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Kendrick mass defect analysis — a tool for high-resolution Orbitrap mass spectrometry of native lignin

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Abstract

Lignin is the second most abundant biopolymer in nature and a promising renewable feedstock for the production of aromatic compounds, composite materials, sorbents, etc. Being a complex mixture of oligomeric molecules with an irregular structure, natural lignin is an extremely difficult object to study. Its molecular level characterization requires advanced analytical techniques among which atmospheric pressure photoionization Orbitrap mass spectrometry holds a promising place. In the present study, Kendrick mass defect (KMD) analysis was proposed to facilitate the visualization and interpretation of Orbitrap mass spectra of the biopolymer on an example of Siberian pine dioxane lignin preparation. The use of the typical guaiacylpropane structure C10H12O4 as a Kendrick base unit made it possible to effectively identify oligomer series with different polymerization degrees and structurally related compounds, as well as to reliably determine the elemental compositions and structures of oligomers with high molecular weights (> 1 kDa). For the first time, KMD analysis was applied to the interpretation of the complex tandem mass spectra of lignin oligomers, rapid discrimination of the product ion series, and the establishment of the main collision-induced dissociation pathways. It was demonstrated that especially promising was the use of KMD filtering in the study of broadband fragmentation tandem mass spectra, which allows for the structural characterization of all oligomers with a particular degree of polymerization.

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The data that support the findings of this study are available in the supporting information of this article.

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Acknowledgements

This study was performed using an instrumentation of the Core Facility Center “Arktika” of the Lomonosov Northern (Arctic) Federal University.

Funding

This research was funded by Russian Science Foundation, grant number 21-73-20275.

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  1. Laboratory of Natural Compounds Chemistry and Bioanalytics, Core Facility Center “Arktika”, M.V. Lomonosov Northern (Arctic) Federal University, Northern Dvina Emb. 17, 163002, Arkhangelsk, Russia

    Ilya I. Pikovskoi & Dmitry S. Kosyakov

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  1. Ilya I. Pikovskoi
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  2. Dmitry S. Kosyakov
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Correspondence to Ilya I. Pikovskoi.

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Pikovskoi, I.I., Kosyakov, D.S. Kendrick mass defect analysis — a tool for high-resolution Orbitrap mass spectrometry of native lignin. Anal Bioanal Chem 415, 3525–3534 (2023). https://doi.org/10.1007/s00216-023-04742-3

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