄可龙 钟明 鲁曼霞

文章页码:1244 - 1248

关键词:穗花杉双黄酮;罗伯斯特双黄酮;ESI-MS;质谱裂解特征

Key words:amentoflavone; robustaflavone; ESI-MS; fragmentation pathway

摘    要:采用负离子检测模式下的电喷雾多级串联质谱(ESI-MS)方法对穗花杉双黄酮和罗伯斯特双黄酮的质谱行为进行研究,讨论C3′—C8″与C3′—C6″连接的双黄酮类化合物结构特征与质谱裂解行为之间的异同。实验结果表明:2种C—C连接的双黄酮类化合物在相同的质谱条件下均可以在C环发生0,4键断裂,生成质荷比m/z=375的碎片离子。此离子峰为C—C连接的双黄酮类化合物共有的特征离子峰;但是由于C—C连接位置的不同,这一对同分异构体的裂解途径也存在着明显差异。C3′—C6″连接的罗伯斯特双黄酮,由于空间构型的影响,在质谱条件下,C4′位的羟基更易于与C5″或者C7″位上的羟基发生分子内脱水,生成丰度响应值较高的碎片离子m/z为519和309。这2个碎片离子是罗伯斯特双黄酮的特征碎片离子,可用于区分穗花杉双黄酮和罗伯斯特双黄酮。

Abstract:

Amentoflavone and robustaflavone were investigated by negative ion electrospray ionization tandem mass spectrometry (ESI-MS). The relationship between their structural features and the corresponding characteristic ions fragmentation behavior was discussed. The results show that bi-flavonoid linkage of C3′—C8″and C3′—C6″ has the same fragmentation pathways. Under the condition of bi-flavonoid linkage, the bond of C-ring breaks at 0, 4 positions, and then gives the principal fragment ion at m/z=375 by losing of neutral species. For amentoflavone and robustaflavone, the positions at m/z=375 in MS spectrum may belong to the characteristic fragment ion. However, there are different fragmentation pathways because of the difference of the position of C—C linkage between amentoflavone and robustaflavone. C3′—C6″linkage may induce the changes in stereostructure. The dehydration will be easy between C4′—OH and C5″—OH or C4′—OH and C7″′—OH. For robustaflavone, the m/z=519 and m/z=309 are the characteristic ions, which may be used to distinguish between amentoflavone and robustaflavone.

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