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Title: Tricin-lignins: occurrence and quantitation of tricin in relation to phylogeny

We report tricin [5,7-dihydroxy-2-(4-hydroxy-3,5-dimethoxyphenyl)-4H-chromen-4-one], a flavone, was recently established as an authentic monomer in grass lignification that likely functions as a nucleation site. It is linked onto lignin as an aryl alkyl ether by radical coupling with monolignols or their acylated analogs. However, the level of tricin that incorporates into lignin remains unclear. Herein, three lignin characterization methods: acidolysis; thioacidolysis; and derivatization followed by reductive cleavage; were applied to quantitatively assess the amount of lignin-integrated tricin. Their efficiencies at cleaving the tricin-(4'–O–β)-ether bonds and the degradation of tricin under the corresponding reaction conditions were evaluated. A hexadeuterated tricin analog was synthesized as an internal standard for accurate quantitation purposes. Thioacidolysis proved to be the most efficient method, liberating more than 91% of the tricin with little degradation. A survey of different seed-plant species for the occurrence and content of tricin showed that it is widely distributed in the lignin from species in the family Poaceae (order Poales). Tricin occurs at low levels in some commelinid monocotyledon families outside the Poaceae, such as the Arecaceae (the palms, order Arecales) and Bromeliaceae (Poales), and the non-commelinid monocotyledon family Orchidaceae (Orchidales). One eudicotyledon was found to have tricin (Medicago sativa, Fabaceae). The contentmore » of lignin-integrated tricin is much higher than the extractable tricin level in all cases. Finally, lignins, including waste lignin streams from biomass processing, could therefore provide a large and alternative source of this valuable flavone, reducing the costs, and encouraging studies into its application beyond its current roles.« less
Authors:
 [1] ;  [2] ;  [3] ;  [4] ;  [5] ;  [6] ;  [2] ;  [7]
  1. Univ. of Wisconsin, Madison, WI (United States). DOE Great Lakes Bioenergy Research Center, Wisconsin Energy Institute and Department of Biological System Engineering
  2. Instituto de Recursos Naturales y Agrobiologia de Sevilla (IRNAS), CSIC, Seville (Spain)
  3. Univ. of Wisconsin, Madison, WI (United States). DOE Great Lakes Bioenergy Research Center, Wisconsin Energy Institute and Department of Biochemistry; South China University of Technology, Guangzhou (China). State Key Laboratory of Pulp and Paper Engineering
  4. Univ. of Wisconsin, Madison, WI (United States). DOE Great Lakes Bioenergy Research Center, Wisconsin Energy Institute and Department of Biochemistry
  5. The University of Auckland (New Zealand). School of Chemical Sciences
  6. The University of Auckland (New Zealand). School of Biological Sciences
  7. Univ. of Wisconsin, Madison, WI (United States). DOE Great Lakes Bioenergy Research Center, Wisconsin Energy Institute, Department of Biological System Engineering, and Department of Biochemistry
Publication Date:
Grant/Contract Number:
FC02-07ER64494; AI02-06ER64299
Type:
Published Article
Journal Name:
The Plant Journal
Additional Journal Information:
Journal Volume: 88; Journal Issue: 6; Journal ID: ISSN 0960-7412
Publisher:
Society for Experimental Biology
Research Org:
Univ. of Wisconsin, Madison, WI (United States); Agricultural Research Service, MD (United States)
Sponsoring Org:
USDOE Office of Science (SC), Biological and Environmental Research (BER) (SC-23)
Country of Publication:
United States
Language:
English
Subject:
59 BASIC BIOLOGICAL SCIENCES; thioacidolysis; acidolysis; derivatization followed by reductive cleavage; Poaceae; tricin-d6; stable isotopically labeled internal standard; liquid chromatography-mass spectrometry; multiple reaction monitoring
OSTI Identifier:
1330903
Alternate Identifier(s):
OSTI ID: 1330904; OSTI ID: 1427721

