Cocoa: Production, Chemistry, and Use

A Caligiani, A Marseglia, and G Palla, University of Parma, Parma, Italy

ã 2016 Elsevier Ltd. All rights reserved.

Cocoa Tree and Beans and have an optimum taste. Therefore they are considered an
excellent quality cocoa. The Criollo is rarely used alone; most
Cocoa beans represent the seeds of the fruits of cocoa tree frequently it is used to fortify other mixtures having a weak and
(Theobroma cacao L., order Sterculiacae), which is a native not persistent aroma. It can be subdivided into Central
species of tropical humid forests on the lower eastern equato- American Criollo and Venezuelan Criollo. The Forastero
rial slopes of the Andes in South America. Cocoa was domes- cacao (foreigner) corresponds to the subspecies ‘sphaerocar-
ticated and consumed for the first time by the Mayas and pum’ and resulted from dissemination toward the Amazon
Aztecs. The growth of the cocoa tree requires warm-humid Valley in Northern Brazil and the Guyanas. In the nineteenth
climates with temperatures between 20 and 30
C and high century, Forastero cocoa seeds were taken from South America
and constant humidity, conditions found in areas about 20
to the islands of Sao Tomé of West Africa, then to Ghana. From
latitude north and south of the Equator. Abundant and well- Ghana, Forastero spread to other African countries, the most
distributed rainfalls are essential because the cocoa tree toler- important of which are the Ivory Coast, Cameroon, and Nige-
ates a dry season of up to 3 months a year. The cocoa tree is a ria. In these countries, there was an immediate increase in
rather delicate plant that does not tolerate direct strong winds cultivated area, and they are now the largest producers of
and direct sunlight. In fact, it is generally grown in the shade of cocoa in the world. Forastero represents about 85% of the
other tall trees (banana trees and coconut palms). Trees can world’s cocoa production because it is very strong, resistant to
reach up to 20 m in height, but are usually kept below 5 m. The disease, and easily cultivated, especially in Africa. The seeds
fruit is 10–30 cm long and 7–10 cm wide and weighs have a strong flavor, not very aromatic and of poor quality, and
400–1000 g. It is an indehiscent drupe called a pod or are generally used in a mixture with other more valuable
‘cabosside.’ It can be spherical, cylindrical, pointed or blunt, varieties. Forastero cocoa is now a group very differentiated
smooth, or wrinkled. The pericarp has a thickness of in several subspecies and hybrids. The best-known Forasteros
10–15 mm and can be of different colors depending on the are the ‘Amelonados’ with pods resembling melon, which were
ripeness and variety, turning from green to yellow, from red to the predominant types traditionally cultivated in West African
orange. The optimum ripeness of the fruit varies according to countries. The Amazonian subgroups show a wide genetic
the variety and generally lasts from 4.5 to 7 months. The fruit is variability. Some Forastero plants growing in particular areas
harvested twice a year (in February/March and April/July). The give cocoa of excellent quality (cru) such as Arriba, the national
summer harvest usually produces fruit of better quality. The cocoa of Ecuador.
seeds, in the number of 20–60 per fruit, are arranged in regular Natural hybridization between Criollo and Forastero led
rows and immersed in a mucilaginous acidic pulp containing to the origin of a third variety of cocoa named ‘Trinitario,’
glucose and fructose and are called beans. Cocoa beans are the not found in the wild. It has been reported that the Criollo
only economically valuable part of cocoa tree because they population from Venezuela and the Amelonado-type Forastero
represent the raw material for the production of cocoa-based from Guyana could have been involved in hybridization lead-
products. Each cocoa bean consists of two cotyledons (nibs) ing to the production of Trinitario. It is difficult to specify
and a small embryo, all enclosed in a skin (shell). The cotyle- the characters of Trinitarios as they may have pod and bean
dons contain two types of cells: storage or parenchyma cells, characters ranging from those typical of Criollos to those of
containing fat globules, protein and starch granules, and pig- Forasteros.
mented cells, containing polyphenols and methylxanthines.

