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Hydroxycinnamates in lignification

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Abstract

Hydroxycinnamates incorporate into lignins by various mechanisms. The polysaccharide esters of ferulate, in particular, and the range of dehydrodiferulates and higher oligomers in grasses, participate in free-radical (cross-)coupling reactions during lignification to become integrally bound into the lignin polymer, resulting in extensive cross-linking between lignins and polysaccharides. Monolignol-hydroxycinnamate (primarily monolignol-p-coumarate) conjugates are primary building blocks for lignins, again in grasses (but analogously with monolignol acetates and p-hydroxybenzoates in other plants); radical coupling reactions of the monolignol moiety of the conjugate result in lignins with pendant p-coumarate units acylating a variety of lignin structures. Recent evidence suggests that even the hydroxycinnamic acids themselves can be monomers in lignification in wild-type and transgenic plants, undergoing radical cross-coupling reactions to incorporate into the polymer with interesting consequences. The compatibility of ferulate, in particular, with lignification suggests that plants able to utilize monolignol-ferulate conjugates in their primary monomer supply will be particularly well suited for subsequent chemical delignification, potentially improving processes for biomass conversion to biofuels, and for chemical pulping.

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Abbreviations

CCR:

Cinnamoyl-CoA reductase

NMR:

Nuclear magnetic resonance (spectroscopy)

DHP:

Dehydrogenation polymer (synthetic lignin)

AFEX:

Ammonia fiber expansion (process)

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Acknowledgments

We gratefully acknowledge partial funding for through the DOE Energy Biosciences program (#DE-AI02-00ER15067) and the USDA-NRI (#2003-35503-13820), along with new funding from Stanford University’s Global Climate and Energy Program (GCEP) to pursue approaches toward lignin modification; some aspects of this research were funded in by the DOE Great Lakes Bioenergy Research Center (www.greatlakesbioenergy.org), which is supported by the US Department of Energy, Office of Science, Office of Biological and Environmental Research, through Cooperative Agreement DE-FC02-07ER64494 between The Board of Regents of the University of Wisconsin System and the US Department of Energy. The author is grateful to many coworkers and collaborators who worked on many of these aspects, including but not limited to: Mirko Bunzel, John Grabber, Ron Hatfield, Fachuang Lu, Hoon Kim, Takuya Akiyama, Jane Marita, Paul Schatz, Junpeng Peng, Richard Helm, Stéphane Quideau, Catherine Lapierre, Wout Boerjan, Clint Chapple, Gösta Brunow, and Hans Jung.

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  1. Departments of Biochemistry and Biological Systems Engineering, University of Wisconsin-Madison, Madison, WI, 53706, USA

    John Ralph

  2. The DOE Great Lakes Bioenergy Research Center, University of Wisconsin-Madison, Madison, WI, 53706, USA

    John Ralph

  3. Department of Biochemistry (Enzyme Institute), 1710 University Avenue, Madison, WI, 53706-4087, USA

    John Ralph

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Ralph, J. Hydroxycinnamates in lignification. Phytochem Rev 9, 65–83 (2010). https://doi.org/10.1007/s11101-009-9141-9

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