文献类型：期刊文献

英文题名：HPLC-DAD and HPLC-ESI-MS separation, determination and identification of the spin-labeled diastereoisomers of podophyllotoxin

作者：Zhao, Lei[1,2];Liu, Zhen-Ling[1];Fan, Peng-Cheng[3];Zhang, Zhi-Wei[1];Liu, Xiong[2];Zhan, Yun-Jing[2];Tian, Xuan[1]

第一作者：Zhao, Lei;赵磊

通信作者：Tian, X[1]

机构：[1]Lanzhou Univ, State Key Lab Appl Organ Chem, Lanzhou 730000, Peoples R China;[2]Gansu Coll Tradit Chinese Med, Dept Pharm, Lanzhou, Peoples R China;[3]Gen Hosp Lanzhou, Dept Pharm, Lanzhou, Peoples R China

第一机构：Lanzhou Univ, State Key Lab Appl Organ Chem, Lanzhou 730000, Peoples R China

通信机构：[1]corresponding author), Lanzhou Univ, State Key Lab Appl Organ Chem, Lanzhou 730000, Peoples R China.

年份：2009

卷号：32

期号：9

起止页码：1323

外文期刊名：JOURNAL OF SEPARATION SCIENCE

收录：;EI(收录号：20092912192146);Scopus(收录号：2-s2.0-67650095692);WOS:【SCI-EXPANDED(收录号:WOS:000266341200009)】；

基金：This research was supported in part by the Natural Science Foundation of Gansu Province (3ZS061-A25-024). Our hearty thanks go to Professor Cui-Rong Sun and Ms. Juan-Juan Chen (Zhejiang University)for performing the HPLC-ESI/MS analysis.

语种：英文

外文关键词：Diastereoisomers separation; High-performance liquid chromatography-electrospray tandem mass spectrometry; Nitroxide; Podophyllotoxin; Relative abundance

摘要：Spin-labeled nitroxide derivatives of podophyllotoxin had better antitumor activity and less toxicity than that of the parent compounds. However, the 2-H configurations of these spin-labeled derivatives cannot be determined by nuclear magnetic resonance (NMR) methods. In the present paper, a high-performance liquid chromatography-diode array detection (HPLC-DAD) and a high-performance liquid chromatography-electrospray pray ionization tandem mass spectrometry (HPLC-ESI/MS/MS) method were developed and validated for the separation, identification of four pairs of diastereoisomers of spin-labeled derivatives of podophyllotoxin at C-2 position. In the HPLC-ESI/MS spectra, each pair of diastereoisomers of the spin-labeled derivatives in the mixture was directly confirmed and identified by [M+H](+) ions and ion ratios of relative abundance of [M-ROH+H](+) (ion 397) to [M+H](+). When the [M-ROH+H](+) ions (at m/z 397) were selected as the precursor ions to perform the MS/MS product ion scan. The product ions at m/z 313, 282, and 229 were the common diagnostic ions. The ion ratios of relative abundance of the [M-ROH+H](+) (ion 397) to [M+H](+), [A+H](+) (ion 313) to [M-ROH+H](+), [A+H-OCH3](+) (ion 282) to [M-ROH+H](+) and [M-ROH-ArH+H](+) (ion 229) to [M-ROH+H](+) of each pair of diastereoisomers of the derivatives specifically exhibited a stereochemical effect. Thus, by using identical chromatographic conditions, the combination of DAD and MS/MS data permitted the separation and identification of the four pairs of diastereoisomers of spin-labeled derivatives of podophyllotoxin at C-2 in the mixture.