Cocoa Beans Harvesting, Fermentation, and Drying

Cocoa Varieties and Geographical Diffusion
These steps of the process are carried out in the countries of
Two major botanical groups of cocoa are currently recognized: origin. Fresh cocoa seeds undergo fermentation and a drying
Criollo and Forastero. Criollo (native) corresponds to the sub- process to be ready and stable for transport to the countries in
species ‘cacao’ and represents the original cocoa, previously which they will be processed to chocolate and related products.
consumed by pre-Columbian people. Its diffusion resulted Local or regional variations in cocoa plant materials, fermenta-
from the dissemination through the Andes toward the low- tion procedures, and drying processes lead to a traded good
lands of Venezuela, Colombia, and Ecuador and northward to typical of the country of origin; therefore, the composition of
Central America and Mexico, and to a large number of Carib- the fermented cocoa beans, which is one of the most important
bean Islands. Today the subspecies Criollo is found in Mexico, factors influencing taste and flavor of the cocoa products,
Colombia, and Venezuela. It represents only 5% of the world’s depends not only on the cocoa variety but also on the geographic
production due to its great susceptibility to disease; making it origin.
difficult to cultivate. Criollo pods are green to red; the seeds are Cocoa bean fermentation can be considered the first key
pale, ferment easily, have a pleasant and penetrating aroma, stage in cocoa products and chocolate production because

Encyclopedia of Food and Health http://dx.doi.org/10.1016/B978-0-12-384947-2.00177-X 185

