Publication Details

Category Text Publication
Reference Category Journals
DOI 10.1002/jms.3435
Title (Primary) Mass spectrometric detection, identification, and fragmentation of arseno-phytochelatins
Author Schmied-Tobies, M.I.H.; Arroyo-Abad, U.; Mattusch, J.; Reemtsma, T.
Journal Journal of Mass Spectrometry
Year 2014
Department ANA
Volume 49
Issue 11
Page From 1148
Page To 1155
Language englisch
Keywords arsenic; complexation; analysis; plants; heavy metals; toxicity
UFZ wide themes RU3;
Abstract 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
Persistent UFZ Identifier
Schmied-Tobies, M.I.H., Arroyo-Abad, U., Mattusch, J., Reemtsma, T. (2014):
Mass spectrometric detection, identification, and fragmentation of arseno-phytochelatins
J. Mass Spectrom. 49 (11), 1148 - 1155