采用高效液相色谱/电喷雾串联质谱分析三尖杉中墨西哥醇型和胡椒林型柠檬苦素。

Analysis of mexicanolide- and phragmalin-type limonoids from Heynea trijuga using high-performance liquid chromatography/electrospray tandem mass spectrometry.

机构信息

State Key Laboratory of Phytochemistry and Plant Resources in West China, Kunming Institute of Botany, Chinese Academy of Sciences, Kunming, Yunnan, China.

出版信息

Rapid Commun Mass Spectrom. 2013 Jun 15;27(11):1203-12. doi: 10.1002/rcm.6563.

DOI:10.1002/rcm.6563

PMID:23650033

Abstract

RATIONALE

Limonoids, a class of tetranortriterpenoids, exhibit various biological effects, including acting as potent antifeedants and insect growth-regulators against various pests. The analysis of phragmalin- and mexicanolide-type limonoids by collision-induced dissociation tandem mass spectrometry (CID-MS/MS) has not been reported.

METHODS

A high-performance liquid chromatography/electrospray ionization (HPLC/ESI)-MS/MS method was developed to investigate the fragmentation patterns of M+NH4 ions for nine reference phragmalin- and mexicanolide-type limonoids. The method was also used in the identification of limonoid compounds in botanic extracts of Heynea trijuga.

RESULTS

The losses of side chains and the furan part were the major fragmentation patterns. However, there was variation in the relative abundances of product ions resulting from the same fragmentation pathways. A total of 89 phragmalin- and mexicanolide-type limonoids in botanic extracts of Heynea trijuga were detected and 50 of these compounds were identified or tentatively characterized based on elemental constituents, fragmentation pathways, and the profile of the major product ions of reference compounds. In addition, the isomers could be tentatively distinguished.

CONCLUSIONS

An HPLC/ESI-MS/MS method was developed and could be used to simultaneously identify and screen phragmalin- and mexicanolide-type limonoids in botanic extracts of Heynea trijuga.

摘要

原理

柠檬苦素类化合物是一类四环三萜类化合物，具有多种生物活性，包括作为有效的拒食剂和昆虫生长调节剂来防治各种害虫。利用碰撞诱导解离串联质谱（CID-MS/MS）对 phragmalin- 和 mexicanolide 型柠檬苦素类化合物的分析尚未有报道。

方法

建立了高效液相色谱/电喷雾电离（HPLC/ESI）-MS/MS 方法，用于研究 9 种参考 phragmalin- 和 mexicanolide 型柠檬苦素类化合物的 M+NH4 离子碎裂模式。该方法还用于鉴定三叶黑荆（Heynea trijuga）植物提取物中的柠檬苦素类化合物。

结果

侧链和呋喃部分的丢失是主要的碎裂模式。然而，同一碎裂途径产生的产物离子的相对丰度存在差异。在三叶黑荆植物提取物中共检测到 89 种 phragmalin- 和 mexicanolide 型柠檬苦素类化合物，其中 50 种根据元素组成、碎裂途径和参考化合物主要产物离子的特征谱进行了鉴定或初步表征。此外，还可以对异构体进行初步区分。