186 Cocoa: Production, Chemistry, and Use

the series of biochemical reactions occurring in the beans is oligopeptides, essential precursors for the development of
necessary for inducing the pleasant characteristics of cocoa- cocoa aroma, arising from the reaction of amino acids with
based products. sugars (Maillard reactions) during the subsequent step of
The fully ripe cocoa pods are carefully cut from the trees, are roasting.
gathered into heaps, and can be stored for 2–5 days. This The duration of fermentation ranges from 1.5 to 10 days,
enhances prefermentation activity inside the pods. The har- depending on the cocoa variety, climate, volume of cocoa
vested pods are broken by hitting against a hard surface, and mass, and the method adopted. Criollo ferments in a relatively
the seeds are extracted from the fruit together with the sur- shorter period of 2–3 days, whereas Forastero takes 5–7 days.
rounding sugary mucilaginous pulp (wet beans) and kept for For the manufacturer of chocolate or cocoa powders the
fermentation immediately. The fresh bean is bitter and is not degree of fermentation of the beans is a major quality criterion.
suitable for manufacture of cocoa products because it does not Fully fermented cocoa beans have a brown color. It has been
have any flavor, aroma, or taste of cocoa products. All the shown that too high contents of nonfermented (slaty color) or
standard methods of fermentation essentially involve keeping partly fermented (violet color) beans result in a lack of cocoa
together in heaps, baskets, boxes, or perforated barrels a mass flavor in the end product. The slaty beans cause a very acid and
of a reasonable quantity of wet beans for periods ranging from astringent flavor profile, whereas the violet beans cause a bitter
4 to 6 days and mixing the mass of beans on alternate days. The and harsh flavor.
natural beans’ fermentations are generally carried out accord- The fermented beans have a moisture content of about
ing to a traditional process. Among the various methods 55%, too high to permit the storage of the beans. The moisture
adopted for fermentation in the different cocoa-producing content has to be lowered to about 6% for safe storage and
countries, the heap, tray, and box methods are considered the transportation. Immediately after fermentation, cocoa beans
standard, widely adopted methods. The real substrate of the are sun-dried or dried utilizing hot air. Depending on climatic
fermentation is not the bean, but the surrounding pulp that conditions, the beans are exposed to the sun for about 12–20
contains about 84.5% water, 10% glucose and fructose, 2.7% days. This method generally gives good-quality beans in tradi-
pentosan, 0.7% sucrose, 0.6% protein, 0.7% acids, and 0.8% tional areas of cocoa production where the weather is suffi-
inorganic acids and therefore it is a good substrate where a ciently sunny, as in West Africa. In the areas where the climate
wide range of microorganisms can develop. Wild yeasts remains unsuitable for drying, artificial drying methods
(Kloeckera and Saccharomyces spp.) and bacteria of genera became necessary, utilizing hot air with a maximum tempera-
such as Lactobacillus, Bacillus, Pediococcus, Acetobacter, and Glu- ture of about 60
C. The humidity % after drying is 5–8%, with
conobacter, are involved in cocoa fermentation, determining a weight loss of two-thirds with respect to the fresh bean. The
alcoholic, lactic acid, and acetic acid fermentations. dried beans are packed in jute bags of about 60 kg capacity and
The first consequence of fermentation is the loss of most of traded to transformation countries, where all the following
the pulp around the beans because the pulp substrates are steps (Figure 1) for production of chocolate and cocoa prod-
broken down through microbial action; however, more impor- ucts will take place.
tant are the biochemical changes inside the cocoa beans that
contribute to a reduction of their bitterness and astringency
and improve their color and flavor. Processing of Fermented Cocoa Beans: Roasting
In the first stage of the fermentation, yeasts proliferate and and Production of Cocoa Liquor
convert sugars to alcohol, then the development of lactic acid
bacteria occurs, which contributes to sugar breakdown produc- A key step of chocolate production is roasting. Roasting is
ing lactic acid. After the pulp has run off, the conditions performed in the transformation countries, and flavor is
become more aerobic, and the presence of oxygen allows acetic formed during this step from the precursors developed during
acid bacteria to take over from the yeasts and convert alcohol fermentation and drying of cocoa beans. The aroma precursors
to acetic acid. Acids that are synthesized from pulp sugars move in cocoa beans, which include free amino acids,
into the beans and lower the internal pH. The acetic acid low-molecular-weight peptides, and reducing sugars, develop
diffusing through the beans causes a breakdown of the poly- into the cocoa specific aroma through Maillard reactions dur-
phenol and lipid membranes of the vacuoles of the cell, and ing roasting.
the cell contents become mixed, allowing various enzymatic Before roasting, cocoa beans are cleaned to remove stones,
reactions to take place. One of the most important conse- metals, and other extraneous materials. Beans are cleaned by
quences is the oxidation of polyphenols and their conversion passing through a series of screens and magnets. In some cases
to insoluble forms due to the reactions with proteins; these a preroasting process is applied. The roasting can be performed
reactions are responsible not only for the removal of the bitter on whole cocoa beans or on cocoa nibs. In most cases the
taste from the beans but also for the strong reduction of total traditional roasting is performed on whole cocoa beans by
polyphenol content, thus affecting the antioxidant and health hot air treatment, and cocoa shells are removed by aspiration
properties of cocoa. Oxidation of polyphenols is also respon- (winnowing). Temperatures of roasting are generally lower
sible for the change of bean color, from violet to brown. that 150
C and for times of from 30 to 120 min. Roasted
During and after fermentation, another fundamental biochem- cocoa beans are then lightly crushed to avoid dust formation,
ical change occurs: internal beans’ autolytic enzymes, in par- obtaining cocoa nibs.
ticular carboxypeptidase and aspartic endoprotease, are Roasted cocoa nibs are milled to break down the cell walls
activated by the low pH; the proteins in the cotyledons and expose the cocoa butter. The resulting product is a homo-
undergo hydrolysis, giving rise to amino acids and geneous flowing cocoa paste called cocoa liquor containing
 Cocoa: Production, Chemistry, and Use 187

FERMENTED DRIED BEANS

Cleaning

Roasting

Winnowing COCOA SHELLS

Grinding

COCOA NIBS

Milling

COCOA LIQUOR
Alkalinization Mixing Sugar, milk etc.

