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Various ferulic acid (FA) dimers occurring in plant cell walls, such as 8-5-, 8-O-4-, 5-5-, and 8-8-coupled dimers, are effective antioxidants and potential antimicrobials. It is necessary to access these diferulates as reference compounds to validate those isolated from plants. 3,6-bis(4-hydroxy-3-methoxyphenyl)-tetrahydrofuro-[3,4-c]furan-1,4-dione, a 8-8-coupled FA dilactone generated from ferulic acid via radical coupling, has been used to synthesize 8-8-coupled FA dimers although few reports investigated the distribution of products and mechanisms involved in the transformation of FA dilactone. In this work, the FA dilactone, obtained from FA by a peroxidase-catalyzed radical coupling, was reacted under various base/acid conditions. Effects of reaction conditions and workup procedures on the distribution of products were investigated by GC-MS. The isolated products from such treatments of FA dilactone were characterized by NMR. New derivatives of FA dimer including 2-(4-hydroxy-3-methoxybenzylidene)-3-(hydroxyl-(4-hydroxy-3-methoxyphenyl)methyl)succinic acid and 2-(bis(4-hydroxy-3-methoxyphenyl)-methyl)-succinic acid were produced from NaOH treatment. Another novel 8-8-coupled cyclic FA dimer, diethyl 6-hydroxy-1-(4-hydroxy-3-methoxyphenyl)-7-methoxy-1,2-dihydronaphthalene-2,3-dicarboxylate was identified in products from FA dilactone treated by dry HCl in absolute ethanol. Mechanisms involved in such transformations were proposed.

Phenolic esters have attracted considerable interest due to the potential they offer for peroxidase catalysed cross-linking of cell wall polysaccharides. Particularly, feruloyl residues undergo radical coupling reactions that result in cross-linking (intra- /intermolecular) between polysaccharides, between polysaccharides and lignin and, between polysaccharides and proteins. This review addresses for the first time different studies in which it is established that cross-linking by dehydrodiferulates contributes to maize’s defences to pests and diseases. Dehydrodiferulate cross-links are involved in maize defence mechanisms against insects such as the European, Mediterranean, and tropical corn borers and, storage pest as the maize weevil. In addition, cross-links are also discussed to be involved in genetic resistance of maize to fungus diseases as Gibberella ear and stalk rot. Resistance against insects and fungus attending dehydrodiferulates could go hand in hand. Quantitative trait loci mapping for these cell wall components could be a useful tool for enhancing resistance to pest and diseases in future breeding programs., Most of the latest corn borer studies by the authors’ group were supported by the Plan Nacional I+D+I (AGL2003-00961, AGL2006-1314, AGL2009-09611)

Ferulic acid dehydrodimers (DFA) and dehydrotrimers (TriFA) ester-linked to plant cell wall polymers may cross-link not only cell wall polysaccharides but also other cell wall components including proteins and lignin, thus enhancing the rigidity and potentially affecting the enzymatic degradation of the plant cell wall. Corn, wheat, and mixed-cereal distiller’s dried grains with solubles (DDGS) were investigated for composition of DFAs and TriFAs by reversed phase high-performance liquid chromatography with ultraviolet detection. Corn DDGS contained 5.3 and 5.9 times higher contents of total DFAs than wheat and mixed-cereal DDGS, respectively. Furthermore, the contents of total TriFAs were 5.7 and 6.3 times higher in corn DDGS than in wheat and mixed-cereal DDGS, respectively. In addition, both corn grains and corresponding DDGS had similar profiles of individual DFAs and TriFAs, indicating that ferulic acid cross-links in the corn cell wall are presumably not modified during fermentation and DDGS processing.

Ferulic acid (FA) groups esterified to the arabinan side chains of pectic polysaccharides can be oxidatively cross-linked in vitro by horseradish peroxidase (HRP) catalysis in the presence of hydrogen peroxide (H(2)O(2)) to form ferulic acid dehydrodimers (diFAs). The present work investigated whether the kinetics of HRP catalyzed cross-linking of FA esterified to α-(1,5)-linked arabinans are affected by the length of the arabinan chains carrying the feruloyl substitutions. The kinetics of the HRP-catalyzed cross-linking of four sets of arabinan samples from sugar beet pulp, having different molecular weights and hence different degrees of polymerization, were monitored by the disappearance of FA absorbance at 316 nm. MALDI-TOF/TOF-MS analysis confirmed that the sugar beet arabinans were feruloyl-substituted, and HPLC analysis verified that the amounts of diFAs increased when FA levels decreased as a result of the enzymatic oxidation treatment with HRP and H(2)O(2). At equimolar levels of FA (0.0025-0.05 mM) in the arabinan samples, the initial rates of the HRP-catalyzed cross-linking of the longer chain arabinans were slower than those of the shorter chain arabinans. The lower initial rates may be the result of the slower movement of larger molecules coupled with steric phenomena, making the required initial reaction of two FAs on longer chain arabinans slower than on shorter arabinans.