Dehydrodimerization of pterostilbene during electrospray ionization mass spectrometry

• Published in: Rapid communications in mass spectrometry Vol. 27; no. 11; pp. 1260 - 1266
• Main Authors: Raji, Misjudeen, Amad, Ma'an, Emwas, Abdel-Hamid
• Format: Journal Article
• Language: English
• Published: England Blackwell Publishing Ltd 15-06-2013; Wiley Subscription Services, Inc
• Subjects: Concentration (composition); Dimerization; Dimers; Ionization; Mass spectrometry; Molecular Structure; Nuclear magnetic resonance; Scavengers; Solvents; Spectrometry, Mass, Electrospray Ionization - methods; Stilbenes - chemistry
• ISSN: 0951-4198; 1097-0231
• DOI: 10.1002/rcm.6571

RATIONALE
Pterostilbene is a member of the hydroxystilbene family of compounds commonly found in plants such as blueberry and grapes. During the analysis of this compound by electrospray ionization mass spectrometry (ESI‐MS), an ion was observed that corresponds to the dehydrodimer of pterostilbene in mass‐to‐charge ratio. Since such unexpected dimerization may lead to decreased monomer signal during quantitative analysis, it was of interest to identify the origin and structure of the observed pterostilbene dimer and examine the experimental conditions that influence its formation.
METHODS
Liquid Chromatography/Mass Spectrometry (LC/MS), Nuclear Magnetic Resonance (NMR), and High‐Field Asymmetric Waveform Ion Mobility Spectrometry (FAIMS) were used to examine the origin of the dimerization products. The structure of the formed pterostilbene dimer was examined by performing MSn analysis on the dimer ion. Effects of solvent composition, analyte concentration, radical scavenger, and other experimental conditions on the dimerization were also studied.
RESULTS
LC/MS and NMR analyses clearly showed that the starting solution did not contain the pterostilbene dimer. Solvent type and radical scavenger concentration were found to have pronounced effects on the dimer formation. Particularly, presence of acetonitrile or ammonium acetate had favorable effects on the extent of dimerization during ESI‐MS analysis whereas hydroquinone and butylated hydroquinone had negative effects. Dimer formation decreased at high flow rates and when fused‐silica capillary was used as the spray needle.
CONCLUSIONS
The data indicate that this dimerization occurs as a result of solution‐phase electrochemical reactions taking place during the electrospray process. A possible structure for this dimer was proposed based on the MSn analysis and was similar to that of the enzymatically derived pterostilbene dehydrodimer already reported in the literature. Copyright © 2013 John Wiley & Sons, Ltd.