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Towards lignin-protein crosslinking: amino acid adducts of a lignin model quinone methide

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A Correction to this article was published on 28 May 2019

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Abstract

The polyaromatic structure of lignin has long been recognized as a key contributor to the rigidity of plant vascular tissues. Although lignin structure was once conceptualized as a highly networked, heterogeneous, high molecular weight polymer, recent studies have suggested a very different configuration may exist in planta. These findings, coupled with the increasing attention and interest in efficiently utilizing lignocellulosic materials for green materials and energy applications, have renewed interest in lignin chemistry. Here we focus on quinone methides (QMs)—key intermediates in lignin polymerization—that are quenched via reaction with cell-wall-available nucleophiles. Reactions with alcohol and uronic acid groups of hemicelluloses, for example, can lead to lignin-carbohydrate crosslinks. Our work is a first step toward exploring potential QM reactions with nucleophilic groups in cell wall proteins. We conducted a model compound study wherein the lignin model compound guaiacylglycerol-β-guaiacyl ether 1, was converted to its QM 2, then reacted with amino acids bearing nucleophilic side-groups. Yields for the QM-amino acid adducts ranged from quantitative in the case of QM-lysine 3, to zero (no reaction) in the cases of QM-threonine (Thr) 10 and QM-hydroxyproline (Hyp) 11. The structures of the QM-amino acid adducts were confirmed via 1D and 2D nuclear magnetic resonance (NMR) spectroscopy and density functional theory (DFT) calculations, thereby extending the lignin NMR database to include amino acid crosslinks. Some of the QM-amino acid adducts formed both syn- and anti-isomers, whereas others favored only one isomer. Because the QM-Thr 10 and QM-Hyp 11 compounds could not be experimentally prepared under conditions described here but could potentially form in vivo, we used DFT to calculate their NMR shifts. Characterization of these model adducts extends the lignin NMR database to aid in the identification of lignin-protein linkages in more complex in vitro and in vivo systems, and may allow for the identification of such linkages in planta.

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Change history

  • 28 May 2019

    The manuscript initially failed to cite the work of Dr. Cong et al., which was the basis for this effort. We apologize for this error.

  • 28 May 2019

    The manuscript initially failed to cite the work of Dr. Cong et al., which was the basis for this effort. We apologize for this error.

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Acknowledgments

This research was supported as part of The Center for Lignocellulose Structure and Formation, an Energy Frontier Research Center funded by the US Department of Energy, Office of Science, Office of Basic Energy Sciences under Award Number DE-SC0001090, and the DOE Great Lakes Bioenergy Research Center (DOE Office of Science BER DE-FC02-07ER64494). The authors would like to thank and acknowledge the Center for Lignocellulose Structure and Formation (CLSF) and the members thereof. Student fellowships were provided by the USDA National Needs Program and the National Science Foundation. The authors would like to thank Dr. Alan Benesi and Dr. Wenbin Luo for assistance in acquiring NMR spectra of the lignin model compounds, Dr. James Miller for acquiring mass spec data, and Dr. Josh Stapleton for providing assistance with UV/Vis. The primary author would also like to acknowledge Paul Munson and Curtis Frantz for valuable discussion, and valuable interactions with Dan Gall and other members of the Wisconsin lab.

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Authors and Affiliations

  1. Department of Agricultural and Biological Engineering, The Pennsylvania State University, 226 Forest Resources Building, University Park, PA, 16802, USA

    Brett G. Diehl

  2. Department of Geosciences, The Pennsylvania State University, 305 Deike Building, University Park, PA, 16802, USA

    Heath D. Watts

  3. Department of Geosciences and the Earth and Environmental Systems Institute, The Pennsylvania State University, 335 Deike Building, University Park, PA, 16802, USA

    James D. Kubicki

  4. Department of Biochemistry and DOE Great Lakes Bioenergy Research Center, Wisconsin Energy Institute, Madison, WI, 53726, USA

    Matthew R. Regner & John Ralph

  5. Department of Agricultural and Biological Engineering, The Pennsylvania State University, 209 Agricultural Engineering Building, University Park, PA, 16802, USA

    Nicole R. Brown

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  1. Brett G. Diehl
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Correspondence to Brett G. Diehl.

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Diehl, B.G., Watts, H.D., Kubicki, J.D. et al. Towards lignin-protein crosslinking: amino acid adducts of a lignin model quinone methide. Cellulose 21, 1395–1407 (2014). https://doi.org/10.1007/s10570-014-0181-y

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