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168 Textbook of Pharmacognosy
Stearic acid or octadecanoic acid CH3(CH2)16COOH or (C18H36O2)
Linoleic acid or octadecadienoic acid (C18H32O2)
Linolenic acid or octadecatrienoic acid
(CH2CH=CH)3(CH2)7COOH or (C18H30O2)
CH
3
Oleic acid or octadecenoic acid CH3(CH2)7CH=CH(CH2)7COOH
or (C18H34O2)
History of Linseed Oil
Common flax was one of the first crops domesticated by man, and is thought to have originated in the Mediterranean region of Europe. Archeological remains indicate that several plants were first cultivated almost about the same time in Mesopotamia which included flax, emmer wheat, barley, einkorn wheat, peas, lentils, chickpeas and bitter vetch. The people of the Stone Age living near the Swiss Lake produced flax and utilised the fibre and the seed. The linen cloth made from flax was used to wrap the mummies in the early Egyptian tombs (5000 BC). The Babylonians were the earliest people to cultivate flax as a source of food and irrigation ditches were formed along the Tigris and Euphrates rivers of the Fertile Crescent (2000 BC) to ensure a good water supply for the flax fields. Homer (8th century BC) in his epic poem, the Iliad, wrote that linen was used for cord and sail-cloth and this was an indication that the Greeks cultivated flax plants and also consumed the seeds. The ‘Father of Medicine’, Hippocrates (460–377 BC), also recognised the medicinal value of flax in relieving many intestinal disorders upon prescription to patients. The early colonists in the United States grew flax for their home use. The plant has been known to be cultivated for its seed since very ancient times and it is one of the oldest cultivated plants known to man. The 8th century King of France, Charlemagne regarded flax very highly for its health benefits and
Systematic Pharmacognostic Study of Lipids 169
also made a detailed entry pertaining to the cultivation and use of flax for food and medicine in his medical law books and also ordered his subjects to consume it to maintain good health and also to prevent disease. The excavations of the most ancient Egyptian tombs have come up with flax seeds as well as the flax fibre cloth woven from the plant. The commercial production of flax began in 1753. Even today, few still grow flax to make linen for their own use. The first linen mentioned in the Bible was spun from flax according to historians and archaeologists. The linseed oil has been used medicinally by human societies since pre-history. It is believed that the first ancestors of the human race as long ago as 8500 years ago, ate the flax and some wild grasses as a part of their diet. In ancient times, the diet of early humans contained every part of the flax plant.
The plant has been cultivated for its fibre, for at least five millennia. The wall paintings of ancient Egypt depicted the spinning and weaving of linen. The flax fibre was processed into a fine white fabric as early as 3000 BC and this was used to wrap the mummies of the ancient Egyptian Pharaohs. It has been also used as a cool and comfortable fiber in the middle east for centuries, as mentioned several times in the Bible. It was also greatly valued as a commodity by Ancient Greeks and Romans. The flax has been introduced to Northern Europe by Finnish traders. It was known that the ‘Father of the
Nation’, Mahatma Gandhi once said, ‘whenever flax seeds become a regular food item among the people, there will be better health’. Flax is the emblem of Northern
Ireland used by its Assembly. It also appeared on the reverse of the British one pound coin to represent Northern Ireland in 1986 and 1991. Flax is also seen on the badge of the Supreme Court of the United Kingdom representing the Northern Ireland. Common flax is also the national flower of Belarus.
Medicinal Uses
The oil is used in liniments and also as a demulcent, emollient and laxative. The oil is also an expectorant, diuretic. The seeds are aphrodisiac and the roasted seeds are astringent. The mucilage from the seed extracted by cold water is used for the irritable conditions of conjunctiva of the eye. Along with honey it is used for cough and colds. The powdered seed cake is called Linum contusum is popular as linseed meal. The poultice of the meal is used as a soothing application to ulcerated and inflammed surfaces, boils, carbuncles, abscesses, etc. It is also used as a mild counter-irritant for the deep seated inflammations like pneumonia, bronchitis, broncho­pneumonia, pleuritis, pericarditis, peritonitis, arthritis, pelvic cellulitis, etc. Linseed oil is prescribed internally in ‘painter’s colic’, piles and a good laxative. With lime water in equal proportions, it is a popular remedy for burns and scalds as ‘carron oil’. The infusion of the seed called linseed tea with licorice and sugar is internally used as a demulcent in cold, cough, bronchitis, irritations of urinary organs, cystitis, gonorrhoea, stranguary, as injection to the vagina, bladder and the rectum.
