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Title: Arabinose Conjugates Diagnostic of Ferulate-Ferulate and Ferulate-Monolignol Cross-Coupling Are Released by Mild Acidolysis of Grass Cell Walls

Abstract

Ferulate (FA) units esterified to grass arabinoxylans are involved in cross-linking cell wall polymers. Here, this contention is strengthened by the identification of FA homo- and heterodimers esterified to methyl arabinofuranoside (MeAra) units after their release from the xylan by mild acidolysis in dioxane/methanol/HCl. Acidolysis of poorly lignified maize bran cell walls provided diferulate (DFA) isomers, including those from 8–5, 8–O–4, and 5–5 interunit bonding, esterified to one or two MeAra units. Acidolysis of lignified grass samples released crossed dimers esterified to one MeAra unit and derived from the β–O–4 coupling of coniferyl alcohol to FA esters. The evaluation of these heterodimeric esters by LC-UV of their aglycones revealed that the parent structures occur in significant amounts in lignified cell walls (0.5–1 mg/g expressed as FA equivalents). The current results position mild acidolysis as an efficient strategy to obtain improved details regarding the FA-mediated cross-linking of grass cell walls.

Authors:
ORCiD logo [1];  [1];  [1]; ORCiD logo [2]
  1. Univ. Paris-Saclay, Versailles (France)
  2. Univ. of Wisconsin, Madison, WI (United States)
Publication Date:
Research Org.:
Univ. of Wisconsin, Madison, WI (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Biological and Environmental Research (BER)
OSTI Identifier:
1600973
Grant/Contract Number:  
SC0018409
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Agricultural and Food Chemistry
Additional Journal Information:
Journal Volume: 67; Journal Issue: 46; Journal ID: ISSN 0021-8561
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Radical coupling; dehydrodimer; lignification; cell wall cross-link; diferulate; monocot

Citation Formats

Lapierre, Catherine, Voxeur, Aline, Boutet, Stéphanie, and Ralph, John. Arabinose Conjugates Diagnostic of Ferulate-Ferulate and Ferulate-Monolignol Cross-Coupling Are Released by Mild Acidolysis of Grass Cell Walls. United States: N. p., 2019. Web. doi:10.1021/acs.jafc.9b05840.
Lapierre, Catherine, Voxeur, Aline, Boutet, Stéphanie, & Ralph, John. Arabinose Conjugates Diagnostic of Ferulate-Ferulate and Ferulate-Monolignol Cross-Coupling Are Released by Mild Acidolysis of Grass Cell Walls. United States. https://doi.org/10.1021/acs.jafc.9b05840
Lapierre, Catherine, Voxeur, Aline, Boutet, Stéphanie, and Ralph, John. Wed . "Arabinose Conjugates Diagnostic of Ferulate-Ferulate and Ferulate-Monolignol Cross-Coupling Are Released by Mild Acidolysis of Grass Cell Walls". United States. https://doi.org/10.1021/acs.jafc.9b05840. https://www.osti.gov/servlets/purl/1600973.
@article{osti_1600973,
title = {Arabinose Conjugates Diagnostic of Ferulate-Ferulate and Ferulate-Monolignol Cross-Coupling Are Released by Mild Acidolysis of Grass Cell Walls},
author = {Lapierre, Catherine and Voxeur, Aline and Boutet, Stéphanie and Ralph, John},
abstractNote = {Ferulate (FA) units esterified to grass arabinoxylans are involved in cross-linking cell wall polymers. Here, this contention is strengthened by the identification of FA homo- and heterodimers esterified to methyl arabinofuranoside (MeAra) units after their release from the xylan by mild acidolysis in dioxane/methanol/HCl. Acidolysis of poorly lignified maize bran cell walls provided diferulate (DFA) isomers, including those from 8–5, 8–O–4, and 5–5 interunit bonding, esterified to one or two MeAra units. Acidolysis of lignified grass samples released crossed dimers esterified to one MeAra unit and derived from the β–O–4 coupling of coniferyl alcohol to FA esters. The evaluation of these heterodimeric esters by LC-UV of their aglycones revealed that the parent structures occur in significant amounts in lignified cell walls (0.5–1 mg/g expressed as FA equivalents). The current results position mild acidolysis as an efficient strategy to obtain improved details regarding the FA-mediated cross-linking of grass cell walls.},
doi = {10.1021/acs.jafc.9b05840},
journal = {Journal of Agricultural and Food Chemistry},
number = 46,
volume = 67,
place = {United States},
year = {2019},
month = {10}
}

Journal Article:
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Cited by: 11 works
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Figures / Tables:

Table 1 Table 1: GC-MS analysis (electron-impact 70 eV) of the TMS phenolic dimers (analyzed as their TMS derivatives) recovered after alkaline hydrolysis of acidolysis samples. Peak numbers refer to peak notations in Figure 3.

