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Cocoa Industry—From Plant Cultivation to Cocoa Drinks Production
COCOA INDUSTRY—FROM PLANT CULTIVATION TO COCOA DRINKS PRODUCTION
15
Genţiana Mihaela Iulia Predan⁎, Daniela Anca Lazăr⁎, Iulia Ioana Lungu† ⁎
Department of Botany and Microbiology, University of Bucharest, Bucharest, Romania †Department of Biomaterials and Medical Devices, University Politehnica of Bucharest, Bucharest, Romania
15.1 Introduction Cocoa, as a drink, is consumed as a suspension. In addition to stimulating alkaloids, particularly theobromine, cacao products contain substantial amounts of nutrients: fats, carbohydrates, and proteins. Cocoa has to be consumed in large amounts in order to experience a stimulating effect. In order for one to encounter a stimulating reaction, a large quantity of cacao must be consumed. A very important moment in history has been the discovery of America by Columbus. However, interestingly, in Mexico, as well as Central America, cocoa beans have been known and used for more than a thousand years before the big discovery. In the early 17th century, cocoa beans were imported into Germany. Because of its bitter taste, cacao became well-known only after sugar was added in the chocolate composition (Afoakwa et al., 2008). The components that contribute to the flavor and aroma of chocolate are the polyphenols, which have received much attention due to their beneficial implications to human health by preventing cancer, cardiovascular diseases, and other pathologies (Cooper et al., 2008).
15.2 General Description The tropical tree Theobroma cacao L., known as cacao or cocoa, belongs to the family Sterculiaceae, order Malvales (Baharum et al., 2016). In ancient Central America, Mayans and Aztecs used to cultivate cacao trees in order to use their seeds to prepare “chocolatl,” the first Caffeinated and Cocoa Based Beverages. https://doi.org/10.1016/B978-0-12-815864-7.00015-5 © 2019 Elsevier Inc. All rights reserved.
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chocolate-based beverage. The T. cacao L. tree is characterized as being a petit evergreen tropical and subtropical tree originated from the neotropical rainforests (Baharum et al., 2016). The height of the cocoa tree can vary between 5 and 15 m. In order to properly grow, the cocoa tree requires a warm and moist climate, with temperatures ranging from 24°C to 28°C and elevations up to 600 m. Because of their sensitiveness to light and wind, they are usually cultivated under the so-called “cacao mothers,” which are basically coconut or banana trees (Fig. 15.1; Belitz et al., 2009). The cacao trees were found growing in the shade of a “typical” Maya forest garden (Barrera et al., 1977) composed of a mixture of useful native species such as Brosimum alicastrum (ramon, osh), Manilkara achras (chak ya', chico zapote), Pouteria campechiana (caniste), Pouteria mammosa (mamey, zapote mamey), Quararibea guatemalensis, Bursera simaruba (chacaj, palo mulato), Ficus sp., Chrysophyllum cainito (caimito), Annona reticulata (oop, anona colorada), Carica papaya (papaya), Sabal yapa (guano), Caesalpinia yucatanensis, and Lonchocarpus xuul among the native species, and
Fig. 15.1 Part of Theobroma cacao L. tree (original image).
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Cocos nucifera (coconut), Citrus spp. (oranges and lemons), and Musa paradisiaca (banana) as the principal introduced species. Similar composition has been found in many other forests of the Maya area in which a mixture of selected native and introduced trees produces an artificial forest garden (Gomez-Pompa et al., 1987). The tree blooms every season. Small red, yellow, or white flowers (Fig. 15.2) are characteristic and bear 20–50 ripe fruits per tree. Cocoa flowers are grouped together in clusters arising directly from the trunk (cauliflory). The ripe fruits resemble a melon and are usually between 15 and 25 cm long and 7–10 cm wide. The fruit, or “cocoa pod,” has a specific red to brown color and a surface covered in knobs and lines all across. In the wild, cocoa trees are pollinated by midges, and only about 5% of flowers receive enough pollen to start fruit development. When pollination occurs, impressive changes can be observed as the flowers evolve into imposing fruits.
Fig. 15.2 Cocoa flowers arising directly from the trunk (cauliflory).
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The floral meristem produces flowers over the tree’s entire life span. However, seasonal variations can be observed during the floral production (Edwards, 1973). The moment when the flower opens and the anthers release their pollen is synchronized every morning in the early hours. Various small insects, including midges (Ceratopogonidae: Forcipomyia), are responsible for pollination. Unfertilized flowers abscise from the stem about 24–36 h after anthesis. Only 0.5%–5% of flowers develop into mature pods (Carr and Lockwood, 2011). Cacao beans are oval-shaped and flattened, about 2 cm long and 1 cm wide, and weigh about 1 g after drying. The embryo has two thick cotyledons (nibs) and a germ rootlet of 5 mm long and 1 mm thick (Belitz et al., 2009). Even though the fruit can be harvested all year round, it is preferentially harvested twice a year. The summer harvest is larger and of a higher quality. The cacao tree starts developing pods roughly after 5–6 years, having a maximum yield after 20–30 years. However, its life span extends up to 40 years of growth. Another main factor in the flavor of cacao beans is the harvesting time (Belitz et al., 2009). When the pods are fully ripened, they are cut down, collected in piles, and cut open in order for the seeds to be scooped out together with the adjacent pulp. Cocoa seedlings exhibit two growth forms: a vertical (orthotropic) stem, known as a chupon, with spiral phyllotaxi, together with three to five lateral (plagiotropic) fan branches (5/8 phyllotaxi). The point from which the buds grow out sideways from the terminal end of the main stem is known as a jorquette. The phenological growth stages of cocoa plants have been described in detail by Niemenak et al. (2009) using the “extended BBCHscale.” Development can be divided into the following principal growth stages: Growth stage 0: seed germination-vegetative propagation. Growth stage 1: leaf development on the main (vertical) stem, and on the fan branches. Growth stage 2: main stem elongation, formation of a jorquette of fan branches and another chupon. Growth stage 3: fan branch elongation. Growth stage 5: inflorescence emergence. Growth stage 6: flowering. Growth stage 7: development of fruit. Growth stage 8: ripening of fruit and seed. Growth stage 9: senescence. (Note, growth stage 4 does not apply to cocoa, it applies only to cereals) (Carr and Lockwood, 2011).
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Traditionally, cocoa is classified according to trade perceptions of its physical and sensory quality and associated botanical traits, albeit imperfectly (Cheesman, 1944). • Criollo: cultivated on a small scale because of its lack of vigor, although the area is currently expanding due to renewed interest in speciality cocoa. • Forastero: the bulk of the world’s cocoa production is from this type. • Trinitario: usually considered to be the result of crosses between the other two types and is not found in the wild. Material designated as Trinitario is grown commercially in the Caribbean and Papua New Guinea (Carr and Lockwood, 2011).
15.3 Processing of Cocoa Beans The chocolate flavor is obtained by processing the beans, which contains two complex procedures that change their initial chemical and physical features. The initial stage includes fermentation and drying processes, while the second one is based on the composition of the end product. The later includes the following methods: roasting, alkalization, and conching (McShea et al., 2008; Aculey et al., 2010, quoted by Aprotosoaie et al., 2016). The cocoa preprocessing steps (harvest, breaking, fermentation, and drying) are important to ensure the high quality of the beans. For Lagunes Gálvez et al. (2007) fermentation is one of the postharvest step that most affect the quality of the products obtained from cocoa (Fig. 15.3).
15.3.1 Fermentation When handling cacao beans, the most important step is fermentation. During fermentation, the pulp is degraded by the successive action of microorganisms, promoting the rise of temperature to about 50°C and the formation of ethanol and lactic acid, driving to the embryo death, which creates an environment for the formation of flavor and aroma precursors of chocolate, developed through roasting process (Lopez, 1986; Leite et al., 2013). Fermentation is a complex process that takes place at different time periods after the pods are collected and opened. The first phase, also called the anaerobic phase, occurs in the first 24–36 h. The beans, as well as the pulp are uncovered and interact with several microorganisms. The pulp has an acidic profile (pH below 4) and generates ethanol in this phase due to alcoholic fermentation of its sugars by yeasts.
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Manually harvesting
Cocoa beans
Fermentation
Drying
Cocoa pods
Cleaning
Roasting
F. precursor formation F. development
F. and color change
Final F.development and texture improvemnent
Conching
CHOCOLATE
Milling
Cocoa liquor, cocoa mass
Blending
Winnowing
Cocoa nibs
Alkalinization
Pressing
COCOA POWDER
COCOA BUTTER
ChocolateͲ flavored products
COCOA BEVERAGES
Fig. 15.3 Schematic representation of the processing of cocoa beans.
Apart from ethanol production, the pulp sugar fermentation process also generates lactic acid, acetic acid, and carbon dioxide. The second phase takes place after 48–96 h and it is characterized by the inhibition of yeast activity due to several factors: (i) aeration, (ii) alcohol concentration, and (iii) pH increase. The later aspect is attained by citric acid depletion and leads to the production of lactic acid bacteria. Acetic acid bacteria have a very important function in the development of flavor precursors. It has been observed that the optimal fermentation period or the formulation of flavor precursors is 6 days (Giacometti et al., 2015). During the anaerobic phase, sucrose is partially hydrolyzed to reducing sugars, proteins undergo proteolysis to peptides and amino acids, and polyphenols are hydrolyzed and oxidized (Aprotosoaie et al., 2016). During the anaerobic phase, several condensation and oxidation reactions take place. For example, when the oxidation and condensation of protein-polyphenol complex and, respectively, carbonyl-amino occur, these reactions reduce the beans bitterness. Color is also a factor that has an effect on the final flavor. A dark gray color is the c haracteristic
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of unfermented, bitter beans, whereas fully fermented beans have a deep brown color (Afoakwa et al., 2008; Aculey et al., 2010).