Pressing Refining

COCOA CAKE COCOA BUTTER Mixing

Grinding Conching

COCOA POWDER Tempering

CHOCOLATE

Figure 1 An overview on cocoa bean processing.

about 55% fats. To produce cocoa liquor with improved performed by single or multiple refining rollers. Further key
dispersibility, the cocoa nibs can be subjected to an steps in chocolate production are conching and tempering.
alkalinization process (Dutch cocoa process): roasted nibs are Refined chocolate paste is powdery and has a harsh and sour
treated with a diluted alkali solution at 75–100
C, then neu- flavor, and conching is necessary to obtain fine chocolate of
tralized and dried. This treatment causes starch swelling and optimal flavor, smoothness, and texture. Conching is per-
the formation of porous cell structure of cocoa mass that formed in round or oblong rotary conche pots in which the
prevents the formation of sediments in cocoa drinks. chocolate mass is mixed, ground, and kneaded at temperatures
of 65–75
C. Conching times vary from a few hours to many
days, depending on the desired final chocolate quality. Gener-
Production of Cocoa Powder and Cocoa Butter ally during conching steps, flavors, emulsifier, and cocoa butter
are added. The effect of conching on chocolate paste is a
Cocoa powder is widely used in the manufacturing of cocoa- reduction of acidity due to the loss from evaporation of acetic
based products as drinks, cake fillings, ice cream, and so on. To acid and other volatile compounds, loss of moisture, and a
convert cocoa liquor (generally alkalinized cocoa liquor) to more uniform distribution of fats that form a film around each
cocoa powder, a defatting process is performed by pressing cocoa particle.
liquor in a mechanical or hydraulic press at 400–500 bar and Tempering is one of the most critical steps to obtain a
a temperature of 90–100
C. In this way part of the fat (cocoa product with a stable crystalline form of cocoa butter respon-
butter) is removed, and cocoa cake (compressed cocoa pow- sible of the good melting properties and the glossy surface of
der) is produced. Cocoa powder is obtained by grinding cocoa good-quality chocolate. Tempering is performed by cooling
cake. Generally the fat content of cocoa powder is 10–24%. under stirring the cocoa mass derived from conching (from
Cocoa butter obtained from pressing is separated, filtered, and 40–50 to 18–28
C). Cocoa is maintained at this low temper-
reused as an ingredient for chocolate and many cocoa-derived ature for about 10 min, and then is heated to 32
C. In this way
products. the polymorphic form V of cocoa butter is obtained, with a
melting point of 34
C, close to the human body temperature.
Different chocolate typologies are produced (Table 1) and
Production of Chocolate can be classified according to the different percentages of cocoa
liquor and cocoa butter in the final products or according to
Chocolate is obtained from nonalkalinized cocoa liquor mixed the addition of ingredients different from cocoa. Today much
with sucrose, cocoa butter, emulsifying agents (lecithins), of the chocolate consumed is in the form of sweet chocolate,
flavoring compounds (vanillin), and eventually other ingredi- with the addition of sugars (sucrose). Milk chocolate is sweet
ents (milk, hazelnuts, almonds, etc.). Ingredients are mixed to chocolate that in addition contains milk powder. White choc-
obtain a homogeneous chocolate paste that is then refined to olate contains cocoa butter, sugar, and milk, but no cocoa
obtain finer particles of < 30–40 mm. The refining step is liquor.
188 Cocoa: Production, Chemistry, and Use

