Radical coupling reactions of piceatannol and monolignols: A density functional theory study

Elder, Thomas; Carlos del Río, José; Ralph, John; Rencoret, Jorge; Kim, Hoon; Beckham, Gregg T.

doi:10.1016/j.phytochem.2019.04.003

Title: Radical coupling reactions of piceatannol and monolignols: A density functional theory study

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Abstract

Recent experimental work has revealed that the hydroxystilbene piceatannol can function as a monomeric unit in the lignification of palm fruit endocarp tissues. Results indicated that piceatannol homo-couples and cross-couples with monolignols through radical reactions and is integrally incorporated into the lignin polymer. The current work reports on the thermodynamics of the proposed reactions using density functional theory calculations. The results indicated that, in general, the energetics of both homo-coupling and cross-coupling are not dissimilar from those of the monolignol coupling, demonstrating the compatibility of piceatannol with the lignification process. Moreover, the DFT methods appear to predict the correct courses of post-coupling rearomatization reactions.

Authors:

Elder, Thomas ^[1]; Carlos del Río, José ^[2]; Ralph, John ^[3]; Rencoret, Jorge ^[2]; Kim, Hoon ^[3]; Beckham, Gregg T. ^[4]

US Dept. of Agriculture (USDA), Auburn, AL (United States). Forest Service, Southern Research Station
Consejo Superior de Investigaciones Científicas, Seville (Spain). Inst. de Recursos Naturales y Agrobiología de Sevilla
Univ. of Wisconsin-Madison, Madison, WI (United States). Dept. of Energy Great Lakes Bioenergy Research Center, and Dept. of Biochemistry
National Renewable Energy Lab. (NREL), Golden, CO (United States). National Bioenergy Center

Publication Date:: Fri May 03 00:00:00 EDT 2019

Research Org.:: Great Lakes Bioenergy Research Center (GLBRC), Madison, WI (United States); National Renewable Energy Lab. (NREL), Golden, CO (United States)

Sponsoring Org.:: USDOE Office of Science (SC), Biological and Environmental Research (BER); USDOE Office of Energy Efficiency and Renewable Energy (EERE), Sustainable Transportation Office. Bioenergy Technologies Office

Contributing Org.:: Bridges system at the Pittsburgh Supercomputing Center (PSC) and Stampede2 at the Texas Advanced Computing Center (TACC).

OSTI Identifier:: 1546749

Alternate Identifier(s):: OSTI ID: 1514836

Report Number(s):: NREL/JA-2A00-73934
Journal ID: ISSN 0031-9422

Grant/Contract Number:: SC0018409; AC36-08GO28308

Resource Type:: Accepted Manuscript

Journal Name:: Phytochemistry

Additional Journal Information:: Journal Volume: 164; Journal Issue: C; Journal ID: ISSN 0031-9422

Publisher:: Elsevier

Country of Publication:: United States

Language:: English

Subject:: 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Stilbene; Piceatannol; Coniferyl alcohol; Sinapyl alcohol; p-coumaryl alcohol; Quinone methide; Density functional theory (DFT); stilbene; piceatannol; coniferyl alcohol; sinapyl alcohol; quinone methide; density functional theory

Citation Formats


                    Elder, Thomas, Carlos del Río, José, Ralph, John, Rencoret, Jorge, Kim, Hoon, and Beckham, Gregg T. Radical coupling reactions of piceatannol and monolignols: A density functional theory study.  United States: N. p., 2019. 
Web.  doi:10.1016/j.phytochem.2019.04.003.

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                    Elder, Thomas, Carlos del Río, José, Ralph, John, Rencoret, Jorge, Kim, Hoon, & Beckham, Gregg T. Radical coupling reactions of piceatannol and monolignols: A density functional theory study.  United States.  https://doi.org/10.1016/j.phytochem.2019.04.003

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                    Elder, Thomas, Carlos del Río, José, Ralph, John, Rencoret, Jorge, Kim, Hoon, and Beckham, Gregg T. Fri .  
"Radical coupling reactions of piceatannol and monolignols: A density functional theory study".  United States.  https://doi.org/10.1016/j.phytochem.2019.04.003.  https://www.osti.gov/servlets/purl/1546749.

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@article{osti_1546749,

  title        = {Radical coupling reactions of piceatannol and monolignols: A density functional theory study},

  author       = {Elder, Thomas and Carlos del Río, José and Ralph, John and Rencoret, Jorge and Kim, Hoon and Beckham, Gregg T.},

  abstractNote = {Recent experimental work has revealed that the hydroxystilbene piceatannol can function as a monomeric unit in the lignification of palm fruit endocarp tissues. Results indicated that piceatannol homo-couples and cross-couples with monolignols through radical reactions and is integrally incorporated into the lignin polymer. The current work reports on the thermodynamics of the proposed reactions using density functional theory calculations. The results indicated that, in general, the energetics of both homo-coupling and cross-coupling are not dissimilar from those of the monolignol coupling, demonstrating the compatibility of piceatannol with the lignification process. Moreover, the DFT methods appear to predict the correct courses of post-coupling rearomatization reactions.},

  doi          = {10.1016/j.phytochem.2019.04.003},

  journal      = {Phytochemistry},

  number       = C,

  volume       = 164,

  place        = {United States},

  year         = {Fri May 03 00:00:00 EDT 2019},

  month        = {Fri May 03 00:00:00 EDT 2019}

}

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