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Postharvest Biology and Technology of Fruits, Vegetables, and Flowers

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THE ROLE OF POLYPHENOLS 265<br />

Pentose phosphate<br />

pathway Erythrose-4-P<br />

Glucose-1-P<br />

Glucose-6-P<br />

Deoxy-arabino-heptulosonate-7-P<br />

Shikimic acid<br />

5-Enol-pyruvyl-shikimate-3-phosphate<br />

Tryptophan Chorismic acid<br />

Phosphoenolphyruvate (PEP)<br />

Pyruvate<br />

Tyrosine<br />

Shikimic<br />

acid<br />

pathway<br />

Prephenic acid<br />

Arogenic acid<br />

Phenylalanine<br />

PAL<br />

trans-Cinnamic acid<br />

C4H<br />

p-Coumaric acid<br />

4CL<br />

Hydroxycinnamates<br />

Hydroxybenzoates<br />

Coumarins<br />

Lignans<br />

Lignins<br />

Hydrolysable tannins<br />

Acetyl CoA<br />

Malonyl CoA<br />

p-Coumaroyl CoA<br />

CHS<br />

Naringenin Chalcones<br />

Flavonoids<br />

Biflavonoids<br />

Condensed tannins<br />

Malonic<br />

acid<br />

pathway<br />

Fig. 12.2 Biosynthetic pathways <strong>of</strong> major polyphenolic groups present in fruits. Indicated enzymes are as<br />

follows: PAL, phenylalanine ammonia-lyase; C4H, cinnamate 4-hydroxylase; 4CL, 4-hydroxycinnamoyl CoA<br />

ligase; CHS, chalcone synthase.<br />

produce deoxy-arabino-heptulosonate-7-phosphate, which then converts to shikimic acid<br />

(shikimate). Condensation <strong>of</strong> shikimic acid with another molecule <strong>of</strong> PEP results in the<br />

formation <strong>of</strong> 5-enol-pyruvyl-shikimate-3-phosphate (EPSP). Conversion <strong>of</strong> EPSP to chorismic<br />

acid (chorismate) is catalyzed by chorismate synthase by elimination <strong>of</strong> phosphate<br />

from EPSP. Chorismate mutase catalyzes the next step, conversion <strong>of</strong> chorismic acid to<br />

prephenic acid (prehenate), giving the basic phenyl-propanoid skeleton. Prephenic acid acts<br />

as the precursor to three aromatic amino acids: arogenic acid, tyrosine, <strong>and</strong> phenylalanine.<br />

The conversion <strong>of</strong> prehenate to arogenate is catalyzed by pyridoxal 5 ′ -phosphate-dependent<br />

prephenate aminotransferase, <strong>and</strong> arogenate dehydratase catalyzes the subsequent step <strong>of</strong><br />

formation <strong>of</strong> L-phenylalanine from arogenate.<br />

12.5.1 Hydroxycinnamates<br />

Phenylalanine is subsequently deaminated by the action <strong>of</strong> phenylalanine ammonia-lyase<br />

(PAL) producing trans-cinnamic acid. PAL, a tetrameric protein <strong>of</strong> 270–330 kDa, is considered<br />

as the key regulatory enzyme <strong>of</strong> the phenylpropanoid pathway.<br />

trans-Cinnamic acid is subsequently hydroxylated by cinnamate 4-hydroxylase (C4H)<br />

to form p-coumaric acid. p-Coumaric acid further goes through a series <strong>of</strong> hydroxylation<br />

<strong>and</strong> methylation reactions to form many other hydroxycinnamates (C 6 C 3 ) including

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