Table 1 Examples of formulations for different kind of chocolate concentrations of hydrophobic amino acids, such as leucine,
(g/100 g) alanine, and phenylalanine, is explained by the activity of
carboxypeptidase that releases single hydrophobic amino
Chocolate Chocolate Milk White
acids and aspartic endoprotease, which hydrolyzes proteins
Ingredient (50% cocoa) (70% cocoa) chocolate chocolate
preferentially at the hydrophobic amino acids sites. The free
Cocoa liquor 35 70 12 – amino acid content recorded in fermented beans ranges from
Added cocoa 15 – 22 30 500 to 1800 mg/100 g, with a prevalence of the hydrophobic
butter amino acids responsible of the formation of Strecker aldehydes
Sugar 50 30 51 50 and pyrazines, important compounds for cocoa aroma.
Whole milk – – 15 20 Among nonprotein amino acids, relevant contents of gamma-
powder aminobutyric acids, ranging from 30 to 100 mg/100 g, were
detected in fermented cocoa beans, therefore cocoa can be
considered an important natural source of this inhibitory neu-
Chemical Composition rotransmitter amino acid.
Lipids Low amounts (20 mg kg1) of biogenic amines deriving
from microbial decarboxylation of amino acids occurring dur-
Cocoa fat (cocoa butter) represents about 50–58% of the cocoa ing fermentation, as 2-phenylethylamine, tyramine and trypt-
beans, and its triacylglycerols (97–98% of cocoa butter) mainly amine have been found in cocoa. Biogenic amines can be also
consist of palmitic acid (25% of total fatty acids), stearic acid originated by thermal decarboxylation of amino acids, so their
(37%), and oleic acid (34%), with a low amount of linoleic amount is higher in roasted products.
acid (3%). Oleic acid is primarily esterified at the 2-position of
glycerol, so the main triacylglycerols are 1,3-dipalmito-2-olein,
1-palmito-3-stearo-2-olein, and 1,3-distearo-2-olein. Cocoa Carbohydrates and Organic Acids
butter is solid at room temperature and melts at temperatures The primary carbohydrates in fermented dried cocoa beans are
between 30 and 40
C, depending on the polymorphic form. starch (6%) and cellulose (9%). Soluble carbohydrates include
The amount of cocoa butter in chocolate is 21–35%, depend- glucose, fructose, sucrose (0.08–1.5%), raffinose, and sta-
ing on the addition of cocoa butter to the cocoa liquor. chyose. Sucrose is partially hydrolyzed during fermentation,
providing reducing sugars precursors of aroma development
during roasting. Fiber fraction aside from cellulose contains
Protein, Peptides, Amino Acids, and Amines
pentoses (1.5%), galactans, and polymers of galacturonic acid.
Proteins make up 10–15% of the dry weight of cocoa seeds, the Fibers are concentrated in cocoa shells.
second most abundant constituent after cocoa fat. Proteins are Organic acids (1.2–1.6%) are primarily formed during
the cocoa fraction that undergoes the most intensive modifica- cocoa bean fermentation, and the most represented are acetic
tion during fermentation, where microbiological and enzy- acid (0.2–0.7%), citric acid (0.4–0.7%), and oxalic acid
matic reactions lead to extensive breakdown of cocoa seed (0.3–0.5%). Acetic acid is partly lost during cocoa processing,
proteins, yielding peptides and amino acids that are the impor- in particular during conching.
tant flavor precursors.
Cocoa beans contain four main proteins, albumin, globu-
Methylxanthines
lin, prolamin, and glutelin. Albumin and globulin are the most
important both quantitatively and qualitatively. Globulins are Cocoa, as coffee and tea, is generally considered a stimulating
vicilin-like storage proteins consisting of three subunits with food, due to the high levels of alkaloids. Theobromine and
molecular masses of 47, 31, and 15 kDa, which are derived caffeine in particular are the principal alkaloids found in cocoa.
from a common 66-kDa precursor. The albumin fraction was Theobromine (3,7-dimethylxanthine) represents 1.2–2% of
identified as a 21-kDa cocoa seed protein having trypsin inhib- cocoa beans, where it is partially bound to tannins in cotyledon
itory properties. During fermentation, peptide and free amino cells. During fermentation, the development of acetic acid per-
acids increase and total protein concentration decreases. The mits the release of theobromine that migrates from cotyledons to
globulin protein fraction is the most degraded during fermen- shells. Cocoa shells in fact contain about 1.5% of theobromine,
tation. Cocoa proteins are cleaved to hydrophilic and hydro- and generally they are reused to extract this alkaloid.
phobic peptides as well as amino acids through autolysis by
two endogenous enzymes, aspartic endoprotease and carboxy-
Polyphenols
peptidase. Fermentation of cocoa beans is fundamental for the
activation of these two enzymes by microbial metabolites Cocoa is a rich source of polyphenols: the defatted unfermented
(such as acetic acid). Changes in the protein composition of cocoa beans contain about 120–180 g kg1 of polyphenolic
cocoa beans have been noted not only during fermentation but compounds, representing one of the most concentrated natural
also as a consequence of roasting. A decrease in total protein, sources. The polyphenols in cocoa beans are stored in the
free amino acids, and albumin are seen during roasting. pigment cells of the cotyledons. Depending on the amount
Regarding amino acids composition, nonfermented beans of anthocyanins, pigment cells are white to deep purple. Three
contain low levels of free amino acids with a 1:1 ratio between groups of polyphenols can be distinguished: catechins or flavan-
hydrophobic/acidic amino acid, whereas in fermented cocoa 3-ols (37%), anthocyanins ( 4%), and proanthocyanidins
seeds this ratio significantly increases to 3:1. The increase in the ( 58%). The main catechin is ()-epicatechin representing up
 Cocoa: Production, Chemistry, and Use 189

