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Volatile Oils.274203841
Volatile Oils.274203841
VOLATILE OILS
All official volatile oils are of vegetable origin. Normally pre-exist in the plant stored in a special secretory tissue (e.g. Citrus peel oil cells or oil ducts in umbelliferous fruits). EXCEPTION: Oil of bitter almond formed by hydrolysis of the glycosides.
Therapeutically (Oil of Eucalyptus) Flavouring (Oil of Lemon) Perfumery (Oil of Rose) Starting materials to synthesize other compounds (Oil of Turpentine) Anti-septic due to high phenols (Oil of Thyme). Also as a preservative (oils interfere with bacterial respiration) Anti-spasmodic (Ginger, Lemon balm, Rosemary, Peppermint, Chamomile, Fennel, Caraway) Aromatherapy
CONCRETES
Prepared from raw materials of vegetable origin (bark, flowers, leafs, roots etc.)
Extracted by HC type solvents, rather than distillation or expression Becomes necessary when the essential oil is adversely affected by hot water or steam (e.g. jasmine). Produces a more true-to-nature fragrance.
CONCRETES
Concretes contain about 50 % wax and 50 % essential oil (jasmine). Ylang ylang (concrete volatile) contains 80 % essential oil and 20 % wax. Advantages of concretes: they are more stable and concentrated than pure essential oils.
POMADES
True pomades are (volatile oil) products of a process known as enfleurage (hot or cold). Enfleurage is used for obtaining aromatic materials from flowers containing volatile oils to produce perfume long after they were cut.
ENFLEURAGE: METHOD
A glass plate is covered with a thin coating of especially prepared and odourless fat (called a chassis). The freshly cut flowers are individually laid on to the fat which in time becomes saturated with their essential oils. The flowers are renewed with fresh material. Eventually the fragrance-saturated fat, known as pomade, may be treated with alcohol to extract the oil from the fat.
RESINOIDS
Prepared from natural resinous material (dried material) by extraction with a non-aqueous solvent, e.g. Petroleum ether or hexane. E.g. Balsams Peru balsam or benzoin; resins (amber or mastic); Oleoresin (copaiba balsam and turpentine); Oleogum resins (frankincense and myrrh)
RESINOIDS
Can be viscous liquids, semi-solid or solid. Usually homogeneous mass of noncrystalline character. Uses: in perfumery as fixatives to prolong the effect of a fragrance.
ABSOLUTES
Obtained from a concrete, pomade, or a resinoid by alcoholic extraction.
Fx OF VOLATILE OILS
In most cases, the biological function of the terpenoids of essential oils remains obscure it is thought that they play an ecological role protection from predators & attraction of pollinators.
LOCALIZATION
Synthesis & accumulation of essential oils are generally associated with the presence of specialized histological structures, often located on or near the surface of the plant:
- Oil cells of Zingiberaceae - Glandular trichomes of Lamiaceae - Secretory cavities of Myrtaceae or Rutaceae - Secretory canals of Apiaceae or Astereraceae (Compositeae)
EXCEPTION: Oils derived from glycosides (e.g. bitter almond oil & mustard oil). Oxygenated compounds responsible for the odour/smell of the oil. They are slightly water soluble Rose water & Orange Water; more alcohol soluble. Most volatile oils are terpenoid. Some are aromatic (benzene) derivatives mixed with terpenes. Some compounds are aromatic, but terpenoid in origin (e.g. Thymol Thyme)
CHEMICAL COMPOSITION
Volatile oils are divided into 2 main classes based on their biosynthetic origin
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Terpene derivatives (formed via the acetate mevalonic acid pathway) Aromatic compounds (formed via the shikimic acid-phenylpropanoid route) Miscellaneous Origin
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A. TERPENES
Terpenes, or terpenoids, are the largest group of secondary products (metabolites). They are all formed from acetyl CoA or glycolytic intermediates.
CLASSIFICATION OF TERPENES
All terpenes are formed from 5-C elements Isoprene is the basic structural element.