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Works referenced in this record:

Mass Spectrometry-Based Fragmentation as an Identification Tool in Lignomics
journal, October 2010

  • Morreel, Kris; Kim, Hoon; Lu, Fachuang
  • Analytical Chemistry, Vol. 82, Issue 19
  • DOI: 10.1021/ac100968g

Identification of ferulate oligomers from corn stover
journal, June 2010

  • Dobberstein, Diane; Bunzel, Mirko
  • Journal of the Science of Food and Agriculture, Vol. 90, Issue 11
  • DOI: 10.1002/jsfa.4017

Feruloylation in Grasses: Current and Future Perspectives
journal, September 2009


Structural Identification of Dehydrotriferulic and Dehydrotetraferulic Acids Isolated from Insoluble Maize Bran Fiber
journal, August 2006

  • Bunzel, Mirko; Ralph, John; Brüning, Philipp
  • Journal of Agricultural and Food Chemistry, Vol. 54, Issue 17
  • DOI: 10.1021/jf061196a

Phenolic acid bridges between polysaccharides and lignin in wheat internodes
journal, January 1990


Profiling of diferulates (plant cell wall cross-linkers) using ultrahigh-performance liquid chromatography-tandem mass spectrometry
text, January 2013

  • Vismeh, Ramin; Lu, Fachuang; Chundawat, Shishir P. S.
  • Rutgers University
  • DOI: 10.7282/t3pc34pv

New ether-linked ferulic acid-coniferyl alcohol dimers identified in grass straws.
journal, October 1995

  • Jacquet, Geraldine; Pollet, Brigitte; Lapierre, Catherine
  • Journal of Agricultural and Food Chemistry, Vol. 43, Issue 10
  • DOI: 10.1021/jf00058a037

Lignin-ferulate cross-links in grasses: active incorporation of ferulate polysaccharide esters into ryegrass lignins
journal, September 1995


Feruloylation in Grasses: Current and Future Perspectives
journal, September 2009


Hydroxycinnamates in lignification
journal, August 2009


Relevance, structure and analysis of ferulic acid in maize cell walls
journal, April 2018


Evaluation of Feruloylated and p -Coumaroylated Arabinosyl Units in Grass Arabinoxylans by Acidolysis in Dioxane/Methanol
journal, May 2018

  • Lapierre, Catherine; Voxeur, Aline; Karlen, Steven D.
  • Journal of Agricultural and Food Chemistry, Vol. 66, Issue 21
  • DOI: 10.1021/acs.jafc.8b01618

Developing Pericarp of Maize: A Model to Study Arabinoxylan Synthesis and Feruloylation
journal, September 2016

  • Chateigner-Boutin, Anne-Laure; Ordaz-Ortiz, José J.; Alvarado, Camille
  • Frontiers in Plant Science, Vol. 7
  • DOI: 10.3389/fpls.2016.01476

Structural Redesigning Arabidopsis Lignins into Alkali-Soluble Lignins through the Expression of p- Coumaroyl-CoA:Monolignol Transferase PMT
journal, January 2016

  • Sibout, Richard; Le Bris, Philippe; Legée, Frédéric
  • Plant Physiology, Vol. 170, Issue 3
  • DOI: 10.1104/pp.15.01877

The phenolic fraction of maize bran: evidence for lignin-heteroxylan association
journal, July 2001


Occurrence and nature of ferulic acid substitution of cell-wall polysaccharides in graminaceous plants
journal, July 1983


Phenilpropanoate identification in young wheat plants by liquid chromatography/tandem mass spectrometry: monomeric and dimeric compounds
journal, August 2010

  • Callipo, Luciano; Cavaliere, Chiara; Fuscoletti, Valentina
  • Journal of Mass Spectrometry, Vol. 45, Issue 9
  • DOI: 10.1002/jms.1800