15.3.2 Drying The bitter taste, acidity, and color of the final beans can also be controlled in the drying phase (Merkus, 2014). The oxidative reactions that take place during the fermentation phase are continued in the drying stage. Several drying techniques have been reported in the literature, however, among them, the most commonly used is sun drying due to its ability to induce a more pronounced chocolate flavor. Moreover, this technique does not give any off-flavors, such as smokey notes, to the final beans, which is one of the main conditions for good quality beans (Afoakwa et al., 2008).
15.3.3 Roasting Roasting is the final step in cocoa beans processing. processing steps fermentation drying cleaning blending thermal pretreatment winnowing roasting The goals of these procedures are to obtain the specific texture of beans, flavor, and the elimination of volatile compounds, such as acetic acid. Moreover, moisture content is decreased up to 1% (Giacometti et al., 2015). During the roasting phase, biogenic amines are formed. These compounds are not volatile and do not have a role in the final products aroma, but they have a significant outcome on the human organisms after they are consumed. Roasting can be carried out through three approaches: whole bean, nib, and liquor roasting. The characteristics of the raw material, its variety, and the specifications of the desired flavor are all important when deciding on the optimal parameters of the roasting method (Ramli et al., 2006). It has been noted that the flavor quality is strictly related to the high degree of roasting. However, overroasting is a negative outcome. The roasting time and temperature must be maintained from 5 to 120 min and between 110°C and 160°C, respectively. The above-mentioned overroasting occurs when the temperature exceeds 160°C and results in a burnt taste of the final product, also known as off-flavor (Saltini et al., 2013; Aprotosoaie et al., 2016). 1. 2. 3. 4. 5. 6. 7. 8.
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15.3.4 Alkalization Alkalization is the treatment of the final cocoa product (mass, liquid, or powder) with alkali. Currently, this method is used for aesthetics and flavor aspects, as well as for increasing the solubility degree of powder-based cocoa in beverages (Giacometti et al., 2015).
15.3.5 Conching Conching is a heat treatment used to determine the final texture and aroma of chocolate. Advantages of this technique include: enhancing the flavor profile, decreasing the concentration of free acids and volatile by-products of the cacao beans (McShea et al., 2008; Giacometti et al., 2015).
15.4 Composition 15.4.1 Proteins and Amino Acids Up to 60% of the total nitrogen volume of fermented beans consists of proteins. The remaining has been established to be made up of amino acids (0.3% amide form and 0.02% as ammonia, formed during the fermentation process) (Belitz et al., 2009).
15.4.2 Theobromine and Caffeine 3,7-Dimethylxanthine, commercially called the bromine, has a similar, yet reduced, effect as caffeine. It is weakly bonded to tannins and released by the acetic acid produced during the fermentation process. Both bromine and caffeine can be found, in small amounts, in cocoa. For example, one cup of cocoa beverage contains 0.1 g of the bromine and 0.01 g of caffeine (Belitz et al., 2009).
15.4.3 Lipids A representative ingredient of cocoa beans is cocoa fat, also known as cocoa butter (Belitz et al., 2009).
15.4.4 Carbohydrates Starch is the predominant carbohydrate. There are several soluble carbohydrates found in cocoa such as stachyose, raffinose, sucrose, glucose, and fructose. During fermentation, sucrose hydrolysis occurs which reduces the sugar content. This has a major effect on the final flavor obtained during the roasting phase. Among the various sugars found in the cacao nib, mesoinositol, phytin, and verbascotetrose can be mentioned (Belitz et al., 2009).
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15.4.5 Phenolic Compounds The nib cotyledons consist of two types of parenchyma cells. The majority of the cells—up to 90%—are smaller in size and consist of protoplasm, starch granules, aleurone grains, and fat globules. Among these small cells, larger cells can be found, which contain phenolic compounds and purines. The polyphenol cells, also known as pigment cells, account for 11%–13% of the whole tissue and are composed of anthocyanins. The later cells have a color range from white to dark purple, depending on their structure. There are three phenol groups found in cacao: (i) catechins— around 37%, (ii) anthocyanins—around 4%, and (iii) leucoanthocyanins—around 58% (Belitz et al., 2009).
15.4.6 Organic Acids About 1.2%–1.6% of organic acids are found in cacao. Of these, citric, acetic, succinic, and malic acid have a significant contribution to the cacao flavor. As mentioned above, these acids are formed during the fermentation phase. The quantity of acetic acid released by the pulp and received by the bean cotyledons has a strict correlation with the fermentation time and the type of drying techniques used (Belitz et al., 2009).
15.4.7 Volatile Compounds and Flavor Substances The cocoa flavor and aroma is strictly dependent on the processing techniques. Unprocessed, fresh beans smell and taste like vinegar. However, improper handling or contamination during the processing stages can lead to low-quality cocoa beans with uncharacteristic taste.
15.5 Uses After cocoa seeds are processed, fat is extracted from the powdery final product. The result is the commercially available product used in the preparation of chocolate and chocolate-based beverages. However, additional processing is made for manufacturing chocolate. The resulted powder is combined with sugar, flavor agents, and extra cocoa fat. Apart from chocolate and beverages, cocoa butter is also used in pastries, sweets, and fabrication of tobacco, soap, and cosmetics (Duke, 1983). Known under different names hot chocolate, chocolate tea, drinking chocolate, or just cocoa, is a heated beverage that has as main components chocolate (shaved, melted, or powder), heated milk or water, and usually a sweetener. “Drinking chocolate” is basically hot
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chocolate, but made with melted chocolate. It is distinctive due to its thicker texture and lesser sweetness (Grivetti and Shapiro, 2009). Mayans referred to hot chocolate as xocōlātl and it was a crucial component of the Aztec culture by 1400 AD (Trivedi, 2002). All around the world, hot chocolate is consumed in various forms. Some examples of names come from Latin America, Italy, Spain, and United States such as “para mesa,” “cioccolata calda,” chocolate a la taza,” and “hot cocoa,” respectively The first coffee shop was opened in 1657 and called Chocolate House. However, chocolate beverages were highly expensive, costing 50–75 pence (~10–15 shillings) a pound (roughly £45–65 in 2016) (Burleigh, 2002). Cornstarch is a widely used as thickening agent for hot chocolate in Europe (mainly Italy and Spain). The Dutch are known for their love for hot chocolate, known as warme chocolademelk, which is served either at home or in cafes. The French prefer serving hot chocolate in the morning, usually accompanied by butter, jam, honey, or Nutella spread on sliced bread which they sometimes dip into the beverage. Germans made a clear difference between hot chocolate made from melted chocolate (Heiße Schokolade Wiener Art) and the one prepared from chocolate powders (Trinkschokolade). It is often served with whipped cream on top. The ingredients for chocolate—cocoa powder and cocoa butter (solids)—are prepared from fermented and roasted cocoa seeds. Typically, a chocolate milk bar consists of 15% cocoa liquor and 20% cocoa powder. The distinctive flavor of chocolate develops during the fermentation process. The fundamental ingredients of chocolate are alkalized cocoa mass, cocoa powder or cocoa butter, sugars, lecithin, and, in the case of milk chocolate, milk powder or crumbs (Merkus, 2014).
15.6 Chocolate Beverages The main chocolate beverages are presented in Table 15.1.
15.7 Health Effects of Cocoa The immune system plays a critical role in the relationship between malnutrition and infection. A way to boost the immune system is to supplement it with antioxidant activity nutrients (Meydani et al., 1998). Cocoa seeds contain a high amount of flavonoids. Low quantities of quercetin, isoquercetin (quercetin-3-O-glucoside), and quercetin3-O-arabinose are also found in cocoa powder. Irrespective of their
Table 15.1 Main Cocoa-Based Beverages Year and Place of the First Commercial Release
First Producer
References/Observations
Name
Main Known Ingredients
Banania
Cocoa, banana flour, cereals, honey, sugar Espresso, drinking chocolate, and whole milk (layered)
1912 (France)
Pierre Lardet
https://en.wikipedia.org/wiki/Banania
~1704 (Turin), Italy
https://en.wikipedia.org/wiki/Bicerin
Bournvita
Malt and chocolate (other original recipe included full-cream milk)
1933, Australia
Traditional Piedmontese product (recognized in 2001) Cadbury
Champurrado
Chocolate, maize flour, water/milk
Precolumbian
Choc-Ola
Chocolate, various recipes
Chocolate liqueur
Sherry, port, chocolate (initially cocoa beans), and sugar
1944, Pennsylvania (United States) Mentioned in France since 1870
Chocolate milk
Chocolate powder, sugar, milk Other ingredients, such as starch, salt. Sometimes: carrageenan, vanilla, or artificial flavoring Sugar, processed cocoa, wheat flour and cola nut, vitamins, Ca, P
Bicerin
Cola Cao
Late 1700s, Ireland
Barcelona (Spain)
Mexican traditional drink Harry Normington, Sr. Popular drink in France in last decades of the 19th century Hans Sloane
Idilia Foods (formerly Nutrexpa)
Discontinued in the UK market in 2008 https://en.wikipedia.org/wiki/ Bournvita https://en.wikipedia.org/wiki/ Champurrado https://en.wikipedia.org/wiki/ Choc-Ola https://en.wikipedia.org/wiki/ Chocolate_liqueur
https://en.wikipedia.org/wiki/ Chocolate_milk
https://en.wikipedia.org/wiki/ Cola_Cao Continued
Table 15.1 Main Cocoa-Based Beverages—cont’d Year and Place of the First Commercial Release
Name
Main Known Ingredients
Egg cream
Milk, carbonated water, and flavored syrup (typically chocolate or vanilla). The drink contains neither eggs nor cream A shot of espresso, cocoa powder, and milk froth Sugar, chocolate, and malt powder mixed with hot or cold water or milk Espresso and hot milk with added chocolate Chocolate-flavored milk Malt extract, sugar, whey, cocoa
New York city
Cornmeal cacao Toasted cacao beans, rice, cinnamon, anise seed, and asquiote Boiled cornmeal, cocoa, and grains Milk, sugar, and chocolate Toasted maize, chocolate, pine nuts, achiote, vanilla, sugar Maize and cacao
Nicaragua Mexico, Veracruz
Marocchino Milo Caffè mocha (mocaccino) Nesquik Ovaltine (Ovomaltine) Pinolillo Pópo Pozol Pucko Tascalate Tejate
First Producer
References/Observations
Initially preferred by Eastern European Jews immigrants
https://en.wikipedia.org/wiki/ Egg_cream
Alessandria, Italia 1934, Sydney, Australia Mocha, Yemen
Thomas Mayne
1948, Switzerland 1904, Switzerland
Nestlé Associated British Foods
1519, Mexico 1954 Sweden Mexico Oaxaca, Mexico
Arla Foods
https://en.wikipedia.org/wiki/ Marocchino https://en.wikipedia.org/wiki/ Milo_(drink) https://en.wikipedia.org/wiki/ Caff%C3%A8_mocha https://en.wikipedia.org/wiki/Nesquik https://en.wikipedia.org/wiki/Ovaltine https://en.wikipedia.org/wiki/Pinolillo https://en.wikipedia.org/ wiki/P%C3%B3po https://en.wikipedia.org/wiki/Pozol https://en.wikipedia.org/wiki/Pucko https://en.wikipedia.org/wiki/ Tascalate https://en.wikipedia.org/wiki/Tejate
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amount, these compounds are considered to have a beneficial effect on the health (Lamuela et al., 2001). Among several other flavonoids found in cocoa powder, the following can be mentioned: hyperoside (quercetin-3-O-galactoside), naringenin, luteolin, apigenin, and some O-glucosides and C-glucosides of these compounds (SánchezRabaneda et al., 2003). The beneficial effects of cacao consumption are associated with human health, especially with the improved condition of the skin (Kim et al., 2016). Cacao provides positive effects on the skin structure and the dermal microcirculation, and its topical preparations are able to protect the skin from the oxidative damages arising from UV radiation (Kim et al., 2016).