CLASSIFICATION OF TERPENES
Terpenes are classified by the number of 5-C atoms they contain 10-Carbon terpenes (contain 2 C-5 units) monoterpenes 15- Carbon terpenes (3 C-5 units) are called sesquiterpenes. 20-carbon terpenes (4 C-5 units) are diterpenes. Larger terpenes (30 Carbons) are called triterpenes (triterpenoids), 40 Carbons called tetraterpenes and polyterpenoids.
TERPENOIDS
Terpenoids contain only the most volatile terpenes (i.e. molecular weight is not too high) mono and sesquiterpenes May occur as oxygenated derivatives, e.g. alcohols, aldehydes, ketones, phenols, oxides & esters.
EXAMPLES OF TERPENES
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i. LIMONENE
Structural classification: Monocyclic terpene Functional Classification: Unsaturated HC
ii. MENTHOL
Structural classification: Monocyclic with hydroxyl group
iii. BORNEOL
Functional Classification: //// Occurrence: Cinnamon
iv. SESQUITERPENES
(Contain 3 isoprene units) Acyclic E.g. Farnesol
B. AROMATIC COMPOUNDS
Many are phenols are phenol esters E.g. Vanillin
Almost entirely volatile without decomposition. Density: Most are less than 1g/ml.
Soluble in ether, chloroform & alcohol. Slightly soluble in water: give it a characteristic odour & taste. Leaves a temporary translucent stain on paper which disappears as the oil volatilizes. Most are colourless. Oxidize on exposure to air and resinify colour becomes darker (odour changes slightly). All are characteristic odours. Most are optically active.
Concretes & Resinoids may be produced i. By solvent extraction ii. By methods using oils & fats iii. By extraction by supercritical gasses
b. SATURATED STEAM
Plant does not come into contact with the water steam is injected through the plant material placed on perforated trays. It is possible to operate under moderate pressure. Advantages: Limits the alteration of the constituents of the oil It shortens the duration of the treatment It conserves energy It can also be conducted on on-line in automated set ups.
c. HYDRODIFFUSION
Pulses of steam is sent through the plant material at very low pressure from (top to bottom). ADVANTAGE: Normally produces a product of high quality. Saves time and energy.
ADVANTAGE: This method is fast, consumes little energy and yields a product which is most often of a higher quality than the traditional steam distillation product.
SOLVENT EXTRACTION
The solvent selection is influenced by technical & economical factors
- Selectivity (being a good solvent for the specific constituents). - Stability (chemical inertness) - Boiling point should not be so high that the solvent can be completely eliminated; nor too low, to limit losses & control cost - Handling safety Solvents most used are aliphatic HCs petroleum ether, hexane, propane & liquid butane. Although benzene is a good solvent, its toxicity increasingly limits is use.
SOLVENT EXTRACTION
At the end of the procedure, the solvent contained in the plant material is recovered by steam injection. Main disadvantages of solvent extraction - Lack of selectivity, many lipophilic substances may end up in the concretes & render further purification necessary. - The toxicity of solvents leads to the restrictive regulations regarding their use - Residues in the final product.
Chromatrographic techniques This permits a good separation of the essential oil from non-volatile lipophilic compounds.
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Occurrence of Chemotypes Influence of the vegetative cycle Influence of environmental factors Influence of preparation method
i. CHEMOTYPES
Chemical breeds commonly occur in plants containing volatile oils, e.g. Thyme (Thymus vulgaris) has 7 different chemotypes, each with slightly different types & amounts of volatile oils.
ENVIRONMENTAL FACTORS
e.g. Peppermint: long days & temperate nights higher yields of oil & menthofuran. Cold nights lead to an increase in menthol. Laurus nobilis (Bay) [volatile oil] is greater in the southern hemisphere than the northern. Citrus: higher temperatures = higher oil content.
ENVIRONMENTAL FACTORS
Cultivation practices also play an important factor to the yield & quality of the final product. Fertilization and the amounts of N, P and K have been studied for various species. The watering regiment also plays an important role.
