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962 21 Coffee, Tea, Cocoa

tinesterase, polygalacturonase, proteinase, alkaline

and acid phosphatases, lipase, catalase,

peroxidase and polyphenol oxidase activities

have been detected in fresh cacao beans. These

enzymes are inactivated to a great extent during

processing.

21.3.2.3.2 Theobromine and Caffeine

Theobromine (3,7-dimethylxanthine), which is

1.2% in cocoa, provides a stimulating effect,

which is less than that of caffeine in coffee.

Therefore, it is of physiological importance.

Caffeine is also present, but in much lower

amounts (average 0.2%). A cup of cocoa contains

0.1 g of theobromine and 0.01 g of caffeine.

Theobromine crystallizes in the form of small

rhombic prisms which sublime at 290 ◦ C without

decomposition. In cocoa beans theobromine is

often weakly bound to tannins and is released by

the acetic acid formed during fermentation of the

beans. Part of this theobromine then diffuses into

the shell.

21.3.2.3.5 Phenolic Compounds

The nib cotyledons consist of two types of

parenchyma cells (Fig. 21.5). More than 90% of

the cells are small and contain protoplasm, starch

granules, aleurone grains and fat globules. The

larger cells are scattered among them and contain

all the phenolic compounds and purines. These

polyphenol storage cells (pigment cells) make up

11–13% of the tissue and contain anthocyanins

and, depending on their composition, are white

to dark purple. Data on the composition of these

cells and that of the total tissue are given in

Table 21.22.

The content of phenolic compounds is also of interest

from the standpoint of chemoprevention.

With 84 mg/g gallic acid equivalents (GAE) and

21.3.2.3.3 Lipids

Cocoa fat (cocoa butter), because of its abundance

and value, is the most significant ingredient of cacao

beans, and is dealt with in detail elsewhere

(cf. 14.3.2.2.3).

Fig. 21.5. A cross-section of cocoa cotyledon tissue

21.3.2.3.4 Carbohydrates

Starch is the predominant carbohydrate. It is

present in nibs but not in shells, a fact useful in

the microscopic examination of cocoa powders

in methods based on the occurrence of starch

as a characteristic constituent. Components of

the dietary fiber are amongst others pentosans,

galactans, mucins containing galac–turonic acid,

and cellulose. Soluble carbohydrates present

include stachyose, raffinose and sucrose (0.08–

1.5%), glucose and fructose. Sucrose hydrolysis,

which occurs during fermentation of the beans,

provides the reducing sugar pool important for

aroma formation during the roasting process.

Mesoinositol, phytin, verbascotetrose, and some

other sugars are found in cocoa nib.

Table 21.22. Composition of polyphenol storage cells

of cacao tissue

Constituent Polyphenol Cotylestorage

dons

cell

(%) (%) a

Catechins 25.0 3.0

Leucocyanidins 21.0 2.5

Polymeric leucocyanidins 17.5 2.1

Anthocyanins 3.0 0.4

Total phenols 66.5 8.0

Theobromine 14.0 1.7

Caffeine 0.5 0.1

Free sugars 1.6

Polysaccharides 3.0

Other compounds 14.4

a As % of dry matter.

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