15.7.1 Potential Anticancer Compounds Apart from being used as a beverage, cocoa was also used, in ancient times, as a medicinal plant for treating different afflictions. Through the early 17th to 20th centuries, more than 100 medicinal uses of cocoa have been recorded (Europe and New Spain). Some examples are as follows: anemia, mental fatigue, tuberculosis, fever, gout, kidney stones, and even poor sexual appetite (Dillinger et al., 2000). It has been reported that the cocoa bean contains a multitude of phytochemicals and physiologically active compounds. For example, Kim et al. (2011) reported that selected procyanidins present in cocoa inhibited tumorigenesis, tumor growth, and angiogenesis. Due to the high antioxidant activity of cocoa-based products, it can prevent or aid damages generated by genotoxic and epigenetic carcinogens and inhibit the early stages of cancer development (Baharum et al., 2016). The beneficial effects attributed to cocoa-based products have been associated with the flavonoids, polyphenols, and procyanidins that are found in their structure. Several reports have been published on the beneficial effects of cocoa which include antioxidant effects (Othman et al., 2007), protection against cardiovascular disease (Corti et al., 2009), and for cancer treatment (Maskarinec, 2009). It has been reported that flavonoids could inhibit several kinases and transcription factors (TFs) through their biological activities. They have been observed to inhibit agiogenesis, induce apoptosis, and do not proliferate, in in vitro studies (Kang et al., 2008; Faria et al., 2006). The cocoa procyanidins, epicatechin, and catechin have significant antioxidant effects (Belščak et al., 2009). Cocoa may be considered a potential agent in cancer treatment. Polyphenols can alter the general means of action of carcinogenesis through different mechanisms. Specifically, polyphenols can cancel
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out the formation of oxidative stress, thereby aiding to the prevention of cancer evolution. Moreover, polyphenol adjustment of oxidative stress in cancer cell alters signal transduction, activation of redox- sensitive TFs, and the expression of specific genes that induce cell proliferation and apoptosis (D’Archivio et al., 2008). It has been reported that pentameric procyanidin from cocoa trees inhibit breast cancer cells. The mitochondriotoxic molecule F16 has been recently studied with regard to its effects on breast cancer. It has been observed that compounds causing mitochondrial depolarization inhibit the tumor growth of breast cancer cells through G1 arrest, apoptosis, or necrosis, depending on the genetic background of the cell (Ramljak et al., 2005). Due to the high nutritional value of cocoa-based products, studies have recommended cocoa as a potential antiproliferative agent (Baharum et al., 2016).
15.7.2 Cardioprotection Several epidemiological studies on polyphenol-rich cocoa and 70% or above cocoa-based chocolate have indicated that they are complementary with a reduction in the development of stroke, atherosclerosis, coronary artery disease, heart failure, and cardiovascular disease-related mortality (Crozier and Hurst, 2014). There are several explanation for this: an improvement in antioxidant status and endothelial function, modulation of the blood pressure, metabolic and antiinflammatory effects, and inhibition of the platelet activation and aggregation (Kothe et al., 2013).
15.7.3 Effects on Blood Pressure Spontaneously hypertensive rates (SHRs) have been subjected to a single oral intake of cocoa powder containing high levels of procyanidins. The results have shown decreased blood pressure. A soluble cocoa fiber intake over a extended period of time indicated reduced hypertension development in SHR (Sánchez et al., 2010). The effects of cocoa on blood pressure may be more pronounced in younger subjects due to their high vascular reactivity to physiological stimuli (Arranz et al., 2013).
15.7.4 Antiinflamatory Effects One of the leading factors for atherogenesis is chronic inflammation. In vitro studies on cocoa polyphenols have indicated that they may have an important role in the alteration of cytokines that participate in the inflammatory response. Moreover, a moderate consumption of cocoa-based goods is correlated with an antiinflammatory
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effect. Furthermore, the consumption of 20 g of dark chocolate twice in a week results in the lowering of the C-reactive protein levels (Allgrove and Davison, 2014).
15.7.5 Antiplatelet Activity One of the main reason for atherosclerotic disease such as acute myocardial infarct, stroke, and peripheral arterial occlusion are platelet dysfunction. In vitro and in vivo studies have demonstrated that cocoa polyphenols possess antithrombotic effects, decreasing platelet activation, aggregation, and adhesion. Meaningful antiplatelet activity was observed in consumers of flavanol-rich cocoa drinks. These beverages must contain around 600 and 900 mg of flavanol content (Aprotosoaie et al., 2016).
15.7.6 Chemoprevention The chemopreventive potential of cocoa, cocoa-derived products, and cocoa polyphenols has been explored in several in vitro and in vivo studies. Cell culture studies focused on the evaluation of the anticarcinogenic properties and elucidation of the molecular mechanisms, whereas the in vivo cancer preventive effects were demonstrated in various animal models of carcinogenesis, human interventional, or epidemiological trials (Martin et al., 2013). Several cancer cell lines were tested and the results indicated that cocoa polyphenols have antioxidant, antiinflammatory, proapoptotic, antiproliferative, antiangiogenetic, and antimetastatic effects.
15.7.7 Neuroprotection Experimental data suggest that cocoa polyphenols have neuroprotective, neuromodulatory, and neurorescue activities. All these properties are proven beneficial in the treatment of aging and neurodegenerative diseases. Cocoa polyphenols possess several advantages with regard to neuroprotection: (i) they cross the blood-brain barrier, (ii) increase the cerebral blood flow, (iii) stimulate brain perfusion, (iv) reduce the cerebral edema, (v) promote the neuronal survival and synaptic plasticity, and (vi) improve neuronal function and different kinds of visual and cognitive tasks (Nehling, 2013).
15.8 Conclusions The T. cacao L. Tree is characterized as being a petit evergreen tropical and subtropical tree originated from the neotropical rainforests. In ancient Central America, Mayans and Aztecs used to cultivate cacao trees in order to use their seeds to prepare “chocolatl,” the first chocolate-based beverage.
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Cocoa has to be consumed in large amounts in order to experience a stimulating effect. The chocolate flavor is obtained by processing the beans, which contains two complex procedures that change their initial chemical and physical features. The initial stage includes fermentation and drying processes, while the second one is based on the composition of the end product. The later includes the following methods: roasting, alkalization, and conching. The chocolate flavor is obtained by processing the beans, which contains two complex procedures that change their initial chemical and physical features. The initial stage includes fermentation and drying processes, while the second one is based on the composition of the end product. The later includes the following methods: roasting, alkalization, and conching. Known under different names, chocolate tea, drinking chocolate, or just cocoa is a heated beverage that has as main components chocolate (shaved, melted, or powder), heated milk or water, and usually a sweetener. “Drinking chocolate” is basically hot chocolate, but made with melted chocolate. It is distinctive due to its thicker texture and lesser sweetness. Due to high polyphenol levels, cocoa has attracted increased attention from nutritional and pharmacological viewpoints. It shows promising antioxidant, cardioprotective, neuroprotective, and chemopreventive potential.
References Aculey, P.C., Snitkjaer, P., Owusu, M., Bassompiere, M., Takrama, J., Norgaard, L., Petersen, M.A., Nielsen, D.S., 2010. Ghanaian cocoa bean fermentation characterized by spectroscopic and chromatographic methods and chemometrics. J. Food Sci. 75 (6), S300–S307. Afoakwa, E.O., Peterson, A., Fowler, M., Ryan, A., 2008. Flavor formation and character in cocoa and chocolate: a critical review. Crit. Rev. Food Sci. Nutr. 48, 840–857. Allgrove, J., Davison, G., 2014. Dark chocolate/cocoa polyphenols and oxidative stress. In: Ross Watson, R., Preedy, V.R., Zibadi, S. (Eds.), Polyphenols in Human Health and Disease. Academic Press, Waltham, pp. 241–249. Aprotosoaie, A.C., Simon Vlad Luca, S.V., Miron, A., 2016. Flavor chemistry of cocoa and cocoa products—an overview. Compr. Rev. Food Sci. Food Saf. 15, 73–91. Arranz, S., Valderas-Martinez, P., Chiva-Blanch, G., Casas, R., Urpi-Sarda, M., LamuelaRaventos, R.M., Estruch, R., 2013. Cardio protective effects of cocoa: clinical evidence from randomized clinical intervention trials in humans. Mol. Nutr. Food Res. 57, 936–947. Baharum, Z., Akim, A.M., Hin, T.Y.Y., Hamid, R.A., Kasran, R., 2016. Theobroma cacao: review of the extraction, isolation, and bioassay of its potential anti-cancer compounds. Trop. Life Sci. Res. 27 (1), 21–42. Barrera, M.A., Gomez-Pompa, A., Vazquez, C., 1977. El manejo de las selvas por los mayas: sus implicaciones agricolas. Biotica 2, 57–60. Belitz, H.-D., Grosch, W., Schieberle, P., 2009. Food Chemistry, fourth revised and extended edition. Springer-Verlag, Berlin, Heidelberg, pp. 959–966.
