Diferulic acids

Diferulic acids (also known as dehydrodiferulic acids) are organic compounds that have the general chemical formula C20H18O8, they are formed by dimerisation of ferulic acid. Curcumin and curcuminoids, though having a structure resembling diferulic acids', are not formed that way but through a condensation process. Just as ferulic acid is not the proper IUPAC name, the diferulic acids also tend to have trivial names that are more commonly used than the correct IUPAC name. Diferulic acids are found in plant cell walls, particularly those of grasses.

Structures

There are currently nine known structures for diferulic acids.[1] They are usually named after the positions on each molecule that form the bond between them. Included in the group are 8,5'-DiFA (DC) (or decarboxylated form) and 8,8'-DiFA (THF) (or tetrahydrofuran form), which are not true diferulic acids, but probably have a similar biological function. The 8,5'-DiFA (DC) lost CO2 during its formation, the 8,8'-DiFA (THF) gained H2O during its formation. 8,5'-DiFA (BF) is the benzofuran form.

Ferulic acid can also form trimers and tetramers, known as triferulic and tetraferulic acids respectively.[2]

Chemical structures of nine known diferulic acids

Occurrences

They have been found in the cell walls of most plants, but are present at higher levels in the grasses (Poaceae) and also sugar beet and Chinese water chestnut.[3]

The 8-O-4'-DiFA tends to predominate in grasses, but 5,5'-DiFA predominates in barley bran.[4][5] Rye bread contains ferulic acid dehydrodimers.[6]

In chufa (tiger nut, Cyperus esculentus) and sugar beet the predominant diferulic acids are 8-O-4'-DiFA and 8,5'-DiFA respectively.[7][8] 8-5' Non cyclic diferulic acid has been identified to be covalently linked to carbohydrate moieties of the arabinogalactan-protein fraction of gum arabic.[9]

Function

Diferulic acids are thought to have a structural function in plant cell walls, where they form cross-links between polysaccharide chains. They have been extracted attached to a few sugar molecules at both ends, but so far no definitive proof of them linking separate polysaccharide chains has been found.[10] In suspension-cultured maize cells, dimerisation of ferulic acid esterified to polysaccharides occurs mostly in the protoplasm, but may occur in the cell walls when peroxide levels increase due to pathogenesis.[11] In suspension-cultured wheat cells, only the 8,5'-diferulic acid is formed intraprotoplasmically with the other dimers being formed in the cell wall.[12]

Preparation

Most diferulic acids are not commercially available and must be synthesised in lab. Synthetic routes have been published, but it is often simpler to extract them from plant material. They can be extracted from plant cell walls (often maize bran) by concentrated solutions of alkali, the resulting solution is then acidified and phase separated into an organic solvent. The resulting solution is evaporated to give a mixture of ferulic acid moieties that can be separated by column chromatography. Identification is often by high performance liquid chromatography with a UV detector or by LC-MS. Alternatively they can be derivatised to make them volatile and therefore suitable for GC-MS. Curcumin can be hydrolyzed (alkaline) to yield two molecules of ferulic acid. Peroxidases can produce dimers of ferulic acid, in the presence of hydrogen peroxide through radical polymerization.[13]

Uses

Diferulic acids are more effective inhibitors of lipid peroxidation and better scavengers of free radicals than ferulic acid on a molar basis.[14]

History

The first diferulic acid discovered was the 5,5'-diferulic acid, and for a while this was thought to be the only one.[15]

