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

Abstract

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:
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 Org.:
UW-Madison Chemistry Department Mass Spectrometry Lab
OSTI Identifier:
1436531
Alternate Identifier(s):
OSTI ID: 1436532; OSTI ID: 1459528
Grant/Contract Number:
SC0018409; FC02-07ER64494
Resource Type:
Journal Article: Published Article
Journal Name:
ChemSusChem
Additional Journal Information:
Journal Volume: 11; Journal Issue: 10; Journal ID: ISSN 1864-5631
Publisher:
ChemPubSoc Europe
Country of Publication:
United States
Language:
English
Subject:
Analytical methods; DFRC; lignin; monolignol conjugates; Synthetic methods

Citation Formats

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., 2018. 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. Fri . "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 = {Fri May 25 00:00:00 EDT 2018},
month = {Fri May 25 00:00:00 EDT 2018}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record at 10.1002/cssc.201800617

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