Polymerization catechin

The HRP-catalyzed polymerization of (-l-)-catechin was carried out in an equivolume mixture of 1,4-dioxane and buffer (pH 7) to give the polymer with molecular weight of 3.0 x 10 in 30% yield. Using methanol as co-solvent improved the polymer yield and molecular weight. In the polymerization of... 

In spite of the recent progress in understanding the biosynthesis of the major building blocks of proanthocyanidins, (-l-)-catechin and (-)-EC, some important questions still remain to be elucidated (e.g., the exact nature of the molecular species that undergo polymerization and the mechanisms of assembly). The biosynthetic pathways for proanthocyanidins have been extensively reviewed [23-28]. A general scheme summarizing proanthocyanidin biosynthesis adapted from [27] and [28] is reported in Fig. 5. 

Flavanols and procyanidins Flavanols, or flavan-3-ols, are synthesized via two routes, with (+) catechins formed from flavan-3,4-diols via leucoanthocyanidin reductase (LAR), and (—) epicatechins from anthocyanidins via anthocyanidin reductase (ANR) (see Fig. 5.4). These flavan-3-ol molecules are then polymerized to condensed tannins (proanthocyanidins or procyanidins), widely varying in the number and nature of their component monomers and linkages (Aron and Kennedy 2008 Deluc and others 2008). It is still not known whether these polymerization reactions happen spontaneously, are enzyme catalyzed, or result from a mixture of both. 

Monitoring of acetaldehyde-induced polymerization of catechin and epicatechin by HPLC-MS demonstrated the formation of several methylmethine-linked flavanol dimers, trimers, and tetramers. Detection of the intermediate ethanol adducts confirmed the mechanism postulated by Timberlake and Bridle, which involves protonation of acetaldehyde in the acidic medium, followed by nucleophilic attack of the resulting carbocation by the flavan unit. The ethanol adduct then loses a water molecule and gives a new carbocation that undergoes nucleophilic attack by another flavanol molecule. Four dimers (C6-C6, C8-C8, and C6-C8, R and S) were formed from each monomeric flavanol. When both epicatechin and catechin units were present, additional isomers containing both types of units were... 

Es-Safi, N.E. et al.. Competition between (+)-catechin and (—)-epicatechin in acetaldehyde-induced polymerization of flavanols. J. Agric. Food Chem. 47, 2088, 1999. 

Kurisawa, M. et al.. Amplification of antioxidant activity and xanthine oxidase inhibition of catechin by enzymatic polymerization. Biomacromolecules, 4, 469, 2003. 

Achmadi, S. et al., Catechin-3-O-rhamnoside chain extender units in polymeric proanthocyanidins from mangrove bark. Phytochemistry, 35, 217, 1994. 

The two principal classes of proanthocyanidins found (10) in plant tissues are the procyanidins (1, R e H) and the prodeTphin-idins (1, R s OH). Proanthocyanidins of mixed anthocyanidin character (1, R = H or OH) have been noted. In any tissue where proanthocyan din synthesis occurs there is invariably found a range of molecular species - from the monomeric flavan-3-ols (catechins, gallocatechins) to the polymeric forms (1) and biosynthetic work (11) suggests a very close relationship between the metabolism of the parent f1avan-3-o1 and the synthesis of proanthocyanidins, Figure 4. 

The flavan-3-ols most occurring in nature are (+)-catechin and (-)-epicatechin (EC), although gallocatechin and epigallocatechin have also been identified [42]. Proanthocyanidins (or condensed tannins) include oligo- and polymeric forms of the monomeric flavanols and will be examined later. Polymerization of monomeric flavanols can occur as a result of auto-oxidation, but more often it is catalyzed by polyphenoloxidase (PPO), an enzyme that is present in most plant tissues [43]. 

Condensed tannins (= proanthocyanidins) unlike hydrolysable tannins, condensed tannins are polymeric flavans that are not readily hydrolysable. They often consist of molecules of catechin and epicatechin joined by carbon-carbon bonds. Hence catechin and epicatechin are referred to as monomers oligomers containing 2-4 (epi)catechin units are referred to as oligomeric procyanidins (OPC). 

From a chemical standpoint tannins are formed by the polymerization of elementary phenolic molecules according to the nature of these molecules, one can distinguish hydrolyzable tannins (gallics) and condensed tannins (catechins). 

Condensed Tannins. The tannins found in grapes and wines are condensed polymers from 3-flavanols (catechins) (17, 18, 19) and from 3,4-flavandiols (leucoanthocyanidins) (20, 21, 22). The monomeric leucoanthocyanidins, like their polymerized forms, display the characteristic, which differentiates them from the catechins, of trans-... 

The phenolic composition of apple consists of cinnamic acids, flavonols, dihydrochalcones, and flavan-3-ols (50,56). In the apple fruit processing industry, hydroxycinnamic acid derivatives and flavan-3-ols are important due to their contribution to the astringency, haze, and browning in apple juice and cider. Chlorogenic acid represents the major hydroxycinnamic acid derivative. The flavan-3-ols (catechins) are present in the monomeric form as well as in oligomeric and polymeric forms (procyanidins) in apple and apple products (56). 

Condensed tannins are also referred to as proanthocyanidins. They are oligomeric or polymeric flavonoids consisting of flavan-3-ol (catechin) units. Hydrolysis under harsh conditions, such as heating in acid, yields anthocyanidins. An example of a condensed tannin is procyanidin B2 (epicatechin-(4 3—>8 )-epicatechin 1.90). In this case the interflavanyl linkage is between C4 of the lower unit, and C8 of the upper unit. The linkage can also be between C4 of one unit and C6 of the second unit. 

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