The study of the chromatographic behavior and a mass spectrometric approach to differentiating the diastereomer pair of the β-O-4 lignin dimer series

Shardrack O. Asare, Kimberly R. Dean, Bert C. Lynn

Research output: Contribution to journalArticlepeer-review

2 Scopus citations

Abstract

Lignin and lignans are natural products found in plant cell walls. Lignin research has historically focused on lignin degradation techniques in the hope of converting lignin into useful aromatic carbon feedstocks. In contrast, investigations of lignans existing as natural product dimers, have been focused on thier interesting biological activities. Many lignan compounds are chemically identical to dimers derived from lignin, and both lignin and lignan dimers can possess multiple chiral centers leading to observations of diastereomer pairs where one diastereomer exhibits the bulk of the activity. For example, the G-(β-O-4′)-G dimer was reported to have a pro-angiogenic activity with one diastereomer of the pair showing enhanced pro-angiogenic activity. Traditional analytical techniques such as nuclear magnetic resonance (NMR) can differentiate the diastereomer pairs of β-O-4 compounds; however, isolation of a pure sample is often required for analysis. This work was aimed at exploring the potential use of tandem mass spectrometry to differentiate diastereomer pairs in the β-O-4 dimer series. Each diastereomer pair in the nine-dimer series was separated by HPLC and interrogated by tandem mass spectrometry. To understand the chromatographic behavior of the diastereomer pair in the β-O-4 dimer series, three commercially available reverse phase HPLC columns were evaluated. A temperature programming experiment using water/acetonitrile isocratic elution showed that the chromatographic retention mechanism of these diastereomers was hydrophobically driven with analytes having more methoxy groups exhibiting larger ΔH0 and higher octanol-water partition coefficient values. Tandem mass spectrometry performed on each of the diastereomers produced fragment ions having different ion abundances. A mechanistic study based on the ion abundance of “sequence-specific ions” and “-48 ions” was used to assign a configuration to each of the pairs of diastereomers in the nine-dimer series. Graphical abstract: [Figure not available: see fulltext.].

Original languageEnglish
Pages (from-to)4037-4048
Number of pages12
JournalAnalytical and Bioanalytical Chemistry
Volume413
Issue number15
DOIs
StatePublished - Jun 2021

Bibliographical note

Publisher Copyright:
© 2021, Springer-Verlag GmbH Germany, part of Springer Nature.

Keywords

  • Diastereomers
  • HPLC
  • Lignans
  • Tandem mass spectrometry

ASJC Scopus subject areas

  • Analytical Chemistry
  • Biochemistry

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