Structural Identification of Dehydrotriferulic and Dehydrotetraferulic Acids Isolated from Insoluble Maize Bran Fiber

Abstract

Two new dehydrotriferulic acids and two dehydrotetraferulic acids were isolated from saponified maize bran insoluble fiber using size exclusion chromatography on Bio-Beads S-X3 followed by Sephadex LH-20 chromatography and semipreparative phenyl-hexyl reversed phase high-performance liquid chromatography. On the basis of UV spectroscopy, mass spectrometry, and one- and two-dimensional NMR experiments, the structures were identified as 8-5(noncyclic)/5-5-dehydrotriferulic acid, 8-8(tetrahydrofuran)/5-5-dehydrotriferulic acid, and 4-O-8/5-5/8-O-4-dehydrotetraferulic acid. The second tetramer was tentatively identified as 4-O-8/5-5/8-5(noncyclic)-dehydrotetraferulic acid. Compounds containing an 8-5(noncyclic)-coupled dimeric unit probably do not exist in planta but are formed from their phenylcoumaran precursors containing an 8-5(cyclic)-coupled dimeric unit during saponification. The presented dehydrotrimers are the first dehydrotriferulates that do not contain an 8-O-4-coupled dimeric unit. The ferulate dehydrotetramers that are reported for the first time are presumed, like the dimers and trimers, to cross-link polysaccharides in the plant. Because both tetramers contain a 5-5/8-O-4-dehydrotriferulate moiety, the predominant dehydrotrimer in maize bran, it is not possible to deduce whether tetramers are formed by coupling of a fourth unit to a preformed dehydrotriferulate or by 5-5-coupling of preformed 8-O-4- and 8-5-dehydrodiferulates. Nevertheless, such compounds document expanded roles for ferulates in cross-linking polysaccharides in plant cell walls.