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A critique on the structural analysis of lignins and application of novel tandem mass spectrometric strategies to determine lignin sequencing

Banoub, Joseph H. and Delmas, Guo-Hua and Joly, Nicolas and Mackenzie, Grahame and Cachet, Nadja and Benjelloun-Mlayah, Bouchra and Delmas, Michel A critique on the structural analysis of lignins and application of novel tandem mass spectrometric strategies to determine lignin sequencing. (2015) Journal of Mass Spectrometry, 50 (1). 5-48. ISSN 1076-5174

(Document in English)

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Official URL: https://doi.org/10.1002/jms.3541


This review is devoted to the application of MS using soft ionization methods with a special emphasis on electrospray ionization, atmospheric pressure photoionization and matrix‐assisted laser desorption/ionization MS and tandem MS (MS/MS) for the elucidation of the chemical structure of native and modified lignins. We describe and critically evaluate how these soft ionization methods have contributed to the present‐day knowledge of the structure of lignins. Herein, we will introduce new nomenclature concerning the chemical state of lignins, namely, virgin released lignins (VRLs) and processed modified lignins (PML). VRLs are obtained by liberation of lignins through degradation of vegetable matter by either chemical hydrolysis and/or enzymatic hydrolysis. PMLs are produced by subjecting the VRL to a series of further chemical transformations and purifications that are likely to alter their original chemical structures. We are proposing that native lignin polymers, present in the lignocellulosic biomass, are not made of macromolecules linked to cellulose fibres as has been frequently reported. Instead, we propose that the lignins are composed of vast series of linear related oligomers, having different lengths that are covalently linked in a criss‐cross pattern to cellulose and hemicellulose fibres forming the network of vegetal matter. Consequently, structural elucidation of VRLs, which presumably have not been purified and processed by any other type of additional chemical treatment and purification, may reflect the structure of the native lignin. In this review, we present an introduction to a MS/MS top–down concept of lignin sequencing and how this technique may be used to address the challenge of characterizing the structure of VRLs. Finally, we offer the case that although lignins have been reported to have very high or high molecular weights, they might not exist on the basis that such polymers have never been identified by the mild ionizing techniques used in modern MS. Copyright © 2015 John Wiley & Sons, Ltd.

Item Type:Article
HAL Id:hal-01886313
Audience (journal):International peer-reviewed journal
Uncontrolled Keywords:
Institution:French research institutions > Centre National de la Recherche Scientifique - CNRS (FRANCE)
Other partners > Fisheries and Oceans Canada (CANADA)
Université de Toulouse > Institut National Polytechnique de Toulouse - Toulouse INP (FRANCE)
Université de Toulouse > Université Toulouse III - Paul Sabatier - UT3 (FRANCE)
Other partners > Compagnie Industrielle de la Matière Végétale - CIMV (FRANCE)
Other partners > Memorial University of Newfoundland - MUN (CANADA)
Laboratory name:
Deposited On:02 Oct 2018 15:49

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