skip to main content
DOE PAGES title logo U.S. Department of Energy
Office of Scientific and Technical Information

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

Abstract

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. DOE Great Lakes Bioenergy Research Center, Wisconsin Energy Institute, University of Wisconsin, Madison WI USA, Department of Biological System Engineering, University of Wisconsin, Madison WI USA
  2. Instituto de Recursos Naturales y Agrobiologia de Sevilla (IRNAS), CSIC, Avenida de la Reina Mercedes, 10 41012 Seville Spain
  3. DOE Great Lakes Bioenergy Research Center, Wisconsin Energy Institute, University of Wisconsin, Madison WI USA, Department of Biochemistry, University of Wisconsin, Madison WI USA, State Key Laboratory of Pulp and Paper Engineering, South China University of Technology, Guangzhou China
  4. DOE Great Lakes Bioenergy Research Center, Wisconsin Energy Institute, University of Wisconsin, Madison WI USA, Department of Biochemistry, University of Wisconsin, Madison WI USA
  5. School of Chemical Sciences, The University of Auckland, Auckland New Zealand
  6. School of Biological Sciences, The University of Auckland, Auckland New Zealand
  7. DOE Great Lakes Bioenergy Research Center, Wisconsin Energy Institute, University of Wisconsin, Madison WI USA, Department of Biological System Engineering, University of Wisconsin, Madison WI USA, Department of Biochemistry, University of Wisconsin, Madison WI USA
Publication Date:
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)
OSTI Identifier:
1330903
Alternate Identifier(s):
OSTI ID: 1330904; OSTI ID: 1427721
Grant/Contract Number:  
AI02-06ER64299; FC02-07ER64494
Resource Type:
Published Article
Journal Name:
The Plant Journal
Additional Journal Information:
Journal Name: The Plant Journal Journal Volume: 88 Journal Issue: 6; Journal ID: ISSN 0960-7412
Publisher:
Wiley-Blackwell
Country of Publication:
United Kingdom
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

Citation Formats

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 Kingdom: N. p., 2016. 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 Kingdom. 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. Thu . "Tricin-lignins: occurrence and quantitation of tricin in relation to phylogeny". United Kingdom. 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 Kingdom},
year = {2016},
month = {11}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record
DOI: 10.1111/tpj.13315

Citation Metrics:
Cited by: 12 works
Citation information provided by
Web of Science

Save / Share:

Works referenced in this record:

Lignin Biosynthesis
journal, June 2003


Tricin, a Flavonoid Monomer in Monocot Lignification
journal, February 2015


Dietary Tricin Suppresses Inflammation-Related Colon Carcinogenesis in Male Crj: CD-1 Mice
journal, November 2009


Acid Degradation of Lignin. Part VII. The Cleavage of Ether Bonds.
journal, January 1972


Winter wheat hull (husk) is a valuable source for tricin, a potential selective cytotoxic agent
journal, June 2013


Isolation and Identification of Flavonoids Accumulated in Proanthocyanidin-free Barley
journal, September 2011

  • Nakano, Hiroshi; Kawada, Naoyuki; Yoshida, Mitsuru
  • Journal of Agricultural and Food Chemistry, Vol. 59, Issue 17
  • DOI: 10.1021/jf2019819

Antiproliferative and antioxidant activities of a tricin acylated glycoside from sugarcane (Saccharum officinarum) juice
journal, April 2007


Chemistry and occurrence of hydroxycinnamate oligomers
journal, July 2009


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

Stable isotopically labeled internal standards in quantitative bioanalysis using liquid chromatography/mass spectrometry: necessity or not?
journal, January 2005

  • Stokvis, Ellen; Rosing, Hilde; Beijnen, Jos H.
  • Rapid Communications in Mass Spectrometry, Vol. 19, Issue 3
  • DOI: 10.1002/rcm.1790

Studies on the Anticariogenic Activity of Oat Hulls
journal, May 1962


Successive and quantitative fractionation and extensive structural characterization of lignin from wheat straw
journal, November 2014


