Density Functional Theory Study of Spirodienone Stereoisomers in Lignin
Abstract
The spirodienone structure in lignin is a relatively recent discovery, and it has been found to occur in lignin of various plant species at concentrations of ~3%, which is sufficiently high to be important for better understanding of its properties and reactivity. The cyclic structure, with a ..beta..-1 bond, has been proposed to be a precursor for acyclic ..beta..-1 linkages in lignin. Previous analytical work has revealed the presence, but not the absolute configuration, of two stereoisomeric forms of spirodienone. The objective of the current work was to determine if there are thermodynamic differences that could help identify the experimentally observed stereoisomers. Results from density functional theory calculations reveal the presence of clusters of stereoisomers with varying stability that may be of use in narrowing the list of possible structures. Furthermore, the bond dissociation enthalpy of the cyclic ring exhibited a particularly high value for the C-O cleavage reaction relative to more conventional ether bonds in lignin, perhaps due to limited electron delocalization possibilities.
- Authors:
-
[1];
[2];
- USDA Forest Service, Auburn, AL (United States). Southern Research Station
- National Renewable Energy Lab. (NREL), Golden, CO (United States)
- Publication Date:
- Research Org.:
- National Renewable Energy Laboratory (NREL), Golden, CO (United States)
- Sponsoring Org.:
- USDOE Office of Energy Efficiency and Renewable Energy (EERE)
- OSTI Identifier:
- 1378887
- Report Number(s):
- NREL/JA-5100-69117
Journal ID: ISSN 2168-0485
- Grant/Contract Number:
- AC36-08GO28308
- Resource Type:
- Accepted Manuscript
- Journal Name:
- ACS Sustainable Chemistry & Engineering
- Additional Journal Information:
- Journal Volume: 5; Journal Issue: 8; Journal ID: ISSN 2168-0485
- Publisher:
- American Chemical Society (ACS)
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 09 BIOMASS FUELS; bond dissociation energy; density functional theory; lignin; spirodienone; stereoisomerism
Citation Formats
Elder, Thomas, Berstis, Laura, Beckham, Gregg T., and Crowley, Michael F. Density Functional Theory Study of Spirodienone Stereoisomers in Lignin. United States: N. p., 2017.
Web. doi:10.1021/acssuschemeng.7b01373.
Elder, Thomas, Berstis, Laura, Beckham, Gregg T., & Crowley, Michael F. Density Functional Theory Study of Spirodienone Stereoisomers in Lignin. United States. https://doi.org/10.1021/acssuschemeng.7b01373
Elder, Thomas, Berstis, Laura, Beckham, Gregg T., and Crowley, Michael F. Wed .
"Density Functional Theory Study of Spirodienone Stereoisomers in Lignin". United States. https://doi.org/10.1021/acssuschemeng.7b01373. https://www.osti.gov/servlets/purl/1378887.
@article{osti_1378887,
title = {Density Functional Theory Study of Spirodienone Stereoisomers in Lignin},
author = {Elder, Thomas and Berstis, Laura and Beckham, Gregg T. and Crowley, Michael F.},
abstractNote = {The spirodienone structure in lignin is a relatively recent discovery, and it has been found to occur in lignin of various plant species at concentrations of ~3%, which is sufficiently high to be important for better understanding of its properties and reactivity. The cyclic structure, with a ..beta..-1 bond, has been proposed to be a precursor for acyclic ..beta..-1 linkages in lignin. Previous analytical work has revealed the presence, but not the absolute configuration, of two stereoisomeric forms of spirodienone. The objective of the current work was to determine if there are thermodynamic differences that could help identify the experimentally observed stereoisomers. Results from density functional theory calculations reveal the presence of clusters of stereoisomers with varying stability that may be of use in narrowing the list of possible structures. Furthermore, the bond dissociation enthalpy of the cyclic ring exhibited a particularly high value for the C-O cleavage reaction relative to more conventional ether bonds in lignin, perhaps due to limited electron delocalization possibilities.},
doi = {10.1021/acssuschemeng.7b01373},
journal = {ACS Sustainable Chemistry & Engineering},
number = 8,
volume = 5,
place = {United States},
year = {Wed Jun 28 00:00:00 EDT 2017},
month = {Wed Jun 28 00:00:00 EDT 2017}
}
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Works referencing / citing this record:
Enzymatic Oxidation of Lignin: Challenges and Barriers Toward Practical Applications
journal, November 2019
- Chan, Jou C.; Paice, Michael; Zhang, Xiao
- ChemCatChem, Vol. 12, Issue 2