한빛사논문
Hoon Kim1*, Jorge Rencoret2, Thomas J. Elder3, José C. del Río2, John Ralph1,4
1Department of Energy Great Lakes Bioenergy Research Center, Wisconsin Energy Institute, University of Wisconsin-Madison, Madison, WI 53726, USA.
2Instituto de Recursos Naturales y Agrobiología de Sevilla(IRNAS), CSIC, Avenida de la Reina Mercedes,10, 41012, Seville, Spain.
3USDA-Forest Service, Southern Research Station 521 Devall Dr. Auburn, AL 36849, USA.
4Department of Biochemistry, University of Wisconsin-Madison, Madison, WI 53706, USA.
*Correspondingauthor : Hoon Kim
Abstract
Hydroxystilbenes 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.
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