Lignification in Sugarcane: Biochemical Characterization, Gene Discovery, and Expression Analysis in Two Genotypes Contrasting for Lignin Content
journal, October 2013

  • Bottcher, A.; Cesarino, I.; Brombini dos Santos, A.
  • PLANT PHYSIOLOGY, Vol. 163, Issue 4
  • DOI: 10.1104/pp.113.225250

Peroxidase-dependent cross-linking reactions of p-hydroxycinnamates in plant cell walls
journal, January 2004


Thioacidolysis of Lignin: Comparison with Acidolysis
journal, January 1985

  • Lapierre, Catherine; Monties, Bernard; Rolando, Christian
  • Journal of Wood Chemistry and Technology, Vol. 5, Issue 2
  • DOI: 10.1080/02773818508085193

An updated classification of Orchidaceae: Updated Classification of Orchidaceae
journal, January 2015

  • Chase, Mark W.; Cameron, Kenneth M.; Freudenstein, John V.
  • Botanical Journal of the Linnean Society, Vol. 177, Issue 2
  • DOI: 10.1111/boj.12234

Antioxidant flavone glycosides from the leaves ofSasa borealis
journal, February 2007

  • Park, Hae-Suk; Lim, Ju Hee; Kim, Hyun Jung
  • Archives of Pharmacal Research, Vol. 30, Issue 2
  • DOI: 10.1007/BF02977689

p -Coumaroyl-CoA:monolignol transferase (PMT) acts specifically in the lignin biosynthetic pathway in Brachypodium distachyon
journal, February 2014

  • Petrik, Deborah L.; Karlen, Steven D.; Cass, Cynthia L.
  • The Plant Journal, Vol. 77, Issue 5
  • DOI: 10.1111/tpj.12420

Isolation, Characterization and Quantification of Tricin and Flavonolignans in the Medicinal Rice Njavara (Oryza sativa L.), as Compared to Staple Varieties
journal, March 2011

  • Mohanlal, Smitha; Parvathy, Rathnam; Shalini, Vasantha
  • Plant Foods for Human Nutrition, Vol. 66, Issue 1
  • DOI: 10.1007/s11130-011-0217-5

New Flavonolignan Glycosides from the Aerial Parts of Zizania latifolia
journal, March 2015


NaIO4/KI/NaCl: a new reagent system for iodination of activated aromatics through in situ generation of iodine monochloride
journal, July 2006


Structural Characterization of Lignin Isolated from Coconut ( Cocos nucifera ) Coir Fibers
journal, February 2013

  • Rencoret, Jorge; Ralph, John; Marques, Gisela
  • Journal of Agricultural and Food Chemistry, Vol. 61, Issue 10
  • DOI: 10.1021/jf304686x

Structural Characterization of Wheat Straw Lignin as Revealed by Analytical Pyrolysis, 2D-NMR, and Reductive Cleavage Methods
journal, December 2011

  • del Río, José C.; Rencoret, Jorge; Prinsen, Pepijn
  • Journal of Agricultural and Food Chemistry, Vol. 60, Issue 23
  • DOI: 10.1021/jf301002n

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

Tricin—a potential multifunctional nutraceutical
journal, December 2009


Plant polyphenols—XII.
journal, May 1964


Structural Elucidation of the Lignins from Stems and Foliage of Arundo donax Linn.
journal, May 2013

  • You, Ting-Ting; Mao, Jian-Zhen; Yuan, Tong-Qi
  • Journal of Agricultural and Food Chemistry, Vol. 61, Issue 22
  • DOI: 10.1021/jf401277v

Whole plant cell wall characterization using solution-state 2D NMR
journal, August 2012


“Non-Taxifolin” Derived Flavonolignans: Phytochemistry and Biology
journal, November 2015


Lignin: Genetic Engineering and Impact on Pulping
journal, January 2003

  • Baucher, Marie; Halpin, Claire; Petit-Conil, Michel
  • Critical Reviews in Biochemistry and Molecular Biology, Vol. 38, Issue 4, p. 305-350
  • DOI: 10.1080/10409230391036757