PREPARATION METHOD
Because of the volatile nature of the constituents of essential oils, the composition of the product obtained by steam distillation is often different from the constituents originally found in the secretory organs of the plant. During steam distillation, the water, acidity and tempereature may induce hydrolysis of the esters. Rearrangements, isomerizations, racemiazations, oxidations and other reactions also occur, all of which change the composition.
HISTORY Cultivated in India from the earliest times. Used by Greeks and Romans and was a common article of commerce in the European Middle Ages.
Grows well in subtropical temperatures with high rainfall. Grown by vegetative means. Mulching or is necessary as the plant rapidly exhausts minerals from the soil. When the stems wither, the rhizomes are ready for collection. Dried.
MACROSCOPICAL FEATURES
Scraped/peeled herb has little resemblance to the fresh herb (loss in weight & shrinkage). Occurs in branched pieces hands or races. Buds No cork Aromatic odour & pungent taste. Unscraped rhizome: resembles scraped herb Covered with cork (brownish layers)
MICROSCOPICAL FEATURES
Cork cells high starch content Cork cells are absent in the scraped drug. Outer zone of flattened parenchyma & inner zone of normal parenchyma. Oil cells scattered in the cortex.
Sesquiterpene HCs
Zingiber officinale
VARIETIES
Chinese Ginger sliced African ginger darker (cortex is grey black in colour); lacks the odour but more pungent than Jamaican herb.
ALLIED DRUGS
Japanese ginger Z. mioga Preserved ginger undried rhizomes preserved by boiling in syrup.
ADULTERANTS
Elettaria cardamomum
GEOGRAPHICAL SOURCES
HISTORY
Mainly obtained from cultivated plants (propagated by seedlings or vegetatively [problematic due to virus infection]). Capsules on the same plant ripen at different times important to collect them before they split.
Fruits are dried slowly (outdoors or indoors). Too rapid drying capsules split & shed seeds Calyx at the apex of the stalk and the stalk at the base may be removed. Fruits are graded with a sift into longs, mediums, shorts & tiny. If they have been sulphur bleached (improved colour), it will be aired outdoors before packed for transport.
MACROSCOPICAL FEATURES
Plant is reed-like - > 4 m, with long leaves growing from the rhizome. Fruits capsular: inferior, ovoid, 1-2 cm long. Apex: shortly beaked & shows floral remains. Base: rounded & shows the remain of a stalk. Internally the capsule is 3-celled; each cell contains x2 row of seeds. Each seed: Slightly angular, 4mm long & 3 mm broad. Colour: dark red-brown (fully ripe seeds) paler in unripe seeds. Strong, pleasant, aromatic odour Pungent taste
MICROSCOPICAL FEATURES
Oil cells Predominant Parenchyma (yellow colour) Cells containing silica Starch grains
ADULTERATION Powdered drug adulterated with the fruit pericarp (powdered). ALLIED HERBS Official variety E. cardamomum var miniscula Other: E. cardamomum var major (more elongated & sometimes 4 cm long with dark brown pericarps) Amomum aromaticum (Bengal cardamom) Amomum subulatum (Nepal cardamom) Amomum cardamomum (Java cardamom)
CHEMICAL CONSTITUENTS
6.2 % volatile oil Abundant starch (up to 50%) Fixed oil (1 10%) Calcium oxalate
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GEOGRAPHICAL SOURCES Cultivated in Sri Lanka, South India, Seychelles, Madagascar, Martinique, Cayenne, Jamaica & Brazil.
PREPARATION OF Cinnamomum
Individually scraped barks are placed inside each other. Compound quills are dried on wooden frames in the open air without exposure to direct sunlight. Sorted into grades.