to 35% of polyphenol content. In smaller amounts, (þ)-catechin World Production and Human Consumption
as well as traces of (þ)-gallocatechin and ()-epigallocatechin
have been found. Procyanidins in cocoa consist of oligomers The cocoa-producing countries are all developing countries
and polymers of catechin and epicatechin. Anthocyanins iden- and localized in Africa, Central America, South America, Asia,
tified in cocoa include cyanidin-3-galactoside and cyanidin-3- and Oceania. World production of cocoa beans is constantly
arabinoside. Small quantities of quercetin, quercetin glycosides, growing: it has increased from 31 000 tons in 1880 to more
naringenin, luteolin, apigenin, clovamide, and phenolic acids than 3 000 000 tons in 2002 and about 5 000 000 tons in 2012.
such as caffeic, ferulic, gallic, and p-coumaric acid have also been Africa is the continent with the highest production (67%). The
found in cocoa products. largest state producer is the Ivory Coast (about 30% of world
The high level of polyphenols in raw cocoa beans is progres- production). World cocoa production has risen at an average
sively reduced during cocoa processing. During fermentation annual growth rate of 3.3% during the period 2002–12.
polyphenols diffuse with cell liquids from their storage cells Between 2002 and 2011/2012, primary cocoa processing
and undergo oxidation to condensed high-molecular mostly growth at an average rate of 2.9% per annum was registered.
insoluble tannins. These reactions are both nonenzymatic and Europe remained by far the largest cocoa-processing region,
enzymatic catalyzed by polyphenol oxidase. It is reported that followed by the United States. However, with an annual
epicatechin and catechin content, respectively, are reduced to growth rate of 5.6%, the largest regional processing increase
10–70% during fermentation. Roasting causes a dramatic occurred in Asia and Oceania. Moreover, in the last 10 years
reduction of some phenolic substances, in particular clovamide, processing in the countries of origin has increased, supported,
together with an overall decrease of the antiradical and antiox- in some countries, by government policies favoring the export
idant properties of cocoa beans/nibs. High temperatures during of value-added semifinished products rather than raw cocoa
the cocoa bean roasting process and also the alkali treatments beans.
on the cocoa powder induce the epimerization reaction of epi- European regions are also the largest cocoa consumers,
catechin to catechin, reducing its bioavailability. Moreover, accounting for 48% of total world consumption of cocoa
some recent works have achieved chiral separations of catechin followed by the Americas, at 33%. Growing consumption has
and epicatechin enantiomers, showing that the prevalent form been observed in Asia and Africa. Consumption of chocolate
of catechin in roasted cocoa products is ()-catechin, a confectionery products increased by 10% between 2002 and
nonnatural in cocoa beans with less bioavailability than 2010 in selected countries, including the major European
(þ)-catechin. countries, the United States, Brazil, Japan, and Australia, corre-
sponding to an annual growth rate of 1.2%. World per capita
Flavor Compounds consumption of cocoa has also seen a similar pattern of growth
over the review period, rising from 0.54 kg in 2002 to 0.61 kg
Chocolate and cocoa flavors reside in their volatile fraction, in 2010.
which is composed of a complex mixture of up to 500 com- Consumer preferences, especially of European and Ameri-
pounds. The aromatic profile of cocoa beans is very complex can consumers, has changed over the last 10 years: chocolate
and is also dependent on the method and duration of fermen- aficionados are asking for single-origin premium chocolate
tation and drying practices applied. Alcohols, aldehydes, and and ‘high cocoa content’ products, with their own distinctive
ketones have been reported as the major groups of compounds flavors. Cocoa industries are driven to use innovation to
found in raw cocoa and at the beginning of the fermentation appeal to consumers in saturated markets: new flavors,
process (1 or 2 days). Alcohols, esters, and acids (acetic acid new packaging, and new sizes but also chocolates with
mainly) were developed in the middle of fermentation health-promoting properties for health-conscious consumers.
(3–5 days), becoming the most important groups of volatile Sustainable sourcing is also growing in importance for con-
compounds at the end of fermentation (6–8 days). Alcohols, sumers: demand for cocoa grown in a responsible manner
esters, and pyrazines contents increased during the sun-drying is rising, as a consequence of the companies’ response to
process. consumer preferences.
Cocoa fermentation is crucial not only to the formation of
significant volatile fractions but also for the development of
See also: Cocoa: Composition and Health Effects.
cocoa–chocolate flavor precursors as amino acids and reducing
sugars. Via Maillard reactions, cocoa roasting converts flavor
precursors formed during fermentation to two main classes of
odorant compounds: pyrazines and Strecker aldehydes, and
three of these had a strong chocolate flavor: 2-ethylpropanal, Further Reading
2-methylbutanal, and 3-methylbutanal. Pyrazines were recog-
Afoakwa EO, Paterson A, Fowler M, and Ryan A (2008) Flavor formation and character
nized as cocoa/nutty notes: 2,3-dimethylpyrazine, trimethyl- in cocoa and chocolate: a critical review. Critical Reviews in Food Science and
pyrazine, tetramethylpyrazine, 3(or 2),5-dimethyl-2(or Nutrition 48(9): 840–857.
3)-ethylpyrazine, 3,5(or 6)-diethyl-2-methylpyrazine, and fur- Kratzer U, Frank R, Kalbacher H, Biehl B, Wöstemeyer J, and Voigt J (2009) Subunit
furylpyrrole. Conching has an effect on cocoa aroma, although structure of the vicilin-like globular storage protein of cocoa seeds and the origin of
cocoa- and chocolate-specific aroma precursors. Food Chemistry 113: 903–913.
no new key odorant is synthesized during the heating process,
Lima LJR, Almeida MH, Rob Nout MJ, and Zwietering MH (2011) Theobroma cacao L.,
and levels of 2-phenyl-5-methyl-2-hexenal, furaneol, and “The food of the Gods”: quality determinants of commercial cocoa beans, with
branched pyrazines are significantly increased, whereas most particular reference to the impact of fermentation. Critical Reviews in Food Science
Strecker aldehydes are lost by evaporation. and Nutrition 51(8): 731–761.
190 Cocoa: Production, Chemistry, and Use

