1. Biomimetic oxidative copolymerization of hydroxystilbenes and monolignols
- Author
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Hoon Kim, Jorge Rencoret, Thomas J. Elder, José C. del Río, John Ralph, Great Lakes Bioenergy Research Center (US), DOE BER Office of Science, Ministerio de Ciencia e Innovación (España), Agencia Estatal de Investigación (España), European Commission, Junta de Andalucía, Extreme Science and Engineering Discovery Environment (US), National Science Foundation (US), US Forest Service, Kim, Hoon, Rencoret, Jorge, Elder T., Río Andrade, José Carlos del, and Ralph, John
- Subjects
Multidisciplinary - Abstract
18 páginas.- 6 figuras.- 4 tablas.- 92 referencias.-Supplementary Materials, ydroxystilbenes are a class of polyphenolic compounds that behave as lignin monomers participating in radical coupling reactions during the lignification. Here, we report the synthesis and characterization of various artificial copolymers of monolignols and hydroxystilbenes, as well as low-molecular-mass compounds, to obtain the mechanistic insights into their incorporation into the lignin polymer. Integrating the hydroxystilbenes, resveratrol and piceatannol, into monolignol polymerization in vitro, using horseradish peroxidase to generate phenolic radicals, produced synthetic lignins [dehydrogenation polymers (DHPs)]. Copolymerization of hydroxystilbenes with monolignols, especially sinapyl alcohol, by in vitro peroxidases notably improved the reactivity of monolignols and resulted in substantial yields of synthetic lignin polymers. The resulting DHPs were analyzed using two-dimensional NMR and 19 synthesized model compounds to confirm the presence of hydroxystilbene structures in the lignin polymer. The cross-coupled DHPs confirmed both resveratrol and piceatannol as authentic monomers participating in the oxidative radical coupling reactions during polymerization., This work was supported by grants from the DOE Great Lakes Bioenergy Research Center, and H.K. and J.Ra. were funded by the DOE BER Office of Science (DE- SC0018409). J.Re. and J.C.d.R. were supported by the projects AGL2017-83036-R and PID2020-118968RB-I00 (funded by MCIN/AEI/10.13039/501100011033 and, as appropriate, by “ERDF A way of making Europe”) and by the Andalusian Regional Government (project P20-00017). T.J.E. was funded by the Extreme Science and Engineering Discovery Environment (XSEDE), supported by the National Science Foundation grant number ACI-1548562. This work was made possible in part by a grant for high-performance computing resources and technical support from the Alabama Supercomputer Authority. This research was supported in part by the U.S. Department of Agriculture, U.S. Forest Service.
- Published
- 2023