Zhang Jiayu, Lu Jianqiu, Zhang Qian, Dai Long, Liu Ying, Tu Pengfei, Qiao Yanjiang
1School of Chinese Pharmacy, Beijing University of Chinese Medicine, Beijing 100102, China.
J Chromatogr Sci. 2014 Feb;52(2):103-14. doi: 10.1093/chromsci/bms253. Epub 2013 Jan 11.
Polymethoxylated flavonoids (PMFs), the particular flavonoid subclass in which all or almost all hydroxyls are capped by methylation, have high oral bioavailability and various activities. A sensitive high-performance liquid chromatography-diode array detection-electrospray ionization tandem mass spectrometry (HPLC-DAD-ESI-MS-MS) method was established to screen and identify the PMFs in the leaves of Murraya exotica. Eight PMF standards, including two polymethoxylated flavones, two polymethoxylated flavanones, two polymethoxylated chalcones and two PMF glycosides, were first to be analyzed in positive mode by collision-induced dissociation MS-MS. On the basis of the ESI-MS, characterizations were deduced, and in the results of the extracted ion chromatogram MS-MS experiment, 26 PMFs, including 18 flavones, five flavanones or chalcones and three PMF glycosides, were screened out from the complex extract of the leaves of M. exotica. Among them, 24 PMFs were hydroxylated polymethoxyflavonoids, whereas the rest were all permethoxylated PMFs. This was the first systematic report on the presence of PMFs in the leaves of M. exotica. The results indicated that the established analytical method could be adopted as a rapid, effective technique for the structural characterization of PMFs from the complex extracts of traditional Chinese medicines.
多甲氧基黄酮(PMFs)是一类特殊的黄酮类化合物,其中所有或几乎所有的羟基都被甲基化修饰,具有较高的口服生物利用度和多种活性。建立了一种灵敏的高效液相色谱-二极管阵列检测-电喷雾电离串联质谱(HPLC-DAD-ESI-MS-MS)方法,用于筛选和鉴定九里香叶片中的PMFs。首先对8种PMF标准品进行分析,包括2种多甲氧基黄酮、2种多甲氧基黄烷酮、2种多甲氧基查耳酮和2种PMF糖苷,采用正离子模式通过碰撞诱导解离质谱-质谱进行分析。基于电喷雾电离质谱(ESI-MS)推导其特征,在提取离子色谱质谱-质谱实验结果中,从九里香叶的复杂提取物中筛选出26种PMFs,包括18种黄酮、5种黄烷酮或查耳酮以及3种PMF糖苷。其中,24种PMFs为羟基化多甲氧基黄酮,其余均为全甲氧基化的PMFs。这是关于九里香叶中存在PMFs的首次系统报道。结果表明,所建立的分析方法可作为一种快速、有效的技术,用于从中药复杂提取物中对PMFs进行结构表征。