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Belščak, A., Komes, D., Horžić, D., Ganić, K.K., Karlović, D., 2009. Comparative study of commercially available cocoa products in terms of their bioactive composition. Food Res. Int. 42 (5–6), 707–716. Burleigh, R., 2002. Chocolate: Riches From the Rainforest. Harry N. Abrams, Ins., Publishers, Chicago. Carr, M.K.V., Lockwood, G., 2011. The water relations and irrigation requirements of cocoa (Theobroma cacao L.): a review. Expl. Agric. 47 (4), 653–676. Cheesman, E.E., 1944. Notes on the nomenclature, classification and possible relationships of cacao populations. Trop. Agric. 21, 144–159. Cooper, K.A., Donovan, J.L., Waterhouse, A.L., Williamson, G., 2008. Cocoa and health: a decade of research. Br. J. Nutr. 99 (1), 1–11. Corti, R., Flammer, A.J., Hollenberg, N.K., Lüscher, T.F., 2009. Cocoa and cardiovascular health. Circulation 119 (10), 1433–1441. Crozier, S.J., Hurst, W.J., 2014. Cocoa polyhenols and cardiovascular health. In: Ross Watson, R., Preedy, V.R., Zibadi, S. (Eds.), Polyphenols in Human Health and Disease. Academic Press, Waltham, pp. 1077–1082. D’Archivio, M., Santangelo, C., Scazzocchio, B., Varì, R., Filesi, C., Masella, R., Giovannini, C., 2008. Modulatory effects of polyphenols on apoptosis induction: relevance for cancer prevention. Int. J. Mol. Sci. 9 (3), 213–228. Dillinger, T.L., Barriga, P., Escárcega, S., Jimenez, M., Salazar Lowe, D., Grivetti, L.E., 2000. Food of the gods: cure for humanity? A cultural history of the medicinal and ritual use of chocolate. J. Nutr. 130 (8S Suppl), 2057S–2072S. Duke, J.A., 1983. Theobroma cacao L. Handbook of Energy Crops. (Unpublished) https:// www.hort.purdue.edu/newcrop/duke_energy/Theobroma_cacao.html#Uses. Edwards, D.F., 1973. Pollination studies on Upper Amazon cocoa clones in Ghana in relation to the production of hybrid seed. J. Hortic. Sci. 48, 247–259. Faria, A., Calhau, C., de Freitas, V., Mateus, N., 2006. Procyanidins as antioxidants and tumor cell growth modulators. J. Agric. Food Chem. 54 (6), 2392–2497. Giacometti J., Jolić S. M., Josić D., 2015. Cocoa processing and impact on composition. In: Preedy VR editor. Processing and Impact on Active Components in Food London/Waltham/San Diego: Academic Press. 605–12. Gomez-Pompa, A., Flores, S., Sosa, V., 1987. The “Pet Kot”: a man-made tropical forest of the Maya. Interciencia 12, 10–15. Grivetti, L.E., Shapiro, H.-Y., 2009. Chocolate: History, Culture, and Heritage. John Wiley and Sons, Hoboken, NJ, 345. Kang, N.J., Lee, K.W., Lee, D.E., Rogozin, E.A., Bode, A.M., Lee, H.J., Dong, Z., 2008. Cocoa procyanidins suppress transformation by inhibiting mitogen-activated protein kinase kinase. J. Biol. Chem. 283 (30), 20664–20673. Kim, J., Lee, K.W., Lee, H.J., 2011. Cocoa (Theobroma cacao) seeds and phytochemicals in human health. In: Preedy, V., Vatson, E.E., Patel, V.B. (Eds.), Nuts and Seeds in Health and Disease Prevention. Academic Press, London, pp. 351–360. Kim, J.E., Song, D., Kim, J., Choi, J., Kim, J.R., Yoon, H.S., Bae, J.S., Han, M., Lee, S., Hong, J.S., Song, D., Seong-Jin Kim, S.J., Son, M.J., Choi, S.W., Chung, J.H., Kim, T.A., Lee, K.W., 2016. Oral supplementation with cocoa extract reduces UVB-induced wrinkles in hairless mouse skin. J. Investig. Dermatol. 136, 1012–1021. Kothe, L., Zimmermann, B.F., Galensa, R., 2013. Temperature influences epimerization and composition of flavanol monomers, dimers and trimers during cocoa bean roasting. Food Chem. 141, 3656–3663. Lagunes Gálvez, S., Loiseau, G., Paredes, J.L., Barel, M., Guiraud, J.P., 2007. Study on the microflora and biochemistry of cocoa fermentation in the Dominican Republic. Int. J. Food Microbiol. 114 (1), 124–130. https://doi.org/10.1016/j.ijfoodmicro.2006.10.041. Mid:17187887. Lamuela, R.M., Andrés-Lacueva, C., Permanyer, J., Izquierdo-Pulido, M., 2001. More antioxidants in cocoa. J. Nutr. 131, 834.
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Leite, P.B., Maciel, L.F., Dpretzka, L.C.F., Soares, S.E., Bispo, E.S., 2013. Phenolic compounds, methylxantines and antioxidant activity in cocoa mass and chocolates produced from “witch broom disease” resistant and non resistant cocoa cultivars. Cienc. Agrotecnol. 37 (3), 244–250. https://doi.org/10.1590/S1413-70542013000300007. Lopez, A.S., 1986. Chemical changes occurring during the processing of cacao. In: Proceedings of the Symposium Cacao Biotechnology, Pennsylvania. University Park, The Pennsylvania State University, Pennsylvania, pp. 19–54. Martin, M.A., Goya, L., Ramos, S., 2013. Potential for preventive effects of cocoa and cocoa polyphenols in cancer. Food Res. Int. 56, 336–351. Maskarinec, G., 2009. Cancer protective properties of cocoa: a review of the epidemiologic evidence. Nutr. Cancer 61 (5), 573–579. McShea, A., Ramiro-Puig, E., Munro, S.B., Casadesus, G., Castell, M., Smith, M.A., 2008. Clinical benefit and preservation of flavonols in dark chocolate manufacturing. Nutr. Rev. 66 (11), 630–641. Merkus, H.G., 2014. Chocolate. In: Merkus, H.G., GMH, M. (Eds.), Particulate Products: Tailoring Properties for Optimal Performance. Springer International Publishing, Heidelberg/New York/Dordrecht/London, pp. 253–272. Meydani, S.N., Meydani, M., Blumberg, J., Leka, L.S., Pedrosa, M., Diamond, R., Schaefer, E.J., 1998. Assessment of the safety of supplementation with different amounts of vitamin E in healthy older adults. Am. J. Clin. Nutr. 68, 311–318. Nehling, A., 2013. The neuroprotective effects of cocoa flavanol and its influence on cognitive performance. Br. J. Clin. Pharmacol. 75, 716–727. Niemenak, N., Cilas, C., Rohsius, C., Bleiholder, H., Meier, U., Lieberei, R., 2009. Phenological growth stages of cacao plants (Theobroma sp.): codification and description according to the BBCH scale. Ann. Appl. Biol. 156, 13–24. Othman, A., Ismail, A., Abdul Ghani, N., Adenan, I., 2007. Antioxidant capacity and phenolic content of cocoa beans. Food Chem. 100 (4), 1523–1530. Ramli, N., Hassan, O., Said, M., Samsudin, W., Idris, N.A., 2006. Influence of roasting conditions on volatile flavor of roasted Malaysian cocoa beans. J. Food Process. Preserv. 30, 280–298. Ramljak, D., Romanczyk, L.J., Metheny-Barlow, L.J., Thompson, N., Knezevic, V., Galperin, M., Ramesh, A., Dickson, R.B., 2005. Pentameric procyanidin from Theobroma cacao selectively inhibits growth of human breast cancer cells. Mol. Cancer Ther. 4 (4), 537–546. Saltini, R., Akkerman, R., Frosch, S., 2013. Optimizing chocolate production through traceability: a review of the influence of farming practices on cocoa bean quality. Food Control 29, 167–187. Sánchez, D., Moulay, L., Muguerza, B., del Mar Quiñones, M., Miguel, M., Aleixandre, A., 2010. Effect of a soluble cocoa fiber-enriched diet in Zucker fatty rats. J. Med. Food 13 (3), 621–628. Sánchez-Rabaneda, F., Jáuregui, O., Casals, I., Andrés-Lacueva, C., Izquierdo-Pulido, M., Lamuela-Raventós, R.M., 2003. Liquid chromatographic/electrospray ionization tandem mass spectrometric study of the phenolic composition of cocoa (Theobroma cacao). J. Mass Spectrom. 38, 35–42. Trivedi, B.P., 2002. Ancient chocolate found in Maya “teapot”. Natl. Geogr. Today. Electronic document, http://news.nationalgeographic.com/news/2002/07/0717_020717_TV chocolate.html. (accessed April 2, 2018).
Further Reading Gomez-Pompa, A., 1987. On Maya silviculture. Mex. Stud. 3, 1–17. Gomez-Pompa, A., Flores, J.S., Fernandez, M.A., 1990. The sacred cacao groves of the Maya. Lat. Am. Antiq. 1 (3), 247–257.