Lan, Wu, Rencoret, Jorge, Lu, Fachuang, Karlen, Steven D., Smith, Bronwen G., Harris, Philip J., del Río, José Carlos, and Ralph, John. Tricin-lignins: occurrence and quantitation of tricin in relation to phylogeny. United States: N. p., Web. doi:10.1111/tpj.13315.
Lan, Wu, Rencoret, Jorge, Lu, Fachuang, Karlen, Steven D., Smith, Bronwen G., Harris, Philip J., del Río, José Carlos, & Ralph, John. Tricin-lignins: occurrence and quantitation of tricin in relation to phylogeny. United States. doi:10.1111/tpj.13315.
Lan, Wu, Rencoret, Jorge, Lu, Fachuang, Karlen, Steven D., Smith, Bronwen G., Harris, Philip J., del Río, José Carlos, and Ralph, John. 2016. "Tricin-lignins: occurrence and quantitation of tricin in relation to phylogeny". United States. doi:10.1111/tpj.13315.
@article{osti_1330903,
title = {Tricin-lignins: occurrence and quantitation of tricin in relation to phylogeny},
author = {Lan, Wu and Rencoret, Jorge and Lu, Fachuang and Karlen, Steven D. and Smith, Bronwen G. and Harris, Philip J. and del Río, José Carlos and Ralph, John},
abstractNote = {We report tricin [5,7-dihydroxy-2-(4-hydroxy-3,5-dimethoxyphenyl)-4H-chromen-4-one], a flavone, was recently established as an authentic monomer in grass lignification that likely functions as a nucleation site. It is linked onto lignin as an aryl alkyl ether by radical coupling with monolignols or their acylated analogs. However, the level of tricin that incorporates into lignin remains unclear. Herein, three lignin characterization methods: acidolysis; thioacidolysis; and derivatization followed by reductive cleavage; were applied to quantitatively assess the amount of lignin-integrated tricin. Their efficiencies at cleaving the tricin-(4'–O–β)-ether bonds and the degradation of tricin under the corresponding reaction conditions were evaluated. A hexadeuterated tricin analog was synthesized as an internal standard for accurate quantitation purposes. Thioacidolysis proved to be the most efficient method, liberating more than 91% of the tricin with little degradation. A survey of different seed-plant species for the occurrence and content of tricin showed that it is widely distributed in the lignin from species in the family Poaceae (order Poales). Tricin occurs at low levels in some commelinid monocotyledon families outside the Poaceae, such as the Arecaceae (the palms, order Arecales) and Bromeliaceae (Poales), and the non-commelinid monocotyledon family Orchidaceae (Orchidales). One eudicotyledon was found to have tricin (Medicago sativa, Fabaceae). The content of lignin-integrated tricin is much higher than the extractable tricin level in all cases. Finally, lignins, including waste lignin streams from biomass processing, could therefore provide a large and alternative source of this valuable flavone, reducing the costs, and encouraging studies into its application beyond its current roles.},
doi = {10.1111/tpj.13315},
journal = {The Plant Journal},
number = 6,
volume = 88,
place = {United States},
year = {2016},
month = {8}
}

Works referenced in this record:

Lignin Biosynthesis
journal, June 2003

Identification of Grass-specific Enzyme That Acylates Monolignols with p-Coumarate
journal, January 2012
  • Withers, Saunia; Lu, Fachuang; Kim, Hoon
  • Journal of Biological Chemistry, Vol. 287, Issue 11, p. 8347-8355
  • DOI: 10.1074/jbc.M111.284497

Lignin Biosynthesis and Structure
journal, May 2010
  • Vanholme, R.; Demedts, B.; Morreel, K.
  • Plant Physiology, Vol. 153, Issue 3, p. 895-905
  • DOI: 10.1104/pp.110.155119

Pathway of p-Coumaric Acid Incorporation into Maize Lignin As Revealed by NMR
journal, October 1994
  • Ralph, John; Hatfield, Ronald D.; Quideau, Stephane
  • Journal of the American Chemical Society, Vol. 116, Issue 21, p. 9448-9456
  • DOI: 10.1021/ja00100a006