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Studies of xylan interactions and cross-linking to synthetic lignins formed by bulk and end-wise polymerization: a model study of lignin carbohydrate complex formation

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Abstract

The mechanism of lignin carbohydrate complex formation by addition of polysaccharides on quinone methide (QM) generated during lignin polymerisation was investigated using a model approach. Dehydrogenation polymers (DHPs, lignin model compounds) were synthesized from coniferyl alcohol in the presence of a glucuronoarabinoxylan (GAX) extracted from oat spelts, by Zutropfverfahren (ZT) and Zulaufverfahren (ZL) methods. The methods ZT and ZL differed in their distribution of QM over the reaction period but generated roughly the same QM amount. Steric exclusion chromatography of the ZT and ZL reaction products showed that only the ZT reaction produced high molar mass compounds. Covalent linkages in the ZT reaction involving ether bonds between GAX moiety and α carbon of the lignin monomer were confirmed by 13C NMR and xylanase-based fractionation. The underlying phenomena were further investigated by examining the interactions between GAX and DHP in sorption experiments. GAX and DHPs were shown to interact to form hydrophobic aggregates. In the ZT process, slow addition permitted polymer reorganisation which led to dehydration around the lignin-like growing chains thereby limiting the addition of water on the quinone methide formed during polymerisation and thus favoured lignin–carbohydrate complex (LCC) formation.

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Abbreviations

CA:

Coniferyl alcohol

CPMAS:

Cross polarization magic angle spinning

DHP:

Dehydrogenation polymer

DMSO:

Dimethyl sulfoxide

GAX:

Glucuronoarabinoxylan

HPAEC:

High-pressure anion exchange chromatography

LCC:

Lignin–carbohydrate complex

LiBr:

Lithium bromide

NMR:

Nuclear magnetic resonance

QM:

Quinone methide

SEC:

Steric-exclusion chromatography

ZL:

Zulaufverfahren

ZT:

Zutropfverfahren

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Acknowledgments

Access to the NMR facilities of the BIBS platform (Biopolymers, Interactions, Structural Biology) of INRA-Nantes was greatly appreciated by the authors.

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Authors and Affiliations

  1. Unité Mixte de Recherche Fractionnement des AgroRessources et Emballages, Institut National de la Recherche Agronomique, Equipe Parois et Matériaux Fibreux, 51686, Reims Cedex 2, France

    Abdellatif Barakat & Brigitte Chabbert

  2. Federal Research Centre for Forestry and Forest Products, Institute for Wood Chemistry and Chemical Technology of Wood, Leuschnerstr. 91, 21031, Hamburg, Germany

    Heiko Winter & Bodo Saake

  3. Unité Biopolymères, Interactions et Assemblages, Institut National de la Recherche Agronomique, Rue de la géraudière, 44316, BP 71627, Nantes Cedex 3, France

    Corinne Rondeau-Mouro & Bernard Cathala

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  1. Abdellatif Barakat
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  2. Heiko Winter
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  3. Corinne Rondeau-Mouro
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  4. Bodo Saake
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  5. Brigitte Chabbert
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  6. Bernard Cathala
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Correspondence to Bernard Cathala.

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Barakat, A., Winter, H., Rondeau-Mouro, C. et al. Studies of xylan interactions and cross-linking to synthetic lignins formed by bulk and end-wise polymerization: a model study of lignin carbohydrate complex formation. Planta 226, 267–281 (2007). https://doi.org/10.1007/s00425-007-0479-1

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  • DOI: https://doi.org/10.1007/s00425-007-0479-1

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