170 Textbook of Pharmacognosy
Other Uses
In addition, the stem fibres find a use in the manufacture of linen cloth. The best quality lint is made from the retted and finely carded fibre. Linseed oil is used as an impregnator in varnish and wood furnishing, as a pigment binder in oil paints, as a plasticiser and hardener in putty and in the production of linoleum. It is edible but is a minor constituent of nutrition because of its strong odour. It is also used as a traditional protective coating for the raw willow of cricket bats, for cue shafts (billiards) and surf boards.
Adulteration
The common adulterants are corn meal, wheat middlings, cake meal and foreign weed seeds. It is also adulterated with cotton seed oil, sunflower oil, resin, mineral oils, mustard oil and fish oils.
COCOA BUTTER
Synonyms
Theobroma oil, Cacao butter, Butter of cacao, Oleum Theobromatis, Butyrum Cacao, Oleum concretum e Semine Theobromae Cacao, Beurre de Cacao (French), Kakao butter (German).
Synonyms for Cocoa
Cocoa plant, chocolate tree, Chocolate, cocoa, Nicaraguan cocoa shade (English), Cacaoboom (Dutch), Kakao (Finnish and Swedish), Cacaoyer, Cacaotier, Cacao (French), Kakaobaum, Kakaopflanze (German), Cacao amarillo, cacao criollo, Cacao forastero (Spanish), Keke shu (Chinese), Cacau (Portuguese), Coklat (Indonesian), Maikona gaha (Sinhalese), Kona maram, Kakkavo (Tamil), Kokkoo (Malayalam), Kho kho (Thai), Kokoe (Burmese), Pokok coklat (Malaysian), Planta del cacao (Italian).
Biological Source
Cocoa butter is a fixed oil (fat) extracted from the roasted seeds (cacao beans—about 40–50%) of Theobroma cacao L. (Family: Sterculiaceae). Theobroma in Latin means the ‘food of the Gods’.
Theobroma cacao
—fruits
Mature fruits of cacao
Systematic Pharmacognostic Study of Lipids 171
Single fruit-unripe Ripe fruits—different stages
Dry fruits and beans
Cocoa beans
Cocoa chocolate
Split opened fruit
172 Textbook of Pharmacognosy
Geographical Source
Cocoa is produced in Ecuador, Colombia, Brazil, Venezula, Guiana, West Indies, Indonesia, Malaysia, Dominican Republic (outside Africa) and Cameroon, Nigeria, Ivory Coast and Ghana (West Africa).
Collection and Preparation
The cocoa seeds are separated from the pods and are allowed to ferment wherein the seeds change their colour from white to dark reddish-brown due to enzymatic reaction (chocolate liquor). Fermentation occurs in tubs, boxes or cavities in the earth, the process lasts 3–9 days, and the temperature is not allowed to rise above 60°C. The seeds are then roasted at 100–140°C, when they lose water and acetic acid and acquire their characteristic odour and taste. Roasting facilitates removal of seed coat. The seeds are cooled as rapidly as possible and testa removed by a ‘nibbling’ machine. The nibs or kernels are separated from the husk by winnowing. The kernels are then fed to hot rollers which yield a pasty mass containing cocoa butter. This is further purified to give cocoa butter. Butter can also be extracted by the broma process. Finally, it is deodourised to remove its undesirable taste.