Prabhakaran Nair KP (2010) Cocoa (Theobroma cacao L.). In: The agronomy and generated from cocoa seed protein by co-operation of an aspartic endoprotease and
economy of important tree crops of the developing world, pp. 132–180. Boston, a carboxypeptidase. Food Chemistry 49: 173–180.
MA: Elsevier. Wollgast J and Anklam E (2000) Review on polyphenols in Theobroma cacao: changes
Rohsius C, Matissek R, and Lieberei R (2006) Free amino acid amounts in raw in composition during the manufacture of chocolate and methodology for
cocoas from different origins. European Food Research and Technology identification and quantification. Food Research International 33: 423–447.
222: 432–438.
Schwan RF and Wheals AE (2004) The microbiology of cocoa fermentation and its role
in chocolate quality. Critical Reviews in Food Science and Nutrition 44(4):
205–221. Relevant Websites
Voigt J, Biehl B, Kamaruddin S, and Wazir S (1993) The major seed proteins of
Theobroma cacao L. Food Chemistry 47: 145–151. http://faostat.fao.org/ – Food and Agriculture Organization of the United Nations.
Voigt J, Biehl B, Heinrichs H, Kamaruddin S, Gaim arsoner G, and Hugi A (1994) http://www.icco.org/ – International Cocoa Organization.
In-vitro formation of cocoa-specific aroma precursors: aroma-related peptides http://worldcocoafoundation.org – World Cocoa Foundation.