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Title: Coupling and Reactions of Lignols and New Lignin Monomers: A Density Functional Theory Study

Abstract

This perspective summarizes and compares computational results for the thermodynamics of bond dissociation, coupling, and rearomatization for a number of noncanonical lignin monomer–lignol combinations that have been found to occur experimentally. The noncanonical lignin monomers discussed are tricin, caffeyl alcohol, 5-hydroxyconiferyl alcohol, and piceatannol. Among dimeric combinations, the results for bond dissociation are generally similar, but in cases for which trimers have been reported (tricin-lignol adducts), this value can be quite variable, with stereochemical and structural preferences. Among the adducts examined thus far, the energies associated with quinone methide formation and rearomatization are not dissimilar and would not impede subsequent polymerization. These fundamental studies may help to elucidate how lignin monomers are incorporated into the lignin polymer, provide leads for targeted genetic modification, and be of use in deconstruction for the production of commodity chemicals.

Authors:
ORCiD logo [1]; ORCiD logo [2]; ORCiD logo [3]; ORCiD logo [2]; ORCiD logo [3]; ORCiD logo [4]; ORCiD logo [4]
  1. US Dept. of Agriculture (USDA), Auburn, Alabama (United States)
  2. Instituto de Recursos Naturales y Agrobiología de Sevilla (IRNAS) (Spain)
  3. Univ. of Wisconsin, Madison, WI (United States)
  4. National Renewable Energy Lab. (NREL), Golden, CO (United States)
Publication Date:
Research Org.:
National Renewable Energy Lab. (NREL), Golden, CO (United States)
Sponsoring Org.:
USDOE Office of Energy Efficiency and Renewable Energy (EERE)
OSTI Identifier:
1660142
Report Number(s):
NREL-JA-2800-77352
Journal ID: ISSN 2168-0485; MainId:26298;UUID:43ce9ffd-6f2e-411b-8db0-064ae15c74f0;MainAdminID:15196
Grant/Contract Number:  
AC36-08GO28308
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
ACS Sustainable Chemistry & Engineering
Additional Journal Information:
Journal Volume: 8; Journal Issue: 30; Journal ID: ISSN 2168-0485
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; tricin; piceatannol; caffeyl alcohol; 5-hydroxyconiferyl alcohol; lignin

Citation Formats

Elder, Thomas, del Río, José C., Ralph, John, Rencoret, Jorge, Kim, Hoon, Beckham, Gregg T., and Crowley, Michael F. Coupling and Reactions of Lignols and New Lignin Monomers: A Density Functional Theory Study. United States: N. p., 2020. Web. doi:10.1021/acssuschemeng.0c02880.
Elder, Thomas, del Río, José C., Ralph, John, Rencoret, Jorge, Kim, Hoon, Beckham, Gregg T., & Crowley, Michael F. Coupling and Reactions of Lignols and New Lignin Monomers: A Density Functional Theory Study. United States. doi:10.1021/acssuschemeng.0c02880.
Elder, Thomas, del Río, José C., Ralph, John, Rencoret, Jorge, Kim, Hoon, Beckham, Gregg T., and Crowley, Michael F. Thu . "Coupling and Reactions of Lignols and New Lignin Monomers: A Density Functional Theory Study". United States. doi:10.1021/acssuschemeng.0c02880.
@article{osti_1660142,
title = {Coupling and Reactions of Lignols and New Lignin Monomers: A Density Functional Theory Study},
author = {Elder, Thomas and del Río, José C. and Ralph, John and Rencoret, Jorge and Kim, Hoon and Beckham, Gregg T. and Crowley, Michael F.},
abstractNote = {This perspective summarizes and compares computational results for the thermodynamics of bond dissociation, coupling, and rearomatization for a number of noncanonical lignin monomer–lignol combinations that have been found to occur experimentally. The noncanonical lignin monomers discussed are tricin, caffeyl alcohol, 5-hydroxyconiferyl alcohol, and piceatannol. Among dimeric combinations, the results for bond dissociation are generally similar, but in cases for which trimers have been reported (tricin-lignol adducts), this value can be quite variable, with stereochemical and structural preferences. Among the adducts examined thus far, the energies associated with quinone methide formation and rearomatization are not dissimilar and would not impede subsequent polymerization. These fundamental studies may help to elucidate how lignin monomers are incorporated into the lignin polymer, provide leads for targeted genetic modification, and be of use in deconstruction for the production of commodity chemicals.},
doi = {10.1021/acssuschemeng.0c02880},
journal = {ACS Sustainable Chemistry & Engineering},
issn = {2168-0485},
number = 30,
volume = 8,
place = {United States},
year = {2020},
month = {7}
}

Journal Article:
Free Publicly Available Full Text
This content will become publicly available on July 9, 2021
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