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Essential oils extracted from a wide variety of plants and herbs have been traditionally employed in the manufacture of foodstuffs, cosmetics, cleaning products, fragrances, herbicides and insecticides. Further, several of these plants have been used in traditional medicine since ancient times as digestives, diuretics, expectorants, sedatives, etc., and are actually available in the market as infusions, tablets and/or extracts.
Essential oils are also popular nowadays due to aromatherapy, a branch of alternative medicine that claims that essential oils and other aromatic compounds have curative effects. Moreover, in the last decades, scientific studies have related many biological properties (antioxidant, anti-inflammatory, antiviral, antibacterial, stimulators of central nervous system, etc.) of several plants and herbs, to some of the compounds present in the essential oil of the vegetal cells. For example, valerenic acid, a sesquiterpenoid compound, and its derivatives (acetoxyvalerenic acid, hydroxyvalerenic acid, valeranone, valerenal) of valerian extract are recognized as relaxant and sedative; lavender extract is used as antiseptic and anti-inflammatory for skin care; menthol is derived from mint and is used in inhalers, pills or ointments to treat nasal congestion; thymol, the major component of thyme essential oil is known for its antimicrobial activity; limonene and eucalyptol appear to be specifically involved in protecting the lung tissue. Therefore, essential oils have become a target for the recovery of natural bioactive substances.
Essential oils are composed by lipophilic substances, containing the volatile aroma components of the vegetal matter, which are also involved in the defense mechanisms of the plants. The essential oil represent a small fraction of plant composition, and is comprised mainly by monoterpenes and sesquiterpenes, and their oxygenated derivatives such as alcohols, aldehydes, ketones, acids, phenols, ethers, esters, etc. The amount of a particular substance in the essential oil composition varies from really high proportions (e.g. around 80-90% w/w of δ-limonene is present in orange essential oil) to traces. Nevertheless, components present in traces are also important, since all of them are responsible for the characteristic natural odor and flavor. Thus, it is important that the extraction procedure applied to recover essential oils from plant matrix can maintain the natural proportion of its original components.
New effective technological approaches to extract and isolate these substances from raw materials are gaining much attention in the research and development field. Traditional approaches to recover essential oil from plant matrix include steam- and hydro-distillation and liquid-solvent extraction. One of the disadvantages of steam-distillation and hydro-distillation methods is related with the thermo ability of the essential oil constituents, which undergo chemical alteration due to the effect of the high temperatures applied (around the normal boiling temperature of water). Therefore, the quality of the essential oil extracted is extremely damaged.
On the other side, the lipophilic character of essential oils requires solvents such as paraffinic fractions (pentane and hexane) to attain an adequate selectivity of the extraction. Further, liquid solvents should have low boiling points, in order to be easily separated from the extract and re-utilized. In this sense, the main drawback is the occurrence of organic toxic residues in the extracted product.
Among innovative process technologies, supercritical fluid extraction (SFE) is indeed the most widely studied application. In practice, SFE is performed generally using carbon dioxide (CO2) for several practical reasons: CO2 has moderately low critical pressure (74 bar) and temperature (32oC), is non-toxic, non-flammable, available in high purity at relatively low cost, and is easily removed from the extract. Supercritical CO2 has a polarity similar to liquid pentane and thus, is suitable for extraction of lipophilic compounds. Thus, taking into account the lipophilic characteristic of plant essential oils, it is obvious that SFE using CO2 emerged as a suitable environmentally benign alternative to the manufacture of essential oil products.
The commercial production of supercritical plant extracts has received increasing interest in recent decades and has brought a wide variety of products that are actually in the market. As mentioned before, supercritical plant extracts are being intensively investigated as potential sources of natural functional ingredients due to their favorable effects on diverse human diseases, with the consequent application in the production of novel functional foods, nutraceuticals and pharmacy products. The reader is referred to several recent works in which is reviewed the supercritical extraction and fractionation of different type of natural matter to produce bioactive substances. The general agreement is that supercritical extracts proved to be of superior quality, i.e. better functional activity, in comparison with extracts produced by hydro-distillation or using liquid solvents using supercritical CO2 (50ºC and 45 MPa) and ethanol Soxhlet extraction. Extraction yields were, respectively, 3.8 and 9.1%. Nevertheless, the supercritical extract comprised 21% of essential oil, while the alcoholic extract contained only 9% of the volatile oil substances. Furthermore, studies related with the antibacterial and antifungal properties of the extract revealed better activity for the supercritical product. Another example of improved biological activity exhibit by supercritical extracts was reported by Glisic et al. demonstrating that supercritical carrot essential oil was much more effective against Bacillus cereus than that obtained by hydro-distillation.
