Polyphenol identification based on systematic and robust high-resolution accurate mass spectrometry fragmentation
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High-mass resolution multi-stage mass spectrometry (MS(n)) fragmentation was tested for differentiation and identification of metabolites, using a series of 121 polyphenolic molecules. The MS(n) fragmentation approach is based on the systematic breakdown of compounds, forming a so-called spectral tree. A chip-based nanoelectrospray ionization source was used combined with an ion-trap, providing reproducible fragmentation, and accurate mass read-out in an Orbitrap Fourier transform (FT) MS enabling rapid assignment of elemental formulas to the molecular ions and all fragment ions derived thereof. The used protocol resulted in reproducible MS(n) fragmentation trees up to MS(5). Obtained results were stable over a 5 month time period, a concentration change of 100-fold, and small changes in normalized collision energy, which is key to metabolite annotation and helpful in structure and substructure elucidation. Differences in the hydroxylation and methoxylation patterns of polyphenolic core structures were found to be reflected by the differential fragmentation of the entire molecule, while variation in a glycosylation site displayed reproducible differences in the relative intensities of fragments originating from the same aglycone fragment ion. Accurate MS(n)-based spectral tree data are therefore a powerful tool to distinguish metabolites with similar elemental formula, thereby assisting compound identification in complex biological samples such as crude plant extracts.
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- Authors
- van der Hooft, J. J. J., Vervoort, J., Bino, R. J., Beekwilder, J., & de Vos, R. C. H.
- Affiliations
- Laboratory of Biochemistry, Wageningen University, Dreijenlaan 3, 6703 HA, Wageningen, The Netherlands, Plant Research International, Wageningen University and Research Centre, POB 16, 6700 AA, Wageningen, The Netherlands, Laboratory of Plant Physiology, Wageningen University, POB 658, 6700 AR, Wageningen, The Netherlands, Centre for Biosystems Genomics, POB 98, 6700 AB, Wageningen, The Netherlands, and Netherlands Metabolomics Centre, Einsteinweg 55, 2333 CC, Leiden, The Netherlands
- Centre for BioSystems Genomics (NL)
- Venue
- Analytical Chemistry
- Publisher
- American Chemical Society (ACS)
- Published
- 2010-12-09
- Volume
- 83
- Issue
- 1
- Pages
- 409-416
- ISSN
- 0003-2700 (ISSN-L)
- 1520-6882
- OpenAlex
- W2148212669
- Cited by
- 99
- References
- 49
- Citations by year
- 2026: 2 · 2022: 4 · 2021: 5 · 2020: 2 · 2019: 4 · 2018: 2 · 2017: 6 · 2016: 8 · 2015: 12 · 2014: 15 · 2013: 18 · 2012: 17
- FWCI
- 5.58
- Type
- journal article
- Language
- en
- Open access
- green
- research.wur.nl
- Locations
- Analytical Chemistry (publishedVersion)
- PubMed (publishedVersion)
- Socio-Environmental Systems Modeling (acceptedVersion)
- Data Archiving and Networked Services (DANS) (submittedVersion)
- Topics
- Physical Sciences › Chemistry › Spectroscopy › Mass Spectrometry Techniques and Applications
- Life Sciences › Biochemistry, Genetics and Molecular Biology › Molecular Biology › Metabolomics and Mass Spectrometry Studies
- Physical Sciences › Chemistry › Spectroscopy › Advanced Proteomics Techniques and Applications
- Keywords
- polyphenols, ion trap, nanoelectrospray ionization, Orbitrap, metabolite identification, glycosylation, plant extracts
- MeSH terms
- Flavonoids, Glycosylation, Hydroxylation, Injections, Phenols, Mass Spectrometry, Stereoisomerism, Time Factors, Reproducibility of Results, Nanotechnology, Metabolomics, Polyphenols
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