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https://en.wikipedia.org/wiki/Banania. https://en.wikipedia.org/wiki/Bicerin. https://en.wikipedia.org/wiki/Bournvita. https://en.wikipedia.org/wiki/Caff%C3%A8_mocha. https://en.wikipedia.org/wiki/Champurrado. https://en.wikipedia.org/wiki/Choc-Ola. https://en.wikipedia.org/wiki/Chocolate_liqueur. https://en.wikipedia.org/wiki/Chocolate_milk. https://en.wikipedia.org/wiki/Cola_Cao. https://en.wikipedia.org/wiki/Egg_cream. https://en.wikipedia.org/wiki/Marocchino. https://en.wikipedia.org/wiki/Milo_(drink. https://en.wikipedia.org/wiki/Nesquik. https://en.wikipedia.org/wiki/Ovaltine. https://en.wikipedia.org/wiki/P%C3%B3po. https://en.wikipedia.org/wiki/Pinolillo. https://en.wikipedia.org/wiki/Pozol. https://en.wikipedia.org/wiki/Pucko. https://en.wikipedia.org/wiki/Tascalate. https://en.wikipedia.org/wiki/Tejate. https://worldstandards.eu/chocolate%20-%20cacao.htm. https://worldstandards.eu/chocolate%20-%20cacao.html.
15
Genţiana Mihaela Iulia Predan⁎, Daniela Anca Lazăr⁎, Iulia Ioana Lungu† ⁎
Department of Botany and Microbiology, University of Bucharest, Bucharest, Romania †Department of Biomaterials and Medical Devices, University Politehnica of Bucharest, Bucharest, Romania
15.1 Introduction Cocoa, as a drink, is consumed as a suspension. In addition to stimulating alkaloids, particularly theobromine, cacao products contain substantial amounts of nutrients: fats, carbohydrates, and proteins. Cocoa has to be consumed in large amounts in order to experience a stimulating effect. In order for one to encounter a stimulating reaction, a large quantity of cacao must be consumed. A very important moment in history has been the discovery of America by Columbus. However, interestingly, in Mexico, as well as Central America, cocoa beans have been known and used for more than a thousand years before the big discovery. In the early 17th century, cocoa beans were imported into Germany. Because of its bitter taste, cacao became well-known only after sugar was added in the chocolate composition (Afoakwa et al., 2008). The components that contribute to the flavor and aroma of chocolate are the polyphenols, which have received much attention due to their beneficial implications to human health by preventing cancer, cardiovascular diseases, and other pathologies (Cooper et al., 2008).
15.2 General Description The tropical tree Theobroma cacao L., known as cacao or cocoa, belongs to the family Sterculiaceae, order Malvales (Baharum et al., 2016). In ancient Central America, Mayans and Aztecs used to cultivate cacao trees in order to use their seeds to prepare “chocolatl,” the first Caffeinated and Cocoa Based Beverages. https://doi.org/10.1016/B978-0-12-815864-7.00015-5 © 2019 Elsevier Inc. All rights reserved.
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chocolate-based beverage. The T. cacao L. tree is characterized as being a petit evergreen tropical and subtropical tree originated from the neotropical rainforests (Baharum et al., 2016). The height of the cocoa tree can vary between 5 and 15 m. In order to properly grow, the cocoa tree requires a warm and moist climate, with temperatures ranging from 24°C to 28°C and elevations up to 600 m. Because of their sensitiveness to light and wind, they are usually cultivated under the so-called “cacao mothers,” which are basically coconut or banana trees (Fig. 15.1; Belitz et al., 2009). The cacao trees were found growing in the shade of a “typical” Maya forest garden (Barrera et al., 1977) composed of a mixture of useful native species such as Brosimum alicastrum (ramon, osh), Manilkara achras (chak ya', chico zapote), Pouteria campechiana (caniste), Pouteria mammosa (mamey, zapote mamey), Quararibea guatemalensis, Bursera simaruba (chacaj, palo mulato), Ficus sp., Chrysophyllum cainito (caimito), Annona reticulata (oop, anona colorada), Carica papaya (papaya), Sabal yapa (guano), Caesalpinia yucatanensis, and Lonchocarpus xuul among the native species, and
Fig. 15.1 Part of Theobroma cacao L. tree (original image).
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Cocos nucifera (coconut), Citrus spp. (oranges and lemons), and Musa paradisiaca (banana) as the principal introduced species. Similar composition has been found in many other forests of the Maya area in which a mixture of selected native and introduced trees produces an artificial forest garden (Gomez-Pompa et al., 1987). The tree blooms every season. Small red, yellow, or white flowers (Fig. 15.2) are characteristic and bear 20–50 ripe fruits per tree. Cocoa flowers are grouped together in clusters arising directly from the trunk (cauliflory). The ripe fruits resemble a melon and are usually between 15 and 25 cm long and 7–10 cm wide. The fruit, or “cocoa pod,” has a specific red to brown color and a surface covered in knobs and lines all across. In the wild, cocoa trees are pollinated by midges, and only about 5% of flowers receive enough pollen to start fruit development. When pollination occurs, impressive changes can be observed as the flowers evolve into imposing fruits.
Fig. 15.2 Cocoa flowers arising directly from the trunk (cauliflory).
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The floral meristem produces flowers over the tree’s entire life span. However, seasonal variations can be observed during the floral production (Edwards, 1973). The moment when the flower opens and the anthers release their pollen is synchronized every morning in the early hours. Various small insects, including midges (Ceratopogonidae: Forcipomyia), are responsible for pollination. Unfertilized flowers abscise from the stem about 24–36 h after anthesis. Only 0.5%–5% of flowers develop into mature pods (Carr and Lockwood, 2011). Cacao beans are oval-shaped and flattened, about 2 cm long and 1 cm wide, and weigh about 1 g after drying. The embryo has two thick cotyledons (nibs) and a germ rootlet of 5 mm long and 1 mm thick (Belitz et al., 2009). Even though the fruit can be harvested all year round, it is preferentially harvested twice a year. The summer harvest is larger and of a higher quality. The cacao tree starts developing pods roughly after 5–6 years, having a maximum yield after 20–30 years. However, its life span extends up to 40 years of growth. Another main factor in the flavor of cacao beans is the harvesting time (Belitz et al., 2009). When the pods are fully ripened, they are cut down, collected in piles, and cut open in order for the seeds to be scooped out together with the adjacent pulp. Cocoa seedlings exhibit two growth forms: a vertical (orthotropic) stem, known as a chupon, with spiral phyllotaxi, together with three to five lateral (plagiotropic) fan branches (5/8 phyllotaxi). The point from which the buds grow out sideways from the terminal end of the main stem is known as a jorquette. The phenological growth stages of cocoa plants have been described in detail by Niemenak et al. (2009) using the “extended BBCHscale.” Development can be divided into the following principal growth stages: Growth stage 0: seed germination-vegetative propagation. Growth stage 1: leaf development on the main (vertical) stem, and on the fan branches. Growth stage 2: main stem elongation, formation of a jorquette of fan branches and another chupon. Growth stage 3: fan branch elongation. Growth stage 5: inflorescence emergence. Growth stage 6: flowering. Growth stage 7: development of fruit. Growth stage 8: ripening of fruit and seed. Growth stage 9: senescence. (Note, growth stage 4 does not apply to cocoa, it applies only to cereals) (Carr and Lockwood, 2011).
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Traditionally, cocoa is classified according to trade perceptions of its physical and sensory quality and associated botanical traits, albeit imperfectly (Cheesman, 1944). • Criollo: cultivated on a small scale because of its lack of vigor, although the area is currently expanding due to renewed interest in speciality cocoa. • Forastero: the bulk of the world’s cocoa production is from this type. • Trinitario: usually considered to be the result of crosses between the other two types and is not found in the wild. Material designated as Trinitario is grown commercially in the Caribbean and Papua New Guinea (Carr and Lockwood, 2011).
15.3 Processing of Cocoa Beans The chocolate flavor is obtained by processing the beans, which contains two complex procedures that change their initial chemical and physical features. The initial stage includes fermentation and drying processes, while the second one is based on the composition of the end product. The later includes the following methods: roasting, alkalization, and conching (McShea et al., 2008; Aculey et al., 2010, quoted by Aprotosoaie et al., 2016). The cocoa preprocessing steps (harvest, breaking, fermentation, and drying) are important to ensure the high quality of the beans. For Lagunes Gálvez et al. (2007) fermentation is one of the postharvest step that most affect the quality of the products obtained from cocoa (Fig. 15.3).
15.3.1 Fermentation When handling cacao beans, the most important step is fermentation. During fermentation, the pulp is degraded by the successive action of microorganisms, promoting the rise of temperature to about 50°C and the formation of ethanol and lactic acid, driving to the embryo death, which creates an environment for the formation of flavor and aroma precursors of chocolate, developed through roasting process (Lopez, 1986; Leite et al., 2013). Fermentation is a complex process that takes place at different time periods after the pods are collected and opened. The first phase, also called the anaerobic phase, occurs in the first 24–36 h. The beans, as well as the pulp are uncovered and interact with several microorganisms. The pulp has an acidic profile (pH below 4) and generates ethanol in this phase due to alcoholic fermentation of its sugars by yeasts.
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Manually harvesting
Cocoa beans
Fermentation
Drying
Cocoa pods
Cleaning
Roasting
F. precursor formation F. development
F. and color change
Final F.development and texture improvemnent
Conching
CHOCOLATE
Milling
Cocoa liquor, cocoa mass
Blending
Winnowing
Cocoa nibs
Alkalinization
Pressing
COCOA POWDER
COCOA BUTTER
ChocolateͲ flavored products
COCOA BEVERAGES
Fig. 15.3 Schematic representation of the processing of cocoa beans.