MACROSCOPICAL FEATURES
Normally received in shorter lengths known as cigar lengths. Consists of a single or double compound quill about 6-10 mm diameter of varying length. Thickness of the quill varies according to grade (good quality: Not > 0.5mm), bark: 10-40mm. External surface: is yellow-brown, shining, wavy lines (pericycle fibres) and occasional scars & holes (leave/twig positions). Inner surface: darker, longitudinally striated. Odour: fragrant Taste: Warm, sweet & aromatic
MICROSCOPICAL FEATURES
Transverse:
absence of epidermis & cork Sclereids (thickened lignified pitted walls) Secondary phloem is composed of phloem parenchyma containing oil & mucilage cells, phloem fibres & medullary rays. Some phloem parenchyma contain tannins. Secretion cells: volatile oils and mucilage Calcium oxalates
Cinnamomum - CONSTITUENTS
Volatile oils (at least 1.2 %) Phlobaphenes Mucilage Calcium Oxalate Starch
Allied Herbs Cayenne Cinnamon C. zeylanicum grown in Brazil not used in Britain C. loureirii from Vietnam Closely resembles C. cassia
LEMON PEEL
Definition: Dried lemon (Limonis Cortex) peel is obtained from the fruit of Citrus limon (Rutaceae).
Distilled Oils Although not official, some lemon oils are produced by distillation, mainly from the residue of the expression processes. It is much cheaper than hand-pressed or machine-made oil.
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MACROSCOPICAL FEATURES
Nutmeg trees are evergreen, growing up to 20 m in height. Nutmegs are oval, 2-3 cm long & 2 cm broad. If not heavily limed, the surface is a brown or grey brown in colour. Odour: Strong & aromatic Taste: Pungent and slightly bitter.
MICROSCOPICAL FEATURES
Potassium acid tartrate crystals Parenchym with thin brown walls Oval oil cells Feathery crystals of fat Few tannin cells (containing tannin & starch)
NUTMEG OIL
Nutmeg oil is distilled from the kernels of Myristica fragrans. CONSTITUENTS Pinene Sabinene Camphene Dipentene Safrole Eugenol & eugenol derivatives Myristicin a benzene: toxic to humans (large does of nutmeg or nutmeg oil may cause convulsions).
MACE
Common mace or Banda mace consists of the dried arillus or arillode of M. fragrans.
CLOVE
DEFINITION: Cloves are the dried flower buds of Syzygium aromaticum (Eugenia caryophyllus), (Myrtaceaea). Geographical Sources Molucca or Clove Islands, Zanzibar, Pemba, Madagascar, Indonesia & Brazil.
HISTORY OF CLOVE
Cloves were used in China as early as 266 BC, and by the 4th century, they were known in Europe, although very expensive. Same as with nutmeg, the Dutch also destroyed all trees from surrounding native islands to secure a monopoly, and cultivated them only in a small group of islands. In 1770, the French managed to introduce clove trees to Mauritius, and started cultivating them there, as well as in Zanzibar, Penang and Sumatra.
MACROSCOPICAL FEATURES
Cloves are 10-17.5 mm long. The head consists of 4 slightly projecting calyx teeth, 4 membranous petals and numerous incurved stamens around a large style. Odour: Spicy & Pungent Taste: Aromatic
MICROSCOPICAL FEATURES
Heavy cuticularized epidermis Numerous oil cells (shizolysigenous) Calcium oxalates (cluster crystals & prisms) Stomata (epidermis of sepals) Starch (Fruit mother cloves) Lignified sclereids
CONSTITUENTS
14-21% Volatile oils Mainly eugenol & isoeugenol Sitosterol Stigmasterol Campesterol Tannins Triterpene acids & esters Glycosides
USES OF CLOVE
Stimulant aromatic Spice For the preparation of volatile oil Sesquiterpenes: potential anticarcinogenic compounds
CLOVE OIL
Oil distilled in Europe and the US normally does not need purification, while oil distilled in other areas (e.g. Madagascar) does. After purification the oil is sold with varying eugenol contents. Oil of cloves is yellow or colourless, is slightly heavier than water.
EUCALYPTUS LEAF
DEFINTION: Eucalyptus leaf consists of the whole or cut dried leaves of the older branches of Eucalyptus globulus, (Myrtaceae). GEOGRAPHICAL SOURCES Portugal, SA, Spain, China, Brazil, Australia, India & Paraguay.
