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Title: Lignin-Derived Thioacidolysis Dimers: Reevaluation, New Products, Authentication, and Quantification

Abstract

Lignin structural studies play an essential role both in understanding the development of plant cell walls and for valorizing lignocellulosics as renewable biomaterials. Dimeric products released by selectively cleaving β–aryl ether linkages between lignin units reflect the distribution of recalcitrant lignin units, but have been neither absolutely defined nor quantitatively determined. Here in this work, 12 guaiacyl-type thioacidolysis dimers were identified and quantified using newly synthesized standards. One product previously attributed to deriving from β–1-coupled units was established as resulting from β–5 units, correcting an analytical quandary. Another longstanding dilemma, that no β–β dimers were recognized in thioacidolysis products from gymnosperms, was resolved with the discovery of two such authenticated compounds. Finally, individual GC response factors for each standard compound allowed rigorous quantification of dimeric products released from softwood lignins, affording insight into the various interunit-linkage distributions in lignins and thereby guiding the valorization of lignocellulosics.

Authors:
ORCiD logo [1]; ORCiD logo [1]; ORCiD logo [2]; ORCiD logo [3]; ORCiD logo [2]
  1. South China University of Technology, Tianhe District, Guangzhou (China). State Key Laboratory of Pulp and Paper Engineering; Univ. of Wisconsin, Madison, WI (United States). Department of Biochemistry and DOE Great Lakes Bioenergy Research Center, Wisconsin Energy Institute
  2. Univ. of Wisconsin, Madison, WI (United States). Department of Biochemistry and DOE Great Lakes Bioenergy Research Center, Wisconsin Energy Institute
  3. Beijing Forestry University, Haidian District, Beijing (China). Beijing Key Laboratory of Lignocellulosic Chemistry
Publication Date:
Research Org.:
Univ. of Wisconsin, Madison, WI (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Biological and Environmental Research (BER) (SC-23)
OSTI Identifier:
1346254
Alternate Identifier(s):
OSTI ID: 1346255; OSTI ID: 1427629
Grant/Contract Number:
FC02-07ER64494; FC02- 07ER64494
Resource Type:
Journal Article: Published Article
Journal Name:
ChemSusChem
Additional Journal Information:
Journal Volume: 10; Journal Issue: 5; Journal ID: ISSN 1864-5631
Publisher:
ChemPubSoc Europe
Country of Publication:
United States
Language:
English
Subject:
59 BASIC BIOLOGICAL SCIENCES; 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; analytical methods; GC-FID; lignin dimers; response factor; synthesis design

Citation Formats

Yue, Fengxia, Lu, Fachuang, Regner, Matt, Sun, Runcang, and Ralph, John. Lignin-Derived Thioacidolysis Dimers: Reevaluation, New Products, Authentication, and Quantification. United States: N. p., 2017. Web. doi:10.1002/cssc.201700101.
Yue, Fengxia, Lu, Fachuang, Regner, Matt, Sun, Runcang, & Ralph, John. Lignin-Derived Thioacidolysis Dimers: Reevaluation, New Products, Authentication, and Quantification. United States. doi:10.1002/cssc.201700101.
Yue, Fengxia, Lu, Fachuang, Regner, Matt, Sun, Runcang, and Ralph, John. Thu . "Lignin-Derived Thioacidolysis Dimers: Reevaluation, New Products, Authentication, and Quantification". United States. doi:10.1002/cssc.201700101.
@article{osti_1346254,
title = {Lignin-Derived Thioacidolysis Dimers: Reevaluation, New Products, Authentication, and Quantification},
author = {Yue, Fengxia and Lu, Fachuang and Regner, Matt and Sun, Runcang and Ralph, John},
abstractNote = {Lignin structural studies play an essential role both in understanding the development of plant cell walls and for valorizing lignocellulosics as renewable biomaterials. Dimeric products released by selectively cleaving β–aryl ether linkages between lignin units reflect the distribution of recalcitrant lignin units, but have been neither absolutely defined nor quantitatively determined. Here in this work, 12 guaiacyl-type thioacidolysis dimers were identified and quantified using newly synthesized standards. One product previously attributed to deriving from β–1-coupled units was established as resulting from β–5 units, correcting an analytical quandary. Another longstanding dilemma, that no β–β dimers were recognized in thioacidolysis products from gymnosperms, was resolved with the discovery of two such authenticated compounds. Finally, individual GC response factors for each standard compound allowed rigorous quantification of dimeric products released from softwood lignins, affording insight into the various interunit-linkage distributions in lignins and thereby guiding the valorization of lignocellulosics.},
doi = {10.1002/cssc.201700101},
journal = {ChemSusChem},
number = 5,
volume = 10,
place = {United States},
year = {Thu Jan 26 00:00:00 EST 2017},
month = {Thu Jan 26 00:00:00 EST 2017}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record at 10.1002/cssc.201700101