Characters
Cocoa butter is a yellowish white or a pale-yellow pure, edible vegetable fat that has a mild chocolate flavour and aroma and bland chocolate-like taste. It is brittle at temperatures below 25°C. It melts between 35 and 37°C. The refractive index of the butter is 1.44556–1.44573. It has an iodine value of 34.8, an acid value of 1.68 and saponification value of 197.7. The oil is freely soluble in ether, chloroform and benzene and boiling dehydrated alcohol and slightly soluble in 95% alcohol. Its saponification value is not less than 188 and not more than 195. Its iodine value is not less than 33 and not more than 38. The butter displays polymorphism with crystals possessing different melting points.
Cocoa butter Cocoa powder—as flakes
Systematic Pharmacognostic Study of Lipids 173
Raw cocoa nibs Cocoa powder
Chemical Constituents
The solid fixed oil consists chiefly of the glycerides of oleic, stearic and palmitic acids. Because of its high content of oleostearin, it is also used as a source of stearic acid. It is one of the stable fats known which contains natural antioxidants that prevent rancidity. The percentage of the constituents—non-saponifiables is 0.2–0.4%, total saturated fats is 57–64%, free fatty acids is 1.08%, total monosaturated fats is 29–43% and total polysaturated fats is 1–5%. The main fatty acids of the butter are represented by oleic acid (29–38%), palmitic acid (22–29%), linoleic acid (1–4%), stearic acid (24–37%), capric acid (0–10%), myristic acid (0–4%), arachidic acid (1%), palmitoleic acid (0–2%), and linolenic acid (0–1%).
Capric acid or decanoic acid CH3(CH2)8COOH or (C10H20O2)
Arachidic acid or eicosanoic acid CH3(CH2)18COOH or (C20H40O2)
History of Cocoa
Cocoa butter has been used for centuries in Africa for its moisturising properties and healing properties, where it has been used to protect and also condition the skin which has been damaged by the sun and the wind. Cocoa tree was originally named kakawa and according to historical records; the people of Mesoamerican civilisation along the Mexican Gulf coast cultivated the tree in 1000 BC. They used the beans for making drinks for
174 Textbook of Pharmacognosy
consumption by the elite class. Later, the tree came to be known as cacao from proto-Mixe-Zoqueqn family of languages, during Olmec civilisation (1150–300 BC). Later, this culture moved to Mayan civilisation by the Izapan civilisation of the lowlands of Chialas of Mexico, Peten of Guatemala and Belize. Historians believe that the word, chocolate or chocolatl originate from the Nahuatl word, xocoatl or cacahuatl meaning ‘bitter water’. Some believe that it is a combination of the Mayan words, choco and haa and the Nauhatl term, atl which resulted in the term ‘chocolate’. There is also another theory according to linguists that the word chicolatl originated from the word, chico-li meaning ‘to beat’ or ‘to stir’ and not chocoatl. It was a Swedish who gave the cocoa plant its binomial, Theobroma cacao which literally meant the ‘food of the Gods’. During 450–500 AD, clay vessels were made for drinking the chocolate, as a status symbol by Mayans. At the end of Mayan civilisation (200 BC to 1550 AD) cocoa beans had become a major Mesoamerican commodity. We know that chocolates are made from cocoa beans that have been cultivated for millions of years in the South American rainforests. The archaeological surveys account for the physical residues of chocolate in some Mayan pots which suggest that Mayans drank chocolate some 2600 years ago. It is also believed that the cocoa plant was cultivated in the Amazon for more than 4000 years. Archaeological evidence comes from the recovery of cocoa beans at Uaxactun, Guatemala (1947) and also from the preserved wood fragments of the cocoa tree at Belize sites (1981) and Pulltrouser area (1984). Similarly, the residue analysis from the ceramic vessels from an early classic period (460–480 AD) tomb at Rio Azul in North-Eastern Guatemala has revealed the presence of theobromine and caffeine. History also accounts for the worshipping of the cocoa tree by the Mayans and Aztecs who offered chocolate to the God as an offering. The cocoa beans were brewed along with maize and capsicum which resulted in a spicy bitter-sweet drink which after fermentation was used for the ceremonies by Aztecs (1500 AD). Aztecs also treated cocoa beans as currency and paid their taxes too, and the beans were used as a currency throughout