Monolignol ferulate conjugates are naturally incorporated into plant lignins
journal, October 2016

  • Karlen, Steven D.; Zhang, Chengcheng; Peck, Matthew L.
  • Science Advances, Vol. 2, Issue 10
  • DOI: 10.1126/sciadv.1600393

DFRC Method for Lignin Analysis. 1. New Method for β-Aryl Ether Cleavage:  Lignin Model Studies
journal, December 1997

  • Lu, Fachuang; Ralph, John
  • Journal of Agricultural and Food Chemistry, Vol. 45, Issue 12
  • DOI: 10.1021/jf970539p

Flavonolignans from Avena s ativa
journal, February 2005

  • Wenzig, Eva; Kunert, Olaf; Ferreira, Daneel
  • Journal of Natural Products, Vol. 68, Issue 2
  • DOI: 10.1021/np049636k

Phenolic constituents of the cell walls of monocotyledons
journal, July 1980


Acid Degradation of Lignin. Part VIII. Low Moleculr Weight Phenols from Acidolysis of Birch Lignin.
journal, January 1973


The occurrence of tricin and its derivatives in plants
journal, January 2016

  • Li, Mi; Pu, Yunqiao; Yoo, Chang Geun
  • Green Chemistry, Vol. 18, Issue 6
  • DOI: 10.1039/C5GC03062E

The Effects on Lignin Structure of Overexpression of Ferulate 5-Hydroxylase in Hybrid Poplar 1
journal, April 2009

  • Stewart, Jaclyn J.; Akiyama, Takuya; Chapple, Clint
  • Plant Physiology, Vol. 150, Issue 2
  • DOI: 10.1104/pp.109.137059

Comparison of the Acetyl Bromide Spectrophotometric Method with Other Analytical Lignin Methods for Determining Lignin Concentration in Forage Samples
journal, June 2004

  • Fukushima, Romualdo S.; Hatfield, Ronald D.
  • Journal of Agricultural and Food Chemistry, Vol. 52, Issue 12, p. 3713-3720
  • DOI: 10.1021/jf035497l

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

Flavonolignans from Hyparrhenia hirta
journal, July 2002


Isolation and Structural Characterization of the Milled Wood Lignin, Dioxane Lignin, and Cellulolytic Lignin Preparations from Brewer’s Spent Grain
journal, January 2015

  • Rencoret, Jorge; Prinsen, Pepijn; Gutiérrez, Ana
  • Journal of Agricultural and Food Chemistry, Vol. 63, Issue 2
  • DOI: 10.1021/jf505808c

Antioxidant Flavone Glycosides from the Leaves of Fargesia robusta
journal, September 2010

  • Van Hoyweghen, Laura; Karalic, Izet; Van Calenbergh, Serge
  • Journal of Natural Products, Vol. 73, Issue 9
  • DOI: 10.1021/np100220g

Hydroxycinnamates in lignification
journal, August 2009


Differences in the chemical structure of the lignins from sugarcane bagasse and straw
journal, October 2015


A Stable-Isotope Dilution GC-MS Approach for the Analysis of DFRC (Derivatization Followed by Reductive Cleavage) Monomers from Low-Lignin Plant Materials
journal, March 2015

  • Schäfer, Judith; Urbat, Felix; Rund, Katharina
  • Journal of Agricultural and Food Chemistry, Vol. 63, Issue 10
  • DOI: 10.1021/jf506221p

    Works referencing / citing this record:

    The lignin toolbox of the model grass Setaria viridis
    journal, June 2019

    • Ferreira, Sávio Siqueira; Simões, Marcella Siqueira; Carvalho, Gabriel Garon
    • Plant Molecular Biology, Vol. 101, Issue 3
    • DOI: 10.1007/s11103-019-00897-9

    The lignin toolbox of the model grass Setaria viridis
    journal, June 2019

    • Ferreira, Sávio Siqueira; Simões, Marcella Siqueira; Carvalho, Gabriel Garon
    • Plant Molecular Biology, Vol. 101, Issue 3
    • DOI: 10.1007/s11103-019-00897-9