Citation Metrics:
Cited by: 3works
Citation information provided by
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  • Cited by 3
  • Lignin structural studies play an essential role both in understanding the development of plant cell walls and for valorizing lignocellulosics as renewable biomaterials. Dimeric products released by selectively cleaving β–aryl ether linkages between lignin units reflect the distribution of recalcitrant lignin units, but have been neither absolutely defined nor quantitatively determined. Here in this work, 12 guaiacyl-type thioacidolysis dimers were identified and quantified using newly synthesized standards. One product previously attributed to deriving from β–1-coupled units was established as resulting from β–5 units, correcting an analytical quandary. Another longstanding dilemma, that no β–β dimers were recognized in thioacidolysis products frommore » gymnosperms, was resolved with the discovery of two such authenticated compounds. Finally, individual GC response factors for each standard compound allowed rigorous quantification of dimeric products released from softwood lignins, affording insight into the various interunit-linkage distributions in lignins and thereby guiding the valorization of lignocellulosics.« less
  • Thioacidolysis is a method used to measure the relative content of lignin monomers bound by β-O-4 linkages. Current thioacidolysis methods are low-throughput as they require tedious steps for reaction product concentration prior to analysis using standard GC methods. A quantitative thioacidolysis method that is accessible with general laboratory equipment and uses a non-chlorinated organic solvent and is tailored for higher-throughput analysis is reported. The method utilizes lignin arylglycerol monomer standards for calibration, requires 1-2 mg of biomass per assay and has been quantified using fast-GC techniques including a Low Thermal Mass Modular Accelerated Column Heater (LTM MACH). Cumbersome steps, includingmore » standard purification, sample concentrating and drying have been eliminated to help aid in consecutive day-to-day analyses needed to sustain a high sample throughput for large screening experiments without the loss of quantitation accuracy. As a result, the method reported in this manuscript has been quantitatively validated against a commonly used thioacidolysis method and across two different research sites with three common biomass varieties to represent hardwoods, softwoods, and grasses.« less
    Cited by 4
  • Thioacidolysis is a method used to measure the relative content of lignin monomers bound by β-O-4 linkages. Current thioacidolysis methods are low-throughput as they require tedious steps for reaction product concentration prior to analysis using standard GC methods. A quantitative thioacidolysis method that is accessible with general laboratory equipment and uses a non-chlorinated organic solvent and is tailored for higher-throughput analysis is reported. The method utilizes lignin arylglycerol monomer standards for calibration, requires 1-2 mg of biomass per assay and has been quantified using fast-GC techniques including a Low Thermal Mass Modular Accelerated Column Heater (LTM MACH). Cumbersome steps, includingmore » standard purification, sample concentrating and drying have been eliminated to help aid in consecutive day-to-day analyses needed to sustain a high sample throughput for large screening experiments without the loss of quantitation accuracy. As a result, the method reported in this manuscript has been quantitatively validated against a commonly used thioacidolysis method and across two different research sites with three common biomass varieties to represent hardwoods, softwoods, and grasses.« less