Structural Characterization of Lignin from Maize ( <i>Zea mays</i> 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: del Rio, Jose C. [Inst. de Recursos Naturales y Agrobiologia de Sevilla (IRNAS), CSIC, Seville (Spain); Instituto de Recursos Naturales y Agrobiología de Sevilla (IRNAS)] (ORCID:0000000230406787); Rencoret, Jorge [Inst. de Recursos Naturales y Agrobiologia de Sevilla (IRNAS), CSIC, Seville (Spain)] (ORCID:0000000327287331); Gutierrez, Ana [Inst. de Recursos Naturales y Agrobiologia de Sevilla (IRNAS), CSIC, Seville (Spain)] (ORCID:0000000288239029); Kim, Hoon [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] (ORCID:0000000174257464); Ralph, John [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] (ORCID:0000000260934521). DOE Contract: FC02-07ER64494; SC0018409. Subjects: 2D NMR; 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; 59 BASIC BIOLOGICAL SCIENCES; Maize kernels; ferulates; hydroxycinnamoyl amides; lignin monomers