Density functional theory study on the coupling and reactions of diferuloylputrescine as a lignin monomer
Abstract
Diferuloylputrescine has been found in a variety of plant species, and recent work has provided evidence of its covalent bonding into lignin. Results from nuclear magnetic resonance spectroscopy revealed the presence of bonding patterns consistent with homo-coupling of diferuloylputrescine and the possibility of cross-coupling with lignin. In the present work, density functional theory calculations have been applied to assess the energetics associated with radical coupling, rearomatization, and dehydrogenation for possible homo-coupled dimers of diferuloylputrescine and cross-coupled dimers of diferuloylputrescine and coniferyl alcohol. Furthermore, the values obtained for these reaction energetics are consistent with those reported for monolignols and other novel lignin monomers. As such, this study shows that there would be no thermodynamic impediment to the incorporation of diferuloylputrescine into the lignin polymer and its addition to the growing list of non-canonical lignin monomers.
- Authors:
-
- USDA-Forest Service, Auburn, AL (United States)
- Inst. de Recursos Naturales y Agrobiología de Sevilla (IRNAS), Seville (Spain)
- Univ. of Wisconsin, Madison, WI (United States)
- Publication Date:
- Research Org.:
- Great Lakes Bioenergy Research Center (GLBRC), Madison, WI (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Biological and Environmental Research (BER)
- OSTI Identifier:
- 1845445
- Alternate Identifier(s):
- OSTI ID: 1962891
- Grant/Contract Number:
- SC0018409; BER DE-SC0018409
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Phytochemistry
- Additional Journal Information:
- Journal Volume: 197; Journal ID: ISSN 0031-9422
- Publisher:
- Elsevier
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Diferuloylputrescine; Homo-couple; Cross-couple; Density functional theory; Coniferyl alcohol; Lignin; Lignification; Feruloyl amide; Radical coupling
Citation Formats
Elder, Thomas, del Río, José C., Ralph, John, Rencoret, Jorge, and Kim, Hoon. Density functional theory study on the coupling and reactions of diferuloylputrescine as a lignin monomer. United States: N. p., 2022.
Web. doi:10.1016/j.phytochem.2022.113122.
Elder, Thomas, del Río, José C., Ralph, John, Rencoret, Jorge, & Kim, Hoon. Density functional theory study on the coupling and reactions of diferuloylputrescine as a lignin monomer. United States. https://doi.org/10.1016/j.phytochem.2022.113122
Elder, Thomas, del Río, José C., Ralph, John, Rencoret, Jorge, and Kim, Hoon. Sat .
"Density functional theory study on the coupling and reactions of diferuloylputrescine as a lignin monomer". United States. https://doi.org/10.1016/j.phytochem.2022.113122. https://www.osti.gov/servlets/purl/1845445.
@article{osti_1845445,
title = {Density functional theory study on the coupling and reactions of diferuloylputrescine as a lignin monomer},
author = {Elder, Thomas and del Río, José C. and Ralph, John and Rencoret, Jorge and Kim, Hoon},
abstractNote = {Diferuloylputrescine has been found in a variety of plant species, and recent work has provided evidence of its covalent bonding into lignin. Results from nuclear magnetic resonance spectroscopy revealed the presence of bonding patterns consistent with homo-coupling of diferuloylputrescine and the possibility of cross-coupling with lignin. In the present work, density functional theory calculations have been applied to assess the energetics associated with radical coupling, rearomatization, and dehydrogenation for possible homo-coupled dimers of diferuloylputrescine and cross-coupled dimers of diferuloylputrescine and coniferyl alcohol. Furthermore, the values obtained for these reaction energetics are consistent with those reported for monolignols and other novel lignin monomers. As such, this study shows that there would be no thermodynamic impediment to the incorporation of diferuloylputrescine into the lignin polymer and its addition to the growing list of non-canonical lignin monomers.},
doi = {10.1016/j.phytochem.2022.113122},
journal = {Phytochemistry},
number = ,
volume = 197,
place = {United States},
year = {Sat Feb 05 00:00:00 EST 2022},
month = {Sat Feb 05 00:00:00 EST 2022}
}
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