Apart from ethanol production, the pulp sugar fermentation process also generates lactic acid, acetic acid, and carbon dioxide. The second phase takes place after 48–96 h and it is characterized by the inhibition of yeast activity due to several factors: (i) aeration, (ii) alcohol concentration, and (iii) pH increase. The later aspect is attained by citric acid depletion and leads to the production of lactic acid bacteria. Acetic acid bacteria have a very important function in the development of flavor precursors. It has been observed that the optimal fermentation period or the formulation of flavor precursors is 6 days (Giacometti et al., 2015). During the anaerobic phase, sucrose is partially hydrolyzed to reducing sugars, proteins undergo proteolysis to peptides and amino acids, and polyphenols are hydrolyzed and oxidized (Aprotosoaie et al., 2016). During the anaerobic phase, several condensation and oxidation reactions take place. For example, when the oxidation and condensation of protein-polyphenol complex and, respectively, carbonyl-amino occur, these reactions reduce the beans bitterness. Color is also a factor that has an effect on the final flavor. A dark gray color is the c haracteristic
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of unfermented, bitter beans, whereas fully fermented beans have a deep brown color (Afoakwa et al., 2008; Aculey et al., 2010).
15.3.2 Drying The bitter taste, acidity, and color of the final beans can also be controlled in the drying phase (Merkus, 2014). The oxidative reactions that take place during the fermentation phase are continued in the drying stage. Several drying techniques have been reported in the literature, however, among them, the most commonly used is sun drying due to its ability to induce a more pronounced chocolate flavor. Moreover, this technique does not give any off-flavors, such as smokey notes, to the final beans, which is one of the main conditions for good quality beans (Afoakwa et al., 2008).
15.3.3 Roasting Roasting is the final step in cocoa beans processing. processing steps fermentation drying cleaning blending thermal pretreatment winnowing roasting The goals of these procedures are to obtain the specific texture of beans, flavor, and the elimination of volatile compounds, such as acetic acid. Moreover, moisture content is decreased up to 1% (Giacometti et al., 2015). During the roasting phase, biogenic amines are formed. These compounds are not volatile and do not have a role in the final products aroma, but they have a significant outcome on the human organisms after they are consumed. Roasting can be carried out through three approaches: whole bean, nib, and liquor roasting. The characteristics of the raw material, its variety, and the specifications of the desired flavor are all important when deciding on the optimal parameters of the roasting method (Ramli et al., 2006). It has been noted that the flavor quality is strictly related to the high degree of roasting. However, overroasting is a negative outcome. The roasting time and temperature must be maintained from 5 to 120 min and between 110°C and 160°C, respectively. The above-mentioned overroasting occurs when the temperature exceeds 160°C and results in a burnt taste of the final product, also known as off-flavor (Saltini et al., 2013; Aprotosoaie et al., 2016). 1. 2. 3. 4. 5. 6. 7. 8.
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15.3.4 Alkalization Alkalization is the treatment of the final cocoa product (mass, liquid, or powder) with alkali. Currently, this method is used for aesthetics and flavor aspects, as well as for increasing the solubility degree of powder-based cocoa in beverages (Giacometti et al., 2015).
15.3.5 Conching Conching is a heat treatment used to determine the final texture and aroma of chocolate. Advantages of this technique include: enhancing the flavor profile, decreasing the concentration of free acids and volatile by-products of the cacao beans (McShea et al., 2008; Giacometti et al., 2015).
15.4 Composition 15.4.1 Proteins and Amino Acids Up to 60% of the total nitrogen volume of fermented beans consists of proteins. The remaining has been established to be made up of amino acids (0.3% amide form and 0.02% as ammonia, formed during the fermentation process) (Belitz et al., 2009).
15.4.2 Theobromine and Caffeine 3,7-Dimethylxanthine, commercially called the bromine, has a similar, yet reduced, effect as caffeine. It is weakly bonded to tannins and released by the acetic acid produced during the fermentation process. Both bromine and caffeine can be found, in small amounts, in cocoa. For example, one cup of cocoa beverage contains 0.1 g of the bromine and 0.01 g of caffeine (Belitz et al., 2009).
15.4.3 Lipids A representative ingredient of cocoa beans is cocoa fat, also known as cocoa butter (Belitz et al., 2009).
15.4.4 Carbohydrates Starch is the predominant carbohydrate. There are several soluble carbohydrates found in cocoa such as stachyose, raffinose, sucrose, glucose, and fructose. During fermentation, sucrose hydrolysis occurs which reduces the sugar content. This has a major effect on the final flavor obtained during the roasting phase. Among the various sugars found in the cacao nib, mesoinositol, phytin, and verbascotetrose can be mentioned (Belitz et al., 2009).
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15.4.5 Phenolic Compounds The nib cotyledons consist of two types of parenchyma cells. The majority of the cells—up to 90%—are smaller in size and consist of protoplasm, starch granules, aleurone grains, and fat globules. Among these small cells, larger cells can be found, which contain phenolic compounds and purines. The polyphenol cells, also known as pigment cells, account for 11%–13% of the whole tissue and are composed of anthocyanins. The later cells have a color range from white to dark purple, depending on their structure. There are three phenol groups found in cacao: (i) catechins— around 37%, (ii) anthocyanins—around 4%, and (iii) leucoanthocyanins—around 58% (Belitz et al., 2009).
15.4.6 Organic Acids About 1.2%–1.6% of organic acids are found in cacao. Of these, citric, acetic, succinic, and malic acid have a significant contribution to the cacao flavor. As mentioned above, these acids are formed during the fermentation phase. The quantity of acetic acid released by the pulp and received by the bean cotyledons has a strict correlation with the fermentation time and the type of drying techniques used (Belitz et al., 2009).
15.4.7 Volatile Compounds and Flavor Substances The cocoa flavor and aroma is strictly dependent on the processing techniques. Unprocessed, fresh beans smell and taste like vinegar. However, improper handling or contamination during the processing stages can lead to low-quality cocoa beans with uncharacteristic taste.
15.5 Uses After cocoa seeds are processed, fat is extracted from the powdery final product. The result is the commercially available product used in the preparation of chocolate and chocolate-based beverages. However, additional processing is made for manufacturing chocolate. The resulted powder is combined with sugar, flavor agents, and extra cocoa fat. Apart from chocolate and beverages, cocoa butter is also used in pastries, sweets, and fabrication of tobacco, soap, and cosmetics (Duke, 1983). Known under different names hot chocolate, chocolate tea, drinking chocolate, or just cocoa, is a heated beverage that has as main components chocolate (shaved, melted, or powder), heated milk or water, and usually a sweetener. “Drinking chocolate” is basically hot
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chocolate, but made with melted chocolate. It is distinctive due to its thicker texture and lesser sweetness (Grivetti and Shapiro, 2009). Mayans referred to hot chocolate as xocōlātl and it was a crucial component of the Aztec culture by 1400 AD (Trivedi, 2002). All around the world, hot chocolate is consumed in various forms. Some examples of names come from Latin America, Italy, Spain, and United States such as “para mesa,” “cioccolata calda,” chocolate a la taza,” and “hot cocoa,” respectively The first coffee shop was opened in 1657 and called Chocolate House. However, chocolate beverages were highly expensive, costing 50–75 pence (~10–15 shillings) a pound (roughly £45–65 in 2016) (Burleigh, 2002). Cornstarch is a widely used as thickening agent for hot chocolate in Europe (mainly Italy and Spain). The Dutch are known for their love for hot chocolate, known as warme chocolademelk, which is served either at home or in cafes. The French prefer serving hot chocolate in the morning, usually accompanied by butter, jam, honey, or Nutella spread on sliced bread which they sometimes dip into the beverage. Germans made a clear difference between hot chocolate made from melted chocolate (Heiße Schokolade Wiener Art) and the one prepared from chocolate powders (Trinkschokolade). It is often served with whipped cream on top. The ingredients for chocolate—cocoa powder and cocoa butter (solids)—are prepared from fermented and roasted cocoa seeds. Typically, a chocolate milk bar consists of 15% cocoa liquor and 20% cocoa powder. The distinctive flavor of chocolate develops during the fermentation process. The fundamental ingredients of chocolate are alkalized cocoa mass, cocoa powder or cocoa butter, sugars, lecithin, and, in the case of milk chocolate, milk powder or crumbs (Merkus, 2014).
