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首页> 外文期刊>Journal of mass spectrometry: JMS >Mass spectrometric detection, identification, and fragmentation of arseno-phytochelatins
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Mass spectrometric detection, identification, and fragmentation of arseno-phytochelatins

机译：质谱检测，鉴定和裂解砷化植物螯合剂

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Phytochelatins (PC) are cystein-rich oligopeptides in plants for coordination with toxic metals and metalloids via their thiol groups. The composition, structure, and mass spectrometric fragmentation of arseno-PC (As-PC) with PC of different degree of oligomerization (PC2-PC5) in solution were studied using liquid chromatography coupled in parallel to inductively coupled plasma mass spectrometry and electrospray ionization quadrupole time-of-flight mass spectrometry. As-PC were detected from As(PC2) to As(PC5) with an increasing number of isomers that differ in the position of thiol groups bound to As. Thermodynamic modeling supported the identification process in case of these isomers. Mass spectrometric fragmentation of the As-PC does not follow the established pattern of peptides but is governed by the formation of series of As-containing annular cations, which coordinate to As via S, N, or O. Structure proposals for 30 As-PC fragment ions in the range m/z 147.92 to m/z 1290.18 are elaborated. Many of these fragment ions are characteristic to several As-PC and may be suited for a screening for As-PC in plant extracts. The mass spectrometric data offer the perspective for a future more sensitive determination of As-PC by means of liquid chromatography tandem mass spectrometry with multiple reaction monitoring.
机译：植物螯合素（PC）是植物中富含半胱氨酸的寡肽，可通过其巯基与有毒金属和准金属配位。研究了液相色谱与电感耦合等离子体质谱和电喷雾电离四极杆并联的液相色谱法研究了溶液中不同低聚度（PC2-PC5）的砷化PC（As-PC）的组成，结构和质谱碎裂飞行时间质谱。从As（PC2）到As（PC5）中检测到As-PC，且异构体的数量不断增加，这些异构体在与As结合的巯基位置上有所不同。在这些异构体的情况下，热力学建模支持了鉴定过程。 As-PC的质谱碎片化未遵循肽的既定模式，而是由一系列含As的环状阳离子的形成控制，这些阳离子通过S，N或O与As协调。30种As-PC的结构建议详细说明了m / z 147.92至m / z 1290.18范围内的碎片离子。这些碎片离子中的许多是几种As-PC的特征，并且可能适合筛选植物提取物中的As-PC。质谱数据为将来通过液相色谱串联质谱联用多反应监测技术更灵敏地测定As-PC提供了前景。

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