Mesoamerica by the time the Aztec empire fell (1376–1520 AD). Mythically, the cocoa tree has been linked to Quetzacoatl, the God of agriculture of Mexicans. Chocolate came to Europe in the 16th century by a Spanish explorer, Don Hernan Cortes (1519). The tradition of drinking hot chocolate began in Spain where the drink was served to travelers and was a common drink with the nobility. Christopher Columbus introduced the chocolate into Spain (1502). The cocoa tree was introduced to the Asia in 1560 and to the Africa in 1590. The chocolate was served in the Spanish court during 1600 to 1650 and it arrived in London in 1657. Later, the drink entered France, and was introduced to England in the 17th century by Sir Hans Sloane. Initially, the brew was sold as medicine by apothecaries in England. C. J. Van Houton, a Dutch chocolate master invented the ‘cocoa press’ (1828) which helped to squeeze out cocoa butter from the beans
Systematic Pharmacognostic Study of Lipids 175
through an alkalising process called ‘dutching’. The first large scale production of chocolate bar was by J. S. Fry and Sons who introduced the use of cocoa powder (1847). Later, in 1853, it was Cadburys who manufactured the chocolate and became the supplier to Queen Victoria, and emerged as one of the leading chocolate manufacturers in the world as we know it today. The milk chocolate was introduced into the market by Henri Nestle and Daniel Peter (1879) in Switzerland by blending cocoa powder and condensed milk along with cocoa butter and cocoa solids.
Medicinal Uses
Cocoa butter has nutritive, stimulant, antiseptic and diuretic properties. The oil is used pharmaceutically in the making of suppositories and also as excipient for pills (oral medicine in capsule form) and as an emollient it is an ingredient of many products in cosmetics, soaps and lotions. It is also recommended as a moisturiser for the prevention of stretch marks in pregnant women, in the treatment of chopped skin and lips. It is a natural preservative. Theobromine in the butter is a diuretic. It is used to prepare biscuits, chocolate, bakery products, pharmaceuticals, ointments and toiletries. It is an additive in cosmetics, shampoos and soaps. It is used to add flavour, scent and smoothness to chocolate, tanning oil, topical lotions, creams and soap. It is used in conditions of eczema and dermatitis as it helps as a barrier between the skin and the environment and also helps in retaining the moisture (body care lotions and moisturisers). The butter also contains cocoa mass polyphenol (CMP) which inhibits the production of immunoglobulin IgE known to aggravate the symptoms of dermatitis and asthma. Butter when used in massaging the skin helps relieve stress, boost the immune system and inhibits the growth of cells of cancer and tumours in addition to preventing the heart disease and eases the arthritis and helps treating conditions such as psoriasis, fibromyalgia and chronic fatigue syndrome according to recent research. The butter is rich in vitamin E which helps to soothe, hydrate and balance the skin and provides collagen assisting with wrinkles (stretch marks in pregnant women) and signs of ageing. The butter is a folk remedy for burns, cough, dry lips, fever, malaria, rheumatism, snake bite and wounds.
Adulteration
Wax, stearin and tallow are the common adulterants in cocoa butter. Mano kernel oil is used as a substitute.
Alternative to Cocoa Butter
The global production of cocoa is in decline due to the failure of the crop, diseases and aging plantations which lead to fluctuations in the price and the necessity for the cocoa industry to find high quality cocoa butter
176 Textbook of Pharmacognosy
alternatives. The studies in this direction explore the potential of a wild mango, Mangifera sylvatica, an under-utilised fruit in South-East Asia, as a new cocoa butter alternative (CBA). The analysis showed that the wild mango butter has a light coloured fat with a similar fatty acid profile (palmitic acid, stearic acid and oleic acid) and triglyceride profile (POP [1,3-dipalmitoyl-2-oleoyl-glycerol], SOS [1,3-distearoyl-2-oleoyl-glycerol] and POS [1-palmitoyl-2-oleoyl-3-stearoyl-glycerol]) to cocoa butter. The thermal and physical properties of CBA are also similar to cocoa butter. In addition, wild mango butter comprises 65% SOS (1,3-distearoyl-2-oleoyl­glycerol) which indicates its potential to become a Cocoa Butter Improver (an enhancement of CBA).
