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Elucidation of the complex molecular structure of wheat straw lignin polymer by atmospheric pressure photoionization quadrupole time-of-flight tandem mass spectrometry

Authors

  • Joseph H. Banoub,

    Corresponding author
    1. Department of Chemistry, Memorial University of Newfoundland, and Fisheries and Oceans Canada, Science Branch, Special Projects, P.O. Box 5667, St John's, Newfoundland, A1C 5X1, Canada
    • Department of Chemistry, Memorial University of Newfoundland and Fisheries and Oceans Canada, Science Branch, Special Projects, P.O. Box 5667, St John's, Newfoundland, A1C 5X1, Canada.
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  • Bouchra Benjelloun-Mlayah,

    1. Compagnie Industrielle de la Matière Végétale (CIMV), 134 Rue Danton, 92300 Levallois-Perret, France
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  • Fabio Ziarelli,

    1. Université P. Cézanne Aix-Marseille III, Faculté des Sciences et Techniques, Avenue de l'Escadrille Normandie-Niemen, 13397 Marseille, France
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  • Nicolas Joly,

    1. Laboratoire de Physico-Chimie des Interfaces et Applications FRE CNRS 2485, Site de Béthune, Fédération Chevreul FR CNRS 2638, Université d'Artois, IUT de Béthune, Département Chimie, BP819, 62408 Béthune cedex, France
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  • Michel Delmas

    1. Compagnie Industrielle de la Matière Végétale (CIMV), 134 Rue Danton, 92300 Levallois-Perret, France
    2. École Nationale Supérieure des Ingénieurs en Arts Chimiques et Technologiques, Institut National Polythechnique de Toulouse, 118 route de Narbonne, 31077 Toulouse Cedex 4, France
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Abstract

Wheat straw lignin was extracted using the novel CIMV procedure which selectively separates the cellulose, hemicelluloses and lignin. Solid-state 13C NMR experiments using cross polarization/magic angle spinning (CP/MAS) were carried out on the extracted wheat straw lignin and some structural indices were revealed. Atmospheric pressure photoionization mass spectrometry (APPI-MS) has proven to be a powerful analytical tool capable of ionizing small to large lignin oligomers, which cannot be ionized efficiently by atmospheric pressure chemical ionization (APCI) and electrospray ionization (ESI). The APPI mass spectra of the extracted wheat straw lignin were recorded in the positive and negative ion modes. Positive ion mode APPI-MS indicated the exact presence of 39 specific oligomeric ions. Negative ion APPI-MS indicated the additional presence of at least 18 specific oligomeric ions. The structural characterization of this novel and complete series of 57 specific related oligomers was achieved by calculating the exact molecular masses measured by high-resolution quadrupole time-of-flight mass spectrometry (QqToF-MS). Some oligomeric species photoionized in both the positive and negative ion modes to form the respective protonated and deprotonated molecules. Low-energy collision-induced dissociation tandem mass spectrometric analyses performed with a QqToF-MS/MS hybrid instrument provided unique dissociation patterns of the complete series of novel precursor ions. These MS/MS analyses provided diagnostic product ions, which enabled us to determine the exact molecular structures and arrangement of the selected 57 different related ionic species. Copyright © 2007 John Wiley & Sons, Ltd.

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