Application of lithium cationization tandem mass spectrometry for structural analysis of lignin model oligomers with β-β′ and β-O-4′ linkages

Masoumeh Dorrani, Bert C. Lynn

Research output: Contribution to journalArticlepeer-review

1 Scopus citations


Structural elucidation of lignin degradation products is a requirement for successfully developing lignin valorization technology. Most of mass spectrometry–based techniques have utilized negative ion mode mass spectrometry for structural elucidation of lignin-derived compounds. Unfortunately, simple deprotonation can lead to in-source fragmentation and may not be suitable for condensed lignin structures without acidic moieties. Herein, we present a lithium cationization methodology for mass spectrometry sequencing of advanced lignin oligomers having β-β′ and β-O-4′ bonding motifs. To do so, two advanced lignin oligomers were first synthesized through a step-by-step synthetic route, and then subjected to two different ESI mass spectrometry techniques in positive ion mode using lithium cations for ionization. An orbitrap mass spectrometer was used to obtain exact mass information, and higher-energy collisional dissociation (HCD) was used to sequence the lignin model oligomers. Based on the sequence-specific fragment ions, sequence rules were proposed. Multi-stage (MSn) collision-induced dissociation (CID) using an ion trap mass spectrometer provided data to investigate the origin of each fragment ion and to further confirm proposed fragmentation pathways. In addition to β-O-4′ bond cleavage, the presented lithium cationization approach led to cleavage of β-β′ bonds on the model oligomers in both ion trap and orbitrap mass spectrometry experiments. Additionally, MSn experiments were used to investigate possible lithium cationization sites on the model oligomers. Lithium cationization in positive ion mode mass spectrometry proved to be a robust tool for characterization and sequencing of advanced lignin oligomers with different bonding motifs. Graphical abstract: [Figure not available: see fulltext.].

Original languageEnglish
Pages (from-to)5755-5771
Number of pages17
JournalAnalytical and Bioanalytical Chemistry
Issue number19
StatePublished - Aug 2022

Bibliographical note

Funding Information:
This research was funded by the National Science Foundation EPSCor Track 2 (OAI 1632854).

Publisher Copyright:
© 2022, Springer-Verlag GmbH Germany, part of Springer Nature.


  • Advanced lignin model oligomer
  • Collision-induced dissociation (CID)
  • Higher-energy collisional dissociation (HCD)
  • Lithium cationization
  • Sequencing
  • Tandem mass spectrometry

ASJC Scopus subject areas

  • Analytical Chemistry
  • Biochemistry


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