The characteristic fragmentation and rearrangement reaction of cationized glucopyranosyloxybenzyl tartrates by tandem mass spectrometry.-猫眼课题宝

DOI：

10.1002/jms.1770

发表时间：

2010-07

期刊：

Journal of mass spectrometry : JMS

影响因子：

通讯作者：

中科院分区：

其他

文献类型：

作者：

Jian Liu;Ruiping Zhang;Jiuming He;Y. Liu;Jiangong Shi;Z. Abliz

葡吡喃糖基氧基苄基酒石酸酯是手参提取物的活性成分。Br. [1]是单-和双（4-β-D-吡喃葡萄糖基氧基苄基）-2-异丁基酒石酸酯的一系列衍生物。G. conopsea是一种传统中药，具有补气、生津、镇静、益智等多种药理作用。[2，3]活性化合物和提取物的药物开发正在进行中。[1，4]结构特异性断裂行为对于鉴定新的类似物和代谢物至关重要。[5-7]因此，我们研究了酒石酸吡喃葡萄糖氧基苄酯的质谱行为。不同类型的碱金属阳离子的比较分析是增强质谱结构解析的有力策略。[8-12]本研究采用正离子电喷雾串联质谱系统地研究了酒石酸葡萄糖氧苄酯与Li+、Na+、K+和NH 4+的加合离子的裂解反应，在[M+ W]+的MS/MS谱图中观察到一个异常重排反应产生的特征离子（W= Li、Na或K），并且通过氘标记和精确的质量测量来探索该反应。此外，还比较了[M+ W]+和[M+ NH 4]+离子所发生的碎裂反应的特点和差异。不同类型的加合离子的比较分析提供了有价值的信息，这些化合物的气相离子化学和结构表征和鉴定。从G.圆锥形Br.（兰科），并通过波谱方法鉴定了它们的结构。[1]这些化合物的结构示于方案1中。将样品溶于移动的流动相（含0.1%（v/v）HCOOH的70%（v/v）乙腈水溶液）中，浓度为10 pmol/µl，并使用液相色谱系统引入质谱仪中。流速为50 μl/min，进样体积为2 μl。将这些化合物各自以10 pmol/μl的浓度溶解在氘代甲醇（CD 3 OD）中，并在室温下保持2 h，以获得氘代衍生物。通过注射泵（直接输注）以10 µl/min的流速将氘代衍生物样品注入ESI源中。使用配备ESI离子源的四极正交飞行时间（QTOF）LC-MS/MS系统（QSTAR EQUIPElite，Applied Biosystem/MDS Sciex）获得高分辨率碰撞诱导解离（CID）光谱。源条件为：喷雾电压，5.5 kV;离子源温度，300 ℃;幕气，25（任意单位）;碰撞气体，5（任意单位）;雾化器气体（GS 1），20（任意单位）;辅助气体（GS 2），40（任意单位）。在所有情况下均使用氮气。聚焦

Glucopyranosyloxybenzyl tartrates, active components of the extract of Gymnadenia conopsea R. Br.(Orchidaceae),[1] are a series of derivatives of mono-and bis (4-β-D-glucopyranosyloxybenzyl)-2-isobutyltartrates. The dried tubers ofG. conopseahave been used as a traditional Chinese medicine with multiple pharmacological effects, including invigorating vital energy, promoting the production of body fluids, having a tranquilizing effect, and enhancing intelligence.[2, 3] Drug developments on active compounds and extracts from this herbal medicine are ongoing.[1, 4] The structuralspecific fragmentation behavior is critical to the identification of the new analogues and metabolites.[5–7] Therefore, we have studied the mass spectrometric behavior of glucopyranosyloxybenzyl tartrates. Comparative analysis of different types of alkali metal cations is a powerful strategy to enhance structural elucidation in mass spectrometry.[8–12]In the present study, the fragmentation reactions of the adduct ions of glucopyranosyloxybenzyl tartrates with Li+, Na+, K+ and NH4+ were investigated systematically by positive ion ESI-MS/MS. A characteristic ion generated by an unusual rearrangement reaction was observed in MS/MS spectra of [M+ W]+(W= Li, Na or K), and this reaction was explored through deuterium labeling and accurate mass measurements. In addition, The characteristics and differences of the fragmentation reactions that the [M+ W]+ and [M+ NH4]+ ions undergo were compared. Comparative analyses of different types of adduct ions offered valuable information for the gas-phase ion chemistry of these compounds and structural characterization and identification. Four glucopyranosyloxybenzyl tartrates (compounds 1–4, purity> 99%) were isolated fromG. conopseaR. Br.(Orchidaceae) and their structures were identified by spectroscopic methods.[1] The structures of these compounds are shown in Scheme 1. The samples were dissolved in the mobile phase (0.1%(v/v) HCOOH in 70%(v/v) acetonitrile in water) to a concentration of 10 pmol/µl and introduced into the mass spectrometer using a liquid chromatography system. The flow rate was 50 µl/min and injection volume was 2 µl. These compounds were each dissolved at a concentration of 10 pmol/µl in deuterated methanol (CD3OD) and kept at room temperature for 2 h to obtain the deuterated derivatives. Samples of the deuterated derivatives were injected into the ESI source via a syringe pump (direct infusion) at a flow rate of 10 µl/min. High resolution collision-induced dissociation (CID) spectra were obtained using a quadrupole orthogonal time-of-flight (QTOF) LC–MS/MS system (QSTAR Elite, Applied Biosystem/MDS Sciex) equipped with an ESI ion source. The source conditions were: spray voltage, 5.5 kV; temperature of ion source, 300◦ C; curtain gas, 25 (arbitrary units); collision gas, 5 (arbitrary units); nebulizer gas (GS1), 20 (arbitrary units); auxiliary gas (GS2), 40 (arbitrary units). Nitrogen gas was used in all cases. The focusing

The characteristic fragmentation and rearrangement reaction of cationized glucopyranosyloxybenzyl tartrates by tandem mass spectrometry.

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