Microwave-Assisted Extraction of Bound Phenolic Acids in Bran and Flour Fractions from Sorghum and Maize Cultivars Varying in Hardness
journal, April 2012

  • Chiremba, Constance; Rooney, Lloyd W.; Beta, Trust
  • Journal of Agricultural and Food Chemistry, Vol. 60, Issue 18
  • DOI: 10.1021/jf300279t

Differentiation of phenylpropanoid acids cyclobutane- and dehydrodimers isomers in barley leaf cell walls with LC/MS/MS system
journal, August 2016

  • Ostrowski, Wojciech; Swarcewicz, Barbara; Nolka, Marta
  • International Journal of Mass Spectrometry, Vol. 407
  • DOI: 10.1016/j.ijms.2016.07.003

Isolation and structural identification of diarabinosyl 8--4-dehydrodiferulate from maize bran insoluble fibre
journal, January 2005


Stereospecificity for the Zinc Borohydride Reduction of α-Aryloxy-β-Hydroxy Ketones
journal, December 1993


Profiling of Oligolignols Reveals Monolignol Coupling Conditions in Lignifying Poplar Xylem
journal, October 2004


Mass Spectrometry-Based Fragmentation as an Identification Tool in Lignomics
journal, October 2010

  • Morreel, Kris; Kim, Hoon; Lu, Fachuang
  • Analytical Chemistry, Vol. 82, Issue 19
  • DOI: 10.1021/ac100968g

Diferulates as structural components in soluble and insoluble cereal dietary fibre
journal, January 2001

  • Bunzel, Mirko; Ralph, John; Marita, Jane M.
  • Journal of the Science of Food and Agriculture, Vol. 81, Issue 7
  • DOI: 10.1002/jsfa.861

Model Studies of Ferulate−Coniferyl Alcohol Cross-Product Formation in Primary Maize Walls:  Implications for Lignification in Grasses
journal, October 2002

  • Grabber, John H.; Ralph, John; Hatfield, Ronald D.
  • Journal of Agricultural and Food Chemistry, Vol. 50, Issue 21, p. 6008-6016
  • DOI: 10.1021/jf0205312

Lignins and Ferulate−Coniferyl Alcohol Cross-Coupling Products in Cereal Grains
journal, October 2004

  • Bunzel, Mirko; Ralph, John; Lu, Fachuang
  • Journal of Agricultural and Food Chemistry, Vol. 52, Issue 21
  • DOI: 10.1021/jf040204p

Identification of 8-O-4/8-5(Cyclic)- and 8-8(Cyclic)/5-5-Coupled Dehydrotriferulic Acids, Naturally Occurring in Cell Walls of Mono- and Dicotyledonous Plants
journal, September 2016

  • Waterstraat, Martin; Bunzel, Diana; Bunzel, Mirko
  • Journal of Agricultural and Food Chemistry, Vol. 64, Issue 38
  • DOI: 10.1021/acs.jafc.6b02720

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

Reductive Cleavage Method for Quantitation of Monolignols and Low-Abundance Monolignol Conjugates
journal, May 2018

  • Regner, Matt; Bartuce, Allison; Padmakshan, Dharshana
  • ChemSusChem, Vol. 11, Issue 10
  • DOI: 10.1002/cssc.201800617

Phenolic acid bridges between polysaccharides and lignin in wheat internodes
journal, January 1990


Ferulate cross-linking in cell walls isolated from maize cell suspensions
journal, November 1995


Acidolysis
book, January 1992


Identification of ferulate oligomers from corn stover
journal, June 2010

  • Dobberstein, Diane; Bunzel, Mirko
  • Journal of the Science of Food and Agriculture, Vol. 90, Issue 11
  • DOI: 10.1002/jsfa.4017

Structural Identification of Dehydrotriferulic and Dehydrotetraferulic Acids Isolated from Insoluble Maize Bran Fiber
journal, August 2006

  • Bunzel, Mirko; Ralph, John; Brüning, Philipp
  • Journal of Agricultural and Food Chemistry, Vol. 54, Issue 17
  • DOI: 10.1021/jf061196a

Works referencing / citing this record:

Improved analysis of arabinoxylan-bound hydroxycinnamate conjugates in grass cell walls
journal, December 2020


Figures/Tables have been extracted from DOE-funded journal article accepted manuscripts.