See also

References
  1. M.Bunzel, J.Ralph and H.Steinhart (2004). "Phenolic compounds as cross-links of plant derived polysaccharides" (PDF). Czech J. Food Sci. 22: 64–67. Archived from the original (PDF) on 2013-12-03.
  2. Bunzel, M; Ralph, J; Brüning, P; Steinhart, H (2006). "Structural identification of dehydrotriferulic and dehydrotetraferulic acids isolated from insoluble maize bran fiber". Journal of Agricultural and Food Chemistry. 54 (17): 6409–18. doi:10.1021/jf061196a. PMID 16910738.
  3. J.Ralph, J.H.Grabber, R.D.Hatfield and G.Wende (1996). "New discoveries relating to diferulates". 1996 USDFRC Research Summary. pp. 70–71.CS1 maint: multiple names: authors list (link)
  4. Ralph, John; Quideau, Stéphane; Grabber, John H.; Hatfield, Ronald D. (1994). "Identification and synthesis of new ferulic acid dehydrodimers present in grass cell walls". Journal of the Chemical Society, Perkin Transactions 1 (23): 3485. doi:10.1039/P19940003485.
  5. Renger, Anja; Steinhart, H. (2000). "Ferulic acid dehydrodimers as structural elements in cereal dietary fibre". European Food Research and Technology. 211 (6): 422–428. doi:10.1007/s002170000201.
  6. H. Boskov Hansen; M. Andreasen; M. Nielsen; L. Larsen; Bach K. Knudsen; A. Meyer; L. Christensen; Å. Hansen (2002). "Changes in dietary fibre, phenolic acids and activity of endogenous enzymes during rye bread-making". European Food Research and Technology. 214: 33–42. doi:10.1007/s00217-001-0417-6.
  7. Parker, Mary L.; Ng, Annie; Smith, Andrew C.; Waldron, Keith W. (2000). "Esterified Phenolics of the Cell Walls of Chufa (Cyperus esculentusL.) Tubers and Their Role in Texture". Journal of Agricultural and Food Chemistry. 48 (12): 6284–91. doi:10.1021/jf0004199. PMID 11141285.
  8. Micard, V.; Grabber, J.H.; Ralph, J.; Renard, C.M.G.C.; Thibault, J.-F. (1997). "Dehydrodiferulic acids from sugar-beet pulp". Phytochemistry. 44 (7): 1365–1368. doi:10.1016/S0031-9422(96)00699-1.
  9. Renard, D; Lavenant-Gourgeon, L; Ralet, MC; Sanchez, C (2006). "Acacia senegal gum: Continuum of molecular species differing by their protein to sugar ratio, molecular weight, and charges". Biomacromolecules. 7 (9): 2637–49. doi:10.1021/bm060145j. PMID 16961328.
  10. Bunzel, Mirko; Allerdings, Ella; Ralph, John; Steinhart, Hans (2008). "Cross-linking of arabinoxylans via 8-8-coupled diferulates as demonstrated by isolation and identification of diarabinosyl 8-8(cyclic)-dehydrodiferulate from maize bran". Journal of Cereal Science. 47: 29–40. doi:10.1016/j.jcs.2006.12.005.
  11. Fry, SC; Willis, SC; Paterson, AE (2000). "Intraprotoplasmic and wall-localised formation of arabinoxylan-bound diferulates and larger ferulate coupling-products in maize cell-suspension cultures". Planta. 211 (5): 679–92. doi:10.1007/s004250000330. PMID 11089681.
  12. Nicolai Obel; Andrea Celia Porchia; Henrik Vibe Scheller (February 2003). "Intracellular feruloylation of arabinoxylan in wheat: Evidence for feruloyl-glucose as precursor". Planta. 216 (4): 620–629. doi:10.1007/s00425-002-0863-9. JSTOR 23387682. PMID 12569404.
  13. Geissmann, T.; Neukom, H. (1971). "Vernetzung von Phenolcarbonsäureestern von Polysacchariden durch oxydative phenolische Kupplung". Helvetica Chimica Acta. 54 (4): 1108–1112. doi:10.1002/hlca.19710540420.
  14. Garcia-Conesa, MT; Plumb, GW; Waldron, KW; Ralph, J; Williamson, G (1997). "Ferulic acid dehydrodimers from wheat bran: Isolation, purification and antioxidant properties of 8-O-4-diferulic acid". Redox report : communications in free radical research. 3 (5–6): 319–23. PMID 9754331.
  15. Hartley, Roy D.; Jones, Edwin C. (1976). "Diferulic acid as a component of cell walls of Lolium multiflorum". Phytochemistry. 15 (7): 1157–1160. doi:10.1016/0031-9422(76)85121-7.
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