skip to main content

DOE PAGESDOE PAGES

Title: Reductive Cleavage Method for Quantitation of Monolignols and Low-Abundance Monolignol Conjugates

As interest in biomass utilization has grown, the manipulation of lignin biosynthesis has received significant attention, such that recent work has demanded more robust lignin analytical methods. As the derivatization followed by reductive cleavage (DFRC) method is particularly effective for structurally characterizing natively acylated lignins, we used an array of synthetic β-ether γ-acylated model compounds to determine theoretical yields for all monolignol conjugates currently known to exist in lignin, and we synthesized a new set of deuterated analogs as internal standards for quantification using GC–MS/MS. Yields of the saturated ester conjugates ranged from 40 to 90 %, and NMR analysis revealed the presence of residual unsaturated conjugates in yields of 20 to 35 %. In contrast to traditional selected-ion-monitoring, we demonstrated the superior sensitivity and accuracy of multiple-reaction-monitoring detection methods, and further highlighted the inadequacy of traditional standards relative to isotopically labeled analogs.
Authors:
ORCiD logo [1] ; ORCiD logo [2] ; ORCiD logo [2] ; ORCiD logo [1] ; ORCiD logo [1]
  1. Univ. of Wisconsin, Madison, WI (United States). Wisconsin Energy Inst., DOE Great Lakes Bioenergy Research Center, and Dept. of Biochemistry
  2. Univ. of Wisconsin, Madison, WI (United States). Wisconsin Energy Inst., DOE Great Lakes Bioenergy Research Center
Publication Date:
Grant/Contract Number:
SC0018409; FC02-07ER64494
Type:
Published Article
Journal Name:
ChemSusChem
Additional Journal Information:
Journal Volume: 11; Journal Issue: 10; Journal ID: ISSN 1864-5631
Publisher:
ChemPubSoc Europe
Research Org:
Univ. of Wisconsin, Madison, WI (United States). Wisconsin Energy Inst., DOE Great Lakes Bioenergy Research Center
Sponsoring Org:
USDOE Office of Science (SC), Biological and Environmental Research (BER) (SC-23); National Institutes of Health (NIH)
Contributing Orgs:
UW-Madison Chemistry Department Mass Spectrometry Lab
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Analytical methods; DFRC; lignin; monolignol conjugates; Synthetic methods
OSTI Identifier:
1436531
Alternate Identifier(s):
OSTI ID: 1436532; OSTI ID: 1459528

Regner, Matt, Bartuce, Allison, Padmakshan, Dharshana, Ralph, John, and Karlen, Steven D. Reductive Cleavage Method for Quantitation of Monolignols and Low-Abundance Monolignol Conjugates. United States: N. p., Web. doi:10.1002/cssc.201800617.
Regner, Matt, Bartuce, Allison, Padmakshan, Dharshana, Ralph, John, & Karlen, Steven D. Reductive Cleavage Method for Quantitation of Monolignols and Low-Abundance Monolignol Conjugates. United States. doi:10.1002/cssc.201800617.
Regner, Matt, Bartuce, Allison, Padmakshan, Dharshana, Ralph, John, and Karlen, Steven D. 2018. "Reductive Cleavage Method for Quantitation of Monolignols and Low-Abundance Monolignol Conjugates". United States. doi:10.1002/cssc.201800617.
@article{osti_1436531,
title = {Reductive Cleavage Method for Quantitation of Monolignols and Low-Abundance Monolignol Conjugates},
author = {Regner, Matt and Bartuce, Allison and Padmakshan, Dharshana and Ralph, John and Karlen, Steven D.},
abstractNote = {As interest in biomass utilization has grown, the manipulation of lignin biosynthesis has received significant attention, such that recent work has demanded more robust lignin analytical methods. As the derivatization followed by reductive cleavage (DFRC) method is particularly effective for structurally characterizing natively acylated lignins, we used an array of synthetic β-ether γ-acylated model compounds to determine theoretical yields for all monolignol conjugates currently known to exist in lignin, and we synthesized a new set of deuterated analogs as internal standards for quantification using GC–MS/MS. Yields of the saturated ester conjugates ranged from 40 to 90 %, and NMR analysis revealed the presence of residual unsaturated conjugates in yields of 20 to 35 %. In contrast to traditional selected-ion-monitoring, we demonstrated the superior sensitivity and accuracy of multiple-reaction-monitoring detection methods, and further highlighted the inadequacy of traditional standards relative to isotopically labeled analogs.},
doi = {10.1002/cssc.201800617},
journal = {ChemSusChem},
number = 10,
volume = 11,
place = {United States},
year = {2018},
month = {5}
}

Works referenced in this record:

Lignin Biosynthesis
journal, June 2003

Changes in secondary metabolism and deposition of an unusual lignin in the ref8 mutant of Arabidopsis
journal, April 2002

Lignin Depolymerization and Conversion A Review of Thermochemical Methods
journal, November 2010
  • Pandey, M. P.; Kim, C. S.
  • Chemical Engineering & Technology, Vol. 34, Issue 1, p. 29-41
  • DOI: 10.1002/ceat.201000270

Biomass Recalcitrance: Engineering Plants and Enzymes for Biofuels Production
journal, February 2007
  • Himmel, M. E.; Ding, S.-Y.; Johnson, D. K.
  • Science, Vol. 315, Issue 5813, p. 804-807
  • DOI: 10.1126/science.1137016

Monolignol Ferulate Transferase Introduces Chemically Labile Linkages into the Lignin Backbone
journal, April 2014

Lignins: Natural polymers from oxidative coupling of 4-hydroxyphenyl- propanoids
journal, January 2004