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Title: Structural Characterization of Lignin from Maize ( Zea mays L.) Fibers: Evidence for Diferuloylputrescine Incorporated into the Lignin Polymer in Maize Kernels

The structure of the phenolic polymer in maize grain fibers, with 5.5% Klason lignin content, has been studied. For this, the milled wood lignin (MWL) and dioxane lignin (DL) preparations were isolated and analyzed. The data indicated that the lignin in maize fibers was syringyl rich, mostly involved in β-aryl ether, resinol, and phenylcoumaran substructures. 2D NMR and derivatization followed by reductive cleavage (DFRC) also revealed the occurrence of associated ferulates together with trace amounts of p-coumarates acylating the γ-OH of lignin side chains, predominantly on S-lignin units. More interesting was the occurrence of diferuloylputrescine, a ferulic acid amide, which was identified by 2D NMR and comparison with a synthesized standard, that was apparently incorporated into this lignin. A phenylcoumaran structure involving a diferuloylputrescine coupled through 8–5' linkages to another diferuloylputrescine (or to a ferulate or a guaiacyl lignin unit) was found, providing compelling evidence for its participation in radical coupling reactions. The occurrence of diferuloylputrescine in cell walls of maize kernels and other cereal grains appears to have been missed in previous works, perhaps due to the alkaline hydrolysis commonly used for composition studies.
Authors:
ORCiD logo [1] ; ORCiD logo [1] ; ORCiD logo [1] ; ORCiD logo [2] ; ORCiD logo [2]
  1. Inst. de Recursos Naturales y Agrobiologia de Sevilla (IRNAS), CSIC, Seville (Spain)
  2. Univ. of Wisconsin, Madison, WI (United States). Wisconsin Energy Inst., Dept. of Energy Great Lakes Bioenergy Research Center; Univ. of Wisconsin, Madison, WI (United States). Dept. of Biochemistry
Publication Date:
Grant/Contract Number:
SC0018409; FC02-07ER64494
Type:
Accepted Manuscript
Journal Name:
Journal of Agricultural and Food Chemistry
Additional Journal Information:
Journal Volume: 66; Journal Issue: 17; Journal ID: ISSN 0021-8561
Publisher:
American Chemical Society
Research Org:
Univ. of Wisconsin, Madison, WI (United States). Wisconsin Energy Inst., Dept. of Energy Great Lakes Bioenergy Research Center
Sponsoring Org:
USDOE Office of Science (SC), Biological and Environmental Research (BER) (SC-23)
Contributing Orgs:
NMR facilities of the General Research Services of the University of Seville (SGI-CITIUS)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; 59 BASIC BIOLOGICAL SCIENCES; 2D NMR; ferulates; hydroxycinnamoyl amides; lignin monomers; Maize kernels
OSTI Identifier:
1459411

del Rio, Jose C., Rencoret, Jorge, Gutierrez, Ana, Kim, Hoon, and Ralph, John. Structural Characterization of Lignin from Maize ( Zea mays L.) Fibers: Evidence for Diferuloylputrescine Incorporated into the Lignin Polymer in Maize Kernels. United States: N. p., Web. doi:10.1021/acs.jafc.8b00880.
del Rio, Jose C., Rencoret, Jorge, Gutierrez, Ana, Kim, Hoon, & Ralph, John. Structural Characterization of Lignin from Maize ( Zea mays L.) Fibers: Evidence for Diferuloylputrescine Incorporated into the Lignin Polymer in Maize Kernels. United States. doi:10.1021/acs.jafc.8b00880.
del Rio, Jose C., Rencoret, Jorge, Gutierrez, Ana, Kim, Hoon, and Ralph, John. 2018. "Structural Characterization of Lignin from Maize ( Zea mays L.) Fibers: Evidence for Diferuloylputrescine Incorporated into the Lignin Polymer in Maize Kernels". United States. doi:10.1021/acs.jafc.8b00880.
@article{osti_1459411,
title = {Structural Characterization of Lignin from Maize ( Zea mays L.) Fibers: Evidence for Diferuloylputrescine Incorporated into the Lignin Polymer in Maize Kernels},
author = {del Rio, Jose C. and Rencoret, Jorge and Gutierrez, Ana and Kim, Hoon and Ralph, John},
abstractNote = {The structure of the phenolic polymer in maize grain fibers, with 5.5% Klason lignin content, has been studied. For this, the milled wood lignin (MWL) and dioxane lignin (DL) preparations were isolated and analyzed. The data indicated that the lignin in maize fibers was syringyl rich, mostly involved in β-aryl ether, resinol, and phenylcoumaran substructures. 2D NMR and derivatization followed by reductive cleavage (DFRC) also revealed the occurrence of associated ferulates together with trace amounts of p-coumarates acylating the γ-OH of lignin side chains, predominantly on S-lignin units. More interesting was the occurrence of diferuloylputrescine, a ferulic acid amide, which was identified by 2D NMR and comparison with a synthesized standard, that was apparently incorporated into this lignin. A phenylcoumaran structure involving a diferuloylputrescine coupled through 8–5' linkages to another diferuloylputrescine (or to a ferulate or a guaiacyl lignin unit) was found, providing compelling evidence for its participation in radical coupling reactions. The occurrence of diferuloylputrescine in cell walls of maize kernels and other cereal grains appears to have been missed in previous works, perhaps due to the alkaline hydrolysis commonly used for composition studies.},
doi = {10.1021/acs.jafc.8b00880},
journal = {Journal of Agricultural and Food Chemistry},
number = 17,
volume = 66,
place = {United States},
year = {2018},
month = {4}
}