Nothias-Scaglia Louis-Félix, Schmitz-Afonso Isabelle, Renucci Franck, Roussi Fanny, Touboul David, Costa Jean, Litaudon Marc, Paolini Julien
Laboratoire de Chimie de Produits Naturels, UMR CNRS SPE 6134, University of Corsica, Corte 20250, France; Institut de Chimie des Substances Naturelles, CNRS, UPR 2301, LabEx CEBA, University Paris-Saclay, 1 avenue de la terrasse, 91198 Gif-sur-Yvette, France.
Institut de Chimie des Substances Naturelles, CNRS, UPR 2301, LabEx CEBA, University Paris-Saclay, 1 avenue de la terrasse, 91198 Gif-sur-Yvette, France.
J Chromatogr A. 2015 Nov 27;1422:128-139. doi: 10.1016/j.chroma.2015.09.092. Epub 2015 Oct 13.
This paper reports our effort to develop a comprehensive HPLC-MS(n)-based dereplication strategy for phorbol ester (PE), deoxyphorbol ester (dPE) and ingenol ester (IE) profiling in plant extracts. This strategy is composed of two sequential analysis exploiting specific hybrid triple quadrupole/linear ion trap instrument modes. A first run was performed using a multiple reaction monitoring (MRM) mode targeting fragmentation of PE and dPE/IE coupled with the acquisition of MS(2) spectrum for the ions at m/z 311 and m/z 313, respectively. A second run was then completed based on precursor ion scan mode (PIS) and automatic MS(2) acquisition for each quasimolecular ion. The developed approach was used to investigate ten Euphorbia extracts showing bioactivity against chikungunya virus replication. Experiments allowed partial annotation of three dPE/IE but no PE was detected. Results suggested that other types of diterpene esters displayed PE- and dPE/IE-like fragmentations. The study of jatrophane ester (JE) standards by CID fragmentation using low and high resolution mass spectrometry confirmed this hypothesis, highlighting challenges and difficulties of diterpene esters profiling within plant extracts. Nonetheless, the present LC-MS(n) method can be easily adapted to profile other types of diterpene esters.
本文报道了我们为开发一种基于高效液相色谱-质谱联用（HPLC-MS(n)）的全面的去重复策略所做的努力，该策略用于分析植物提取物中的佛波酯（PE）、脱氧佛波酯（dPE）和大戟醇酯（IE）。此策略由利用特定的混合三重四极杆/线性离子阱仪器模式的两个连续分析组成。第一次运行使用多反应监测（MRM）模式，靶向PE和dPE/IE的碎片化，并分别采集m/z 311和m/z 313处离子的MS(2)谱图。然后基于前体离子扫描模式（PIS）和对每个准分子离子的自动MS(2)采集完成第二次运行。所开发的方法用于研究十种对基孔肯雅病毒复制具有生物活性的大戟属植物提取物。实验对三种dPE/IE进行了部分注释，但未检测到PE。结果表明，其他类型的二萜酯显示出类似PE和dPE/IE的碎片化。通过使用低分辨率和高分辨率质谱的碰撞诱导解离（CID）碎片化对麻风树酯（JE）标准品进行的研究证实了这一假设，突出了植物提取物中二萜酯分析的挑战和困难。尽管如此，目前的液相色谱-质谱联用（LC-MS(n)）方法可以很容易地适用于分析其他类型的二萜酯。