Indeed, numerous variables have singular effect on the supercritical extraction and fractionation process. Extraction conditions, such as pressure and temperature, type and amount of cosolvent, extraction time, plant location and harvesting time, part of the plant employed, pre-treatment, greatly affect not only yield but also the composition of the extracted material.
Knowledge of the solubility of essential oil compounds in supercritical CO2 is of course necessary, in order to establish favorable extraction conditions. In this respect, several studies have been reported. Nevertheless, when the initial solute concentration in the plant is low, as is the case of essential oils, mass transfer resistance can avoid that equilibrium conditions are attained. Therefore, pretreatment of the plant become crucial to break cells, enhancing solvent contact, and facilitating the extraction. In fact, moderate pressures (9-12 MPa) and temperatures (35-50oC) are sufficient to solubilize the essential oil compounds. Yet, in some cases, higher pressures are applied to contribute to the rupture of the vegetal cells and the liberation of the essential oil. However, other substances such as cuticular waxes are co-extracted and thus, on-line fractionation can be applied to attain the separation of the essential oil from waxes and also other co-extracted substances.
In this review, on the basis of data reported in the literature and own experience, a detailed and thorough analysis of the supercritical extraction and fractionation of plants and herbs to produce essential oils is presented. Furthermore, the supercritical CO2 extraction of several plants (oregano, sage, thyme, rosemary, basil, marjoram and marigold) from Lamiaceae family was accomplished in our supercritical pilot-plant at 30 MPa and 40oC. High CO2 density was applied in order to ensure a complete extraction of the essential oil compounds.
Essential oil also called etheral or volatile oils are volatile odoriferous bodies of an oily character derived mostly form vegetable sources. They occur in small concentrations in special cells, glands or ducts, either in one particular organ of the plant or distributed over many part e.g. Leaves, barks, roots, flowers or fruits. Occasionally, they are present in combination with sugars, as glycosides, e.g. amyodalin in bitter almonds and sinigrin in mustard seeds, and are liberated when the glycosides are hydrolyzed. Essential oils are insoluble in water, but freely soluble in alcohol, either, fatty oils and mineral oils.
They are commonly liquid at ordinary temperature and some of them deposit solid matters on standing most of the essential oils are optically active, are lighter than water and possess high refractive index. They are composed of a number of chemical compounds:- Hydrocarbons, Alcohols, Ethers, Aldehydes Ketones, Oxides and lactones etc.
M. Indica is found largely in the greater part of India upto an altitude of 1200 M. Its bark is dark colour and cracked. Its leaves are clustered near the ouds of the branches. It is coriaceous, pubescent when young almost glabrous when mature the flowers of this tree are dense fasciles near ends of branches. They may be small, calyx, corolla tubular and fleshy.
M. Indica is found in mixed deciduous forests, usually of a somewhat dry type, often growing on rocky and sandy soil and turning on the deccan trap. It is common throughout central India, Mumbai and Andhra Pradesh. It is also common in the drier type of sal forests in Madhya Pradesh. It is much planted in the plains of northern India and Deccon peninsula when forest land is cleared for cultivation, mahua trees are carefully preserved.
Essential Oils:-
Products derived from plants in which the odoriferous characteristics are concentrated. Essential oils are also known as “Volatile” and “etheral” oils, in contradistinction to the fixed or glyceride vegetable and animal oils and the mineral oils. Essential oils have been obtained from about eighty-seven plant families, and at times different essential oils can be secured from different parts of the same plant. For instance, the flowers of the orange tree yield oil of neroli, or oil of orange flowers; the rind yields orange oil, and another essential oil is obtained from the leaves.
Classification. The essential oil can be classified in several ways. According to use, essential oils are divided into three broad classes: (1) those used for perfumery, soap, and cosmetics; (2) those used for flavouring foods and beverages; and (3) those used for therapeutic purposes. According to preparation there are five principal groups of essential oils namely, oils obtained (1) by expression, (2) by distillation, (3) by solvent extraction, (4) by counter current extraction, and (5) by enfleurage. According to sources, essential oils are classified by the eighty-seven plant families mentioned above and also by the various parts of the plant which are utilized (e.g. Fruits, seeds, bud and flowers leave and stem roots, bark, or wood). Classification according to geographical origin is also common since superior types of essential oils are produced in specific geographical areas that have favourable soil and climatic conditions.
Properties. Essential oils are generally colorless to slightly yellowish when freshly distilled but when foreign matter is present, the color may range from red to blue. On standing the oils generally become darker in color. The odor of essential oils is similar to that of the portion of the plant from which they are derived; but since these odorous characteristics are much more concentrated in the essential oil, the odor is often disagreeable. The terpenes they contain are fairly readily oxidized, resulting in a turpentine odor. The specific gravity of these materials varies from 0.84 to 1.18. They are volatile at room temperature and evaporate completely when heated. Most essential oils are only slightly soluble in water; they are more soluble in sugar solutions.