Eucalyptus - DESCRIPTION
MACROSCOPICAL Older dried leaves are grey-brown & have lateral veins. Secretory oil cells are visible in leaves held to the light. MICROSCOPIC Epidermal cells have a thick cuticle. Anisocytic stomata Mesophyll has schizogenous oil glands Calcium oxalate crystals: Prisms & Cluster crystals
Eucalyptus - CONSTITUENTS
Volatile Oil (at least 2 %) sesquiterpene - Antibacterial action against oral pathogens.
EUCALYPTUS OIL
Oil of eucalyptus is distilled from the fresh leaves of various species of Eucalyptus and rectified. They are produced in the same countries which produce the dry herb. Only a certain amount of species produce oil suitable for medicinal use the main criteria is a high cineole content and low amounts of phellandrene and aldehydes.
Suitable oils are obtained from E. polybractea, E. smithii, E. globulus and E. australiana.
FENNEL
DEFINITION: Fennel consists of the dried ripe fruits of Foeniculum vulgare (Umbelliferae).
ACTIVE CONSTITUENTS
1-4 % Volatile oil trans-anethole Antethole Estragole Fenchone Flavonoids Coumarins Glycosides
Foeniculum vulgare
GEOGRAPHICAL SOURCES Wild & Cultivated in Central & Northern Europe, Holland, Denmark, Germany, Russia, Finland, Poland, Hungary, Britain, Egypt, Morocco, Australia & China
MACROSCOPICAL FEATURES
A biennial herb growing up to 1 m in height. Herb: Normally consists of mericarps separated from the pedicels. Fruits are slightly curved, brown & glabrous. Size: 4-7 mm long, 1-3 mm wide Often the stigma & style are still attached. Characteristic aromatic odour & taste
MICROSCOPICAL FEATURES
Pitted sclerenchyma secretory canals Dark, red-brown cells containing a pale yellow or colourless oleoresin Thick cellulose walls Calcium oxalate crystals
ACTIVE CONSTITUENTS
1-7 % Volatile oils Carvone Limonene Carveole 8-20 % Fixed oils Proteins Calcium oxalates Colouring matter Resin
MACROSCOPICAL FEATURES
Annual herb growing 0.7 m in height with white or pink flowers. Drug: Normally consists of whole cremocarps straw yellow & 2-4 mm in diameter when ripe. Considerable variation occurs (e.g. Indian variety > oval). Apex has 2 styles. Fruits have an aromatic odour & spicy taste. Unripe plant: unpleasant mousy odour same odour oil has when made from unripe fruit.
MICROSCOPICAL FEATURES
Outer pericarp: stomata & calcium oxalte prisms. Thick sclerenchyma Testa:= brown flattened cells Endosperm is curved & consists of parenchymous cells containing fixed oils.
ACTIVE CONSTITUENTS
1.8 % Volatile oils Linalool/coriandrol Pinene Terpinene Limonene Cymene Non-linalool alchols & esters Flavonoids Coumarins Phenolic acids High fat content (16-28%) Protein (11-17%)
MACROSCOPICAL FEATURES
All mints have a square stem & creeping rhizome. Black mint, which is the most commonly cultivated variety in England, has purple stems and dark green petiolate leaves tinged with purple. Leaf blades are 3-9 cm long with a grooved petiolate up to 1 cm long. Pinnate venation. Glandular trichomes: bright yellow points (hand lens) Small purple flowers appear in late summer.
MICROSCOPIC FEATURES
Diacytic stomata Multicellular clothing trichomes 2 types of glandular trichomes (one with a unicellar head; with a multicellular head). Calcium oxalate is absent.
Oleum Menthae
Oil of peppermint is obtained from Mentha piperita via steam distillation using the flowering tops. Oil should contain at least 44 % menthol, 15-32 & menthone and 4.5-10 % menthyl acetate.
LESSON TAKE-AWAY
Definitions of Volatile Oils Methods of Production of Volatile Oils Herbs containing Volatile Oils