KOKUM BUTTER
Synonyms
Goa butter, Kokum oil, Mangosteen oil, Black kokum, Cocum (French, Spanish and Italian), Kokam (German), Kokum butter (Indian).
Synonyms for Garcinia
Red mango, Mate mangosteen, Indian berry, Indian tallow tree (English), Kokam, Bhirand kokum (Hindi), Birandel ratamba, Kokambel, Kokan (Gujarati and Maharashtrian), Murgal mara (Tamil), Murgina-huli-mara, Dhupadamara, Murgala, Murginahalli, Punarpuli, Ratambi (Kannada), Punampuli (Malayalam), Beerunda (Konkani), Brindao (pulp of the fruit) or Amsel (bark of the tree) or Ratambasal (Goanese), Vrikshamla, Vrichhamala (Sanskrit), Bhirand, Kokam, Kokambi (Marathi), Kokkam (Malayalam), Garushinia indika (Japanese), Brindonnier (French).
Biological Source
Kokum butter is the fat expressed from the seeds of Garcinia indica (=Garcinia purpurea), (Family: Clusiaceae=Guttiferae). The genus Garcinia is named
after Laurentiers (Jacques) Garcin (1673–1751), a French explorer, physician
Garcinia indica
Fruits
Systematic Pharmacognostic Study of Lipids 177
and a priest who lived in India and collected it as well as first described it. He wrote the first article on the medicinal properties of the fruit in 1697.
Geographical Source
The plant is indigenous to Thailand, Cambodia and China. The plant is a native to the western coastal region of Southern India. In India it grows in the evergreen forests of Konkan (Mangalore), Malabar (Kerala) and Canara (Karnataka) districts of Western India and Assam, Khasi, Jantia hills, West Bengal and Gujarat.
Collection and Preparation
Raw kokum butter is a white coloured fat with a creamish-yellow or even slight-grey tint which is extracted by traditional rural/cottage industry sized oil mills. The fruits are collected manually by hand picking. The branches are shaken with long sticks and the fallen fruits are collected. These are broken by sticks to separate the seeds, picked up by hand. The seeds are gathered from the natural forest habitats. The seeds are cleaned to remove the dust, dirt and foreign matter. The seeds are dried to reduce the moisture content. These are decorticated by wooden mallets. The final product is obtained by crushing the kernels and boiling the pulp in water (in a steam boiler) and skimming off the fat from the top or churning the crushed pulp with water. Pure oil is obtained after double filtration and is cooled to create kokum butter slabs and cubes of different sizes and weight. This is a time consuming process and the yield is about 25% of raw butter.
The kernels from the seeds are churned and boiled in water with caustic soda. This yields hard soap which is decomposed by sulphuric acid leaving tristearin as stearic acid, myristic acid and oleic acid. The melted fat is separated by skimming with hot water twice and decolourised with animal charcoal or Fuller’s earth. The seeds contain 30% of fat. After refining, the fat is equivalent to vanaspati ghee.
Characters
This is a white to light grey or yellowish solid fat with a neutral odour and taste. It is hard and brittle and exceptionally stable. It has an earthy scent. It solidifies below 39°C and its melting point is 39–42°C. It has a saponification value of 191 and an iodine value of 36.9.
Chemical Constituents
Kokum butter contains glycerides of stearic acid (40–45%), oleic acid (40–50%), hydroxyl capric acid (10%), palmitic acid (5–8%) and linoleic acid (2–4%). The fat is slightly bitter. It contains free fatty acids (0.08%), non-saponifiables (0.9%), total saturated fats (52–68%), total monosaturated fats (30–42%) and total polysaturated fats (0–2%). It also contains anti-