15.6 Chocolate Beverages The main chocolate beverages are presented in Table 15.1.
15.7 Health Effects of Cocoa The immune system plays a critical role in the relationship between malnutrition and infection. A way to boost the immune system is to supplement it with antioxidant activity nutrients (Meydani et al., 1998). Cocoa seeds contain a high amount of flavonoids. Low quantities of quercetin, isoquercetin (quercetin-3-O-glucoside), and quercetin3-O-arabinose are also found in cocoa powder. Irrespective of their
Table 15.1 Main Cocoa-Based Beverages Year and Place of the First Commercial Release
First Producer
References/Observations
Name
Main Known Ingredients
Banania
Cocoa, banana flour, cereals, honey, sugar Espresso, drinking chocolate, and whole milk (layered)
1912 (France)
Pierre Lardet
https://en.wikipedia.org/wiki/Banania
~1704 (Turin), Italy
https://en.wikipedia.org/wiki/Bicerin
Bournvita
Malt and chocolate (other original recipe included full-cream milk)
1933, Australia
Traditional Piedmontese product (recognized in 2001) Cadbury
Champurrado
Chocolate, maize flour, water/milk
Precolumbian
Choc-Ola
Chocolate, various recipes
Chocolate liqueur
Sherry, port, chocolate (initially cocoa beans), and sugar
1944, Pennsylvania (United States) Mentioned in France since 1870
Chocolate milk
Chocolate powder, sugar, milk Other ingredients, such as starch, salt. Sometimes: carrageenan, vanilla, or artificial flavoring Sugar, processed cocoa, wheat flour and cola nut, vitamins, Ca, P
Bicerin
Cola Cao
Late 1700s, Ireland
Barcelona (Spain)
Mexican traditional drink Harry Normington, Sr. Popular drink in France in last decades of the 19th century Hans Sloane
Idilia Foods (formerly Nutrexpa)
Discontinued in the UK market in 2008 https://en.wikipedia.org/wiki/ Bournvita https://en.wikipedia.org/wiki/ Champurrado https://en.wikipedia.org/wiki/ Choc-Ola https://en.wikipedia.org/wiki/ Chocolate_liqueur
https://en.wikipedia.org/wiki/ Chocolate_milk
https://en.wikipedia.org/wiki/ Cola_Cao Continued
Table 15.1 Main Cocoa-Based Beverages—cont’d Year and Place of the First Commercial Release
Name
Main Known Ingredients
Egg cream
Milk, carbonated water, and flavored syrup (typically chocolate or vanilla). The drink contains neither eggs nor cream A shot of espresso, cocoa powder, and milk froth Sugar, chocolate, and malt powder mixed with hot or cold water or milk Espresso and hot milk with added chocolate Chocolate-flavored milk Malt extract, sugar, whey, cocoa
New York city
Cornmeal cacao Toasted cacao beans, rice, cinnamon, anise seed, and asquiote Boiled cornmeal, cocoa, and grains Milk, sugar, and chocolate Toasted maize, chocolate, pine nuts, achiote, vanilla, sugar Maize and cacao
Nicaragua Mexico, Veracruz
Marocchino Milo Caffè mocha (mocaccino) Nesquik Ovaltine (Ovomaltine) Pinolillo Pópo Pozol Pucko Tascalate Tejate
First Producer
References/Observations
Initially preferred by Eastern European Jews immigrants
https://en.wikipedia.org/wiki/ Egg_cream
Alessandria, Italia 1934, Sydney, Australia Mocha, Yemen
Thomas Mayne
1948, Switzerland 1904, Switzerland
Nestlé Associated British Foods
1519, Mexico 1954 Sweden Mexico Oaxaca, Mexico
Arla Foods
https://en.wikipedia.org/wiki/ Marocchino https://en.wikipedia.org/wiki/ Milo_(drink) https://en.wikipedia.org/wiki/ Caff%C3%A8_mocha https://en.wikipedia.org/wiki/Nesquik https://en.wikipedia.org/wiki/Ovaltine https://en.wikipedia.org/wiki/Pinolillo https://en.wikipedia.org/ wiki/P%C3%B3po https://en.wikipedia.org/wiki/Pozol https://en.wikipedia.org/wiki/Pucko https://en.wikipedia.org/wiki/ Tascalate https://en.wikipedia.org/wiki/Tejate
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amount, these compounds are considered to have a beneficial effect on the health (Lamuela et al., 2001). Among several other flavonoids found in cocoa powder, the following can be mentioned: hyperoside (quercetin-3-O-galactoside), naringenin, luteolin, apigenin, and some O-glucosides and C-glucosides of these compounds (SánchezRabaneda et al., 2003). The beneficial effects of cacao consumption are associated with human health, especially with the improved condition of the skin (Kim et al., 2016). Cacao provides positive effects on the skin structure and the dermal microcirculation, and its topical preparations are able to protect the skin from the oxidative damages arising from UV radiation (Kim et al., 2016).
15.7.1 Potential Anticancer Compounds Apart from being used as a beverage, cocoa was also used, in ancient times, as a medicinal plant for treating different afflictions. Through the early 17th to 20th centuries, more than 100 medicinal uses of cocoa have been recorded (Europe and New Spain). Some examples are as follows: anemia, mental fatigue, tuberculosis, fever, gout, kidney stones, and even poor sexual appetite (Dillinger et al., 2000). It has been reported that the cocoa bean contains a multitude of phytochemicals and physiologically active compounds. For example, Kim et al. (2011) reported that selected procyanidins present in cocoa inhibited tumorigenesis, tumor growth, and angiogenesis. Due to the high antioxidant activity of cocoa-based products, it can prevent or aid damages generated by genotoxic and epigenetic carcinogens and inhibit the early stages of cancer development (Baharum et al., 2016). The beneficial effects attributed to cocoa-based products have been associated with the flavonoids, polyphenols, and procyanidins that are found in their structure. Several reports have been published on the beneficial effects of cocoa which include antioxidant effects (Othman et al., 2007), protection against cardiovascular disease (Corti et al., 2009), and for cancer treatment (Maskarinec, 2009). It has been reported that flavonoids could inhibit several kinases and transcription factors (TFs) through their biological activities. They have been observed to inhibit agiogenesis, induce apoptosis, and do not proliferate, in in vitro studies (Kang et al., 2008; Faria et al., 2006). The cocoa procyanidins, epicatechin, and catechin have significant antioxidant effects (Belščak et al., 2009). Cocoa may be considered a potential agent in cancer treatment. Polyphenols can alter the general means of action of carcinogenesis through different mechanisms. Specifically, polyphenols can cancel
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out the formation of oxidative stress, thereby aiding to the prevention of cancer evolution. Moreover, polyphenol adjustment of oxidative stress in cancer cell alters signal transduction, activation of redox- sensitive TFs, and the expression of specific genes that induce cell proliferation and apoptosis (D’Archivio et al., 2008). It has been reported that pentameric procyanidin from cocoa trees inhibit breast cancer cells. The mitochondriotoxic molecule F16 has been recently studied with regard to its effects on breast cancer. It has been observed that compounds causing mitochondrial depolarization inhibit the tumor growth of breast cancer cells through G1 arrest, apoptosis, or necrosis, depending on the genetic background of the cell (Ramljak et al., 2005). Due to the high nutritional value of cocoa-based products, studies have recommended cocoa as a potential antiproliferative agent (Baharum et al., 2016).
15.7.2 Cardioprotection Several epidemiological studies on polyphenol-rich cocoa and 70% or above cocoa-based chocolate have indicated that they are complementary with a reduction in the development of stroke, atherosclerosis, coronary artery disease, heart failure, and cardiovascular disease-related mortality (Crozier and Hurst, 2014). There are several explanation for this: an improvement in antioxidant status and endothelial function, modulation of the blood pressure, metabolic and antiinflammatory effects, and inhibition of the platelet activation and aggregation (Kothe et al., 2013).
15.7.3 Effects on Blood Pressure Spontaneously hypertensive rates (SHRs) have been subjected to a single oral intake of cocoa powder containing high levels of procyanidins. The results have shown decreased blood pressure. A soluble cocoa fiber intake over a extended period of time indicated reduced hypertension development in SHR (Sánchez et al., 2010). The effects of cocoa on blood pressure may be more pronounced in younger subjects due to their high vascular reactivity to physiological stimuli (Arranz et al., 2013).
15.7.4 Antiinflamatory Effects One of the leading factors for atherogenesis is chronic inflammation. In vitro studies on cocoa polyphenols have indicated that they may have an important role in the alteration of cytokines that participate in the inflammatory response. Moreover, a moderate consumption of cocoa-based goods is correlated with an antiinflammatory
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effect. Furthermore, the consumption of 20 g of dark chocolate twice in a week results in the lowering of the C-reactive protein levels (Allgrove and Davison, 2014).
15.7.5 Antiplatelet Activity One of the main reason for atherosclerotic disease such as acute myocardial infarct, stroke, and peripheral arterial occlusion are platelet dysfunction. In vitro and in vivo studies have demonstrated that cocoa polyphenols possess antithrombotic effects, decreasing platelet activation, aggregation, and adhesion. Meaningful antiplatelet activity was observed in consumers of flavanol-rich cocoa drinks. These beverages must contain around 600 and 900 mg of flavanol content (Aprotosoaie et al., 2016).
15.7.6 Chemoprevention The chemopreventive potential of cocoa, cocoa-derived products, and cocoa polyphenols has been explored in several in vitro and in vivo studies. Cell culture studies focused on the evaluation of the anticarcinogenic properties and elucidation of the molecular mechanisms, whereas the in vivo cancer preventive effects were demonstrated in various animal models of carcinogenesis, human interventional, or epidemiological trials (Martin et al., 2013). Several cancer cell lines were tested and the results indicated that cocoa polyphenols have antioxidant, antiinflammatory, proapoptotic, antiproliferative, antiangiogenetic, and antimetastatic effects.
15.7.7 Neuroprotection Experimental data suggest that cocoa polyphenols have neuroprotective, neuromodulatory, and neurorescue activities. All these properties are proven beneficial in the treatment of aging and neurodegenerative diseases. Cocoa polyphenols possess several advantages with regard to neuroprotection: (i) they cross the blood-brain barrier, (ii) increase the cerebral blood flow, (iii) stimulate brain perfusion, (iv) reduce the cerebral edema, (v) promote the neuronal survival and synaptic plasticity, and (vi) improve neuronal function and different kinds of visual and cognitive tasks (Nehling, 2013).
15.8 Conclusions The T. cacao L. Tree is characterized as being a petit evergreen tropical and subtropical tree originated from the neotropical rainforests. In ancient Central America, Mayans and Aztecs used to cultivate cacao trees in order to use their seeds to prepare “chocolatl,” the first chocolate-based beverage.
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Cocoa has to be consumed in large amounts in order to experience a stimulating effect. The chocolate flavor is obtained by processing the beans, which contains two complex procedures that change their initial chemical and physical features. The initial stage includes fermentation and drying processes, while the second one is based on the composition of the end product. The later includes the following methods: roasting, alkalization, and conching. The chocolate flavor is obtained by processing the beans, which contains two complex procedures that change their initial chemical and physical features. The initial stage includes fermentation and drying processes, while the second one is based on the composition of the end product. The later includes the following methods: roasting, alkalization, and conching. Known under different names, chocolate tea, drinking chocolate, or just cocoa is a heated beverage that has as main components chocolate (shaved, melted, or powder), heated milk or water, and usually a sweetener. “Drinking chocolate” is basically hot chocolate, but made with melted chocolate. It is distinctive due to its thicker texture and lesser sweetness. Due to high polyphenol levels, cocoa has attracted increased attention from nutritional and pharmacological viewpoints. It shows promising antioxidant, cardioprotective, neuroprotective, and chemopreventive potential.