The principal terpeneless oils and sesquiterpeneless oils are bergamot, grapefruit, lavender, lemon, lime mandarin, orange, orrisroot, peppermint, petitgrain, and spearmint.
Composition. The essential oils are mixtures, generally consisting of a major hydrocarbon portion and of many minor oxygen, nitrogen and sulphur-bearing components. The hydrocarbons are usually terpenes (i.e, polymers or derivatives of the parent substance) isoprene, 3-methyl-1, 3-butadiene, C5H8, sesquiterpenes and polyterpenes. The terpenes, C10H16, may be acryclic, like mycene and ocimene; monocyclic, like limonene, phellandrene, and terpinene; or bicyclic, like bisabolene; bicyclic, like cadinene; or tricylic.
In some essential oils the hydrocarbon content is very high. thus in lemon, orange, and other citrus-peel oils, about 95 per cent of the essential oil consists of terpenes; and over 85 to 90 per cent of calamus, ginger, juniper, and rosemary oils consists of terpene and sesquiterpene hydrocarbons. On the other hand, some oils have a low terpene hydrocarbon content; for instance, from 70 to 90 per cent of oils of cinnamon or cassia is cinnamaldehyde, and some 70 per cent of oil of cloves is eugenol.
Spices which are basically plant products, have a definite role to play in enhancing the taste flavour, relish or piquancy of any food, most of the spices are pagrant, aromatic and pangent. They comprise seeds, bartes, rhizome, leaves fruits and other parts of plants, which belong to varigated species and genera since time immorial, India in renamed to be the wave of spices. Most important spices like black pepper (king of spices) cardamom (queen of spices) cardamom (queen of spices), ginger, chilies and turmeric, which are produced in India import it great reputation and these constitute. The major group of spices. In the list of spices, clave, nutmeg, cinnamon and cassia are known as tree spices, However, spices like fennel, fenugreek, garlic, onion, coriander, cumin, vanilla, saffron; etc.
There are a number of spices used along with food, namely;
1. Common Salt, 2. Coriander, 3. Chill, 4. Haldi, 5. Ajwain & Maithee, 7.Onion and so on; These spices are not used are at a time. For preparation of any dish may be Indian or European, may be vegetarian or non-vegetarian we use more than are shice for its preparation. The combination of all the spices but together for the use of one particular dish as known as ‘masala’ of the spices, the bulk of the dry matter consists of carbohydrater, proteins, tannius, resins, volatile oil, fixed oil, for pigments, mineral, elements, etc. These constituents differ grately in their composition and content in different spices. They have varied physical and chemical properties. Due to this reason, the processing method of different spice, differ widely and required individual expertise in variety operation like curing, drying, cleaning, grading and packing.
Harvesting of each spice is done at a particular store of maturity in a particular manner suitable for it avoiding any sort of damage before processing. It is transported to the processing centre as quickly as possible and stored properly before it is taken to up for processing.
Eucalyptus oils are obtained by distillation of the leaves of Eucalyptus and have aromas characteristic of the particular species used.
The oils are classified in the trade into three broad types according to their composition and main end-use: medicinal, perfumery and industrial. Of these, the most important in terms of volume of production and trade is the medicinal type, characterized by high cineole content in the oil. This, and the perfumery type, is discussed below. The so-called industrial oil, produced from E. dives, now has a very small and diminishing market and is not discussed further.
The medicinal type of oil may be sold as such, neat, in pharmacies and other retail outlets or in the form of sprays, lozenges, cough sweets and ointments or in formulation with other oils. It is used as an inhalant or chest rub to ease breathing difficulties, as a mouthwash in water to refresh or ease the throat, and as a skin rub to provide relief from aches and pains. Anti-plaque solutions in dental hygiene are a recent application. Although employed for medicinal purposes, the pleasant flavour and fragrance properties of cineole-rich eucalyptus oils play an important role in their acceptance and utilization on such a large scale. Eucalyptus oil is also used as a general disinfectant, cleaner and deodorizer about the house.
Of the two principal perfumery oils, that from Eucalyptus citriodora is produced in the greatest volume. It differs from the medicinal oils in containing citrinellal, rather than cineole, as the major constituent. The oil is employed in whole form for fragrance purposes, usually in the lower cost soaps, perfumes and disinfectants, but also as a source of citrinellal for the chemical industry. The citrinellal obtained by fractionation of the crude oil may be used as such as an aroma chemical or converted to other derivatives intended for fragrance use.