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Belščak, A., Komes, D., Horžić, D., Ganić, K.K., Karlović, D., 2009. Comparative study of commercially available cocoa products in terms of their bioactive composition. Food Res. Int. 42 (5–6), 707–716. Burleigh, R., 2002. Chocolate: Riches From the Rainforest. Harry N. Abrams, Ins., Publishers, Chicago. Carr, M.K.V., Lockwood, G., 2011. The water relations and irrigation requirements of cocoa (Theobroma cacao L.): a review. Expl. Agric. 47 (4), 653–676. Cheesman, E.E., 1944. Notes on the nomenclature, classification and possible relationships of cacao populations. Trop. Agric. 21, 144–159. Cooper, K.A., Donovan, J.L., Waterhouse, A.L., Williamson, G., 2008. Cocoa and health: a decade of research. Br. J. Nutr. 99 (1), 1–11. Corti, R., Flammer, A.J., Hollenberg, N.K., Lüscher, T.F., 2009. Cocoa and cardiovascular health. Circulation 119 (10), 1433–1441. Crozier, S.J., Hurst, W.J., 2014. Cocoa polyhenols and cardiovascular health. In: Ross Watson, R., Preedy, V.R., Zibadi, S. (Eds.), Polyphenols in Human Health and Disease. Academic Press, Waltham, pp. 1077–1082. D’Archivio, M., Santangelo, C., Scazzocchio, B., Varì, R., Filesi, C., Masella, R., Giovannini, C., 2008. Modulatory effects of polyphenols on apoptosis induction: relevance for cancer prevention. Int. J. Mol. Sci. 9 (3), 213–228. Dillinger, T.L., Barriga, P., Escárcega, S., Jimenez, M., Salazar Lowe, D., Grivetti, L.E., 2000. Food of the gods: cure for humanity? A cultural history of the medicinal and ritual use of chocolate. J. Nutr. 130 (8S Suppl), 2057S–2072S. Duke, J.A., 1983. Theobroma cacao L. Handbook of Energy Crops. (Unpublished) https:// www.hort.purdue.edu/newcrop/duke_energy/Theobroma_cacao.html#Uses. Edwards, D.F., 1973. Pollination studies on Upper Amazon cocoa clones in Ghana in relation to the production of hybrid seed. J. Hortic. Sci. 48, 247–259. Faria, A., Calhau, C., de Freitas, V., Mateus, N., 2006. Procyanidins as antioxidants and tumor cell growth modulators. J. Agric. Food Chem. 54 (6), 2392–2497. Giacometti J., Jolić S. M., Josić D., 2015. Cocoa processing and impact on composition. In: Preedy VR editor. Processing and Impact on Active Components in Food London/Waltham/San Diego: Academic Press. 605–12. Gomez-Pompa, A., Flores, S., Sosa, V., 1987. The “Pet Kot”: a man-made tropical forest of the Maya. Interciencia 12, 10–15. Grivetti, L.E., Shapiro, H.-Y., 2009. Chocolate: History, Culture, and Heritage. John Wiley and Sons, Hoboken, NJ, 345. Kang, N.J., Lee, K.W., Lee, D.E., Rogozin, E.A., Bode, A.M., Lee, H.J., Dong, Z., 2008. Cocoa procyanidins suppress transformation by inhibiting mitogen-activated protein kinase kinase. J. Biol. Chem. 283 (30), 20664–20673. Kim, J., Lee, K.W., Lee, H.J., 2011. Cocoa (Theobroma cacao) seeds and phytochemicals in human health. In: Preedy, V., Vatson, E.E., Patel, V.B. (Eds.), Nuts and Seeds in Health and Disease Prevention. Academic Press, London, pp. 351–360. Kim, J.E., Song, D., Kim, J., Choi, J., Kim, J.R., Yoon, H.S., Bae, J.S., Han, M., Lee, S., Hong, J.S., Song, D., Seong-Jin Kim, S.J., Son, M.J., Choi, S.W., Chung, J.H., Kim, T.A., Lee, K.W., 2016. Oral supplementation with cocoa extract reduces UVB-induced wrinkles in hairless mouse skin. J. Investig. Dermatol. 136, 1012–1021. Kothe, L., Zimmermann, B.F., Galensa, R., 2013. Temperature influences epimerization and composition of flavanol monomers, dimers and trimers during cocoa bean roasting. Food Chem. 141, 3656–3663. Lagunes Gálvez, S., Loiseau, G., Paredes, J.L., Barel, M., Guiraud, J.P., 2007. Study on the microflora and biochemistry of cocoa fermentation in the Dominican Republic. Int. J. Food Microbiol. 114 (1), 124–130. https://doi.org/10.1016/j.ijfoodmicro.2006.10.041. Mid:17187887. Lamuela, R.M., Andrés-Lacueva, C., Permanyer, J., Izquierdo-Pulido, M., 2001. More antioxidants in cocoa. J. Nutr. 131, 834.
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Leite, P.B., Maciel, L.F., Dpretzka, L.C.F., Soares, S.E., Bispo, E.S., 2013. Phenolic compounds, methylxantines and antioxidant activity in cocoa mass and chocolates produced from “witch broom disease” resistant and non resistant cocoa cultivars. Cienc. Agrotecnol. 37 (3), 244–250. https://doi.org/10.1590/S1413-70542013000300007. Lopez, A.S., 1986. Chemical changes occurring during the processing of cacao. In: Proceedings of the Symposium Cacao Biotechnology, Pennsylvania. University Park, The Pennsylvania State University, Pennsylvania, pp. 19–54. Martin, M.A., Goya, L., Ramos, S., 2013. Potential for preventive effects of cocoa and cocoa polyphenols in cancer. Food Res. Int. 56, 336–351. Maskarinec, G., 2009. Cancer protective properties of cocoa: a review of the epidemiologic evidence. Nutr. Cancer 61 (5), 573–579. McShea, A., Ramiro-Puig, E., Munro, S.B., Casadesus, G., Castell, M., Smith, M.A., 2008. Clinical benefit and preservation of flavonols in dark chocolate manufacturing. Nutr. Rev. 66 (11), 630–641. Merkus, H.G., 2014. Chocolate. In: Merkus, H.G., GMH, M. (Eds.), Particulate Products: Tailoring Properties for Optimal Performance. Springer International Publishing, Heidelberg/New York/Dordrecht/London, pp. 253–272. Meydani, S.N., Meydani, M., Blumberg, J., Leka, L.S., Pedrosa, M., Diamond, R., Schaefer, E.J., 1998. Assessment of the safety of supplementation with different amounts of vitamin E in healthy older adults. Am. J. Clin. Nutr. 68, 311–318. Nehling, A., 2013. The neuroprotective effects of cocoa flavanol and its influence on cognitive performance. Br. J. Clin. Pharmacol. 75, 716–727. Niemenak, N., Cilas, C., Rohsius, C., Bleiholder, H., Meier, U., Lieberei, R., 2009. Phenological growth stages of cacao plants (Theobroma sp.): codification and description according to the BBCH scale. Ann. Appl. Biol. 156, 13–24. Othman, A., Ismail, A., Abdul Ghani, N., Adenan, I., 2007. Antioxidant capacity and phenolic content of cocoa beans. Food Chem. 100 (4), 1523–1530. Ramli, N., Hassan, O., Said, M., Samsudin, W., Idris, N.A., 2006. Influence of roasting conditions on volatile flavor of roasted Malaysian cocoa beans. J. Food Process. Preserv. 30, 280–298. Ramljak, D., Romanczyk, L.J., Metheny-Barlow, L.J., Thompson, N., Knezevic, V., Galperin, M., Ramesh, A., Dickson, R.B., 2005. Pentameric procyanidin from Theobroma cacao selectively inhibits growth of human breast cancer cells. Mol. Cancer Ther. 4 (4), 537–546. Saltini, R., Akkerman, R., Frosch, S., 2013. Optimizing chocolate production through traceability: a review of the influence of farming practices on cocoa bean quality. Food Control 29, 167–187. Sánchez, D., Moulay, L., Muguerza, B., del Mar Quiñones, M., Miguel, M., Aleixandre, A., 2010. Effect of a soluble cocoa fiber-enriched diet in Zucker fatty rats. J. Med. Food 13 (3), 621–628. Sánchez-Rabaneda, F., Jáuregui, O., Casals, I., Andrés-Lacueva, C., Izquierdo-Pulido, M., Lamuela-Raventós, R.M., 2003. Liquid chromatographic/electrospray ionization tandem mass spectrometric study of the phenolic composition of cocoa (Theobroma cacao). J. Mass Spectrom. 38, 35–42. Trivedi, B.P., 2002. Ancient chocolate found in Maya “teapot”. Natl. Geogr. Today. Electronic document, http://news.nationalgeographic.com/news/2002/07/0717_020717_TV chocolate.html. (accessed April 2, 2018).
Further Reading Gomez-Pompa, A., 1987. On Maya silviculture. Mex. Stud. 3, 1–17. Gomez-Pompa, A., Flores, J.S., Fernandez, M.A., 1990. The sacred cacao groves of the Maya. Lat. Am. Antiq. 1 (3), 247–257.
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https://en.wikipedia.org/wiki/Banania. https://en.wikipedia.org/wiki/Bicerin. https://en.wikipedia.org/wiki/Bournvita. https://en.wikipedia.org/wiki/Caff%C3%A8_mocha. https://en.wikipedia.org/wiki/Champurrado. https://en.wikipedia.org/wiki/Choc-Ola. https://en.wikipedia.org/wiki/Chocolate_liqueur. https://en.wikipedia.org/wiki/Chocolate_milk. https://en.wikipedia.org/wiki/Cola_Cao. https://en.wikipedia.org/wiki/Egg_cream. https://en.wikipedia.org/wiki/Marocchino. https://en.wikipedia.org/wiki/Milo_(drink. https://en.wikipedia.org/wiki/Nesquik. https://en.wikipedia.org/wiki/Ovaltine. https://en.wikipedia.org/wiki/P%C3%B3po. https://en.wikipedia.org/wiki/Pinolillo. https://en.wikipedia.org/wiki/Pozol. https://en.wikipedia.org/wiki/Pucko. https://en.wikipedia.org/wiki/Tascalate. https://en.wikipedia.org/wiki/Tejate. https://worldstandards.eu/chocolate%20-%20cacao.htm. https://worldstandards.eu